Uranium 238U/235U isotope ratios as indicators of reduction: Results from an in situ biostimulation experiment at Rifle, Colorado, USA

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

Bopp IV, C.J.; Lundstrom, C.C.; Johnson, T.M.

2010-02-01

The attenuation of groundwater contamination via chemical reaction is traditionally evaluated by monitoring contaminant concentration through time. However, this method can be confounded by common transport processes (e.g. dilution, sorption). Isotopic techniques bypass the limits of concentration methods, and so may provide improved accuracy in determining the extent of reaction. We apply measurements of {sup 238}U/{sup 235}U to a U bioremediation field experiment at the Rifle Integrated Field Research Challenge Site in Rifle, Colorado (USA). An array of monitoring and injection wells was installed on a 100 m{sup 2} plot where U(VI) contamination was present in the groundwater. Acetate-amended groundwatermore » was injected along an up-gradient gallery to encourage the growth of dissimilatory metal reducing bacteria (e.g. Geobacter species). During amendment, U concentration dropped by an order of magnitude in the experiment plot. We measured {sup 238}U/{sup 235}U in samples from one monitoring well by MC-ICP-MS using a double isotope tracer method. A significant {approx}1.00{per_thousand} decrease in {sup 238}U/{sup 235}U occurred in the groundwater as U(VI) concentration decreased. The relationship between {sup 238}U/{sup 235}U and concentration corresponds approximately to a Rayleigh distillation curve with an effective fractionation factor ({alpha}) of 1.00046. We attribute the observed U isotope fractionation to a nuclear field shift effect during enzymatic reduction of U(VI){sub (aq)} to U(IV){sub (s)}.« less

Monitoring CO2 concentration and δ13C in an underground cavity using a commercial isotope ratio infrared spectrometer

NASA Astrophysics Data System (ADS)

Guillon, Sophie; Agrinier, Pierre; Pili, Éric

2015-04-01

CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based isotope ratio infrared spectrometers (IRIS) allow in situ continuous monitoring of CO2 isotopes, and therefore they have a potential for unprecedented understanding of carbon sources and dynamics with a high temporal resolution. Here we present the performance assessment of a commercial IRIS analyzer, including the measurement setup and the data processing scheme that we used. Even if the analyzer performs 1-Hz measurements, an integration time of the order of 1 h is commonly needed to obtain acceptable precision for δ13C. The main sources of uncertainty on δ13C come from the concentration dependence and from the temporal instability of the analyzer. The method is applied to the in situ monitoring of the CO2 carbon isotopes in an underground cavity (Roselend Natural Laboratory, France) during several months. On a weekly timescale, the temporal variability of CO2 is dominated by transient contamination by human breath. Discarding these anthropogenic contaminations, CO2 and δ13C backgrounds do not show diurnal or seasonal fluctuations. A CO2 flux released into the tunnel by the surrounding rocks is measured. The carbon isotope composition of this CO2, identified with a Keeling plot, is consistent with a main production by microbial respiration and a minor production from weathering of carbonate minerals. The presented instrument and application study are relevant to cave monitoring, whether to understand CO2 dynamics in visited and/or painted caves for preservation purposes or to understand paleoclimate recording in speleothems.

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

NASA Astrophysics Data System (ADS)

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time.

Nuclear and isotopic techniques for addressing nutritional problems, with special reference to current applications in developing countries.

PubMed

Iyengar, Venkatesh

2002-03-01

Nuclear and isotopic techniques are valuable tools in human nutritional research studies. Isotopes, both radioactive and nonradioactive, enable detailed evaluations of nutrient intake, body composition, energy expenditure, status of micronutrients, and nutrient bioavailability. In recent times, isotopic methods have been widely used in a number of coordinated research projects and technical cooperation projects of the International Atomic Energy Agency's Nutrition Programme. The doubly labeled water technique combines the use of the stable isotopes oxygen-18 and hydrogen-2 (deuterium) to measure total energy expenditure in free-living human subjects, and to investigate the magnitude and causes of both undernutrition and the emergence of obesity in developing countries. The deuterium dilution technique is a reliable tool to measure breastmilk intake and thereby infant growth and development. In collaboration with the World Health Organization's Growth Monitoring Program, this technique is being used to generate new data on growth standards for children in developing countries. This technique is also used in the measurement of body composition by the estimation of lean body mass and fat mass in individuals. Stable isotopes of iron and zinc have been successfully used to assess the nutritional impact of several nationwide food supplementation-programs conducted on pregnant and lactating women and children in both industrialized and developing countries. Isotopic techniques are especially suitable for monitoring changes in body composition, energy metabolism, and mineral status (with particular reference to osteoporosis) in the elderly. Nuclear methods have also served to develop models for a physiological reference man in Asia in support of radiological health and safety issues, for establishing elemental composition of foods, and for measurement of pollutants in the environment.

A new dimethyl labeling-based SID-MRM-MS method and its application to three proteases involved in insulin maturation.

PubMed

Cheng, Dongwan; Zheng, Li; Hou, Junjie; Wang, Jifeng; Xue, Peng; Yang, Fuquan; Xu, Tao

2015-01-01

The absolute quantification of target proteins in proteomics involves stable isotope dilution coupled with multiple reactions monitoring mass spectrometry (SID-MRM-MS). The successful preparation of stable isotope-labeled internal standard peptides is an important prerequisite for the SID-MRM absolute quantification methods. Dimethyl labeling has been widely used in relative quantitative proteomics and it is fast, simple, reliable, cost-effective, and applicable to any protein sample, making it an ideal candidate method for the preparation of stable isotope-labeled internal standards. MRM mass spectrometry is of high sensitivity, specificity, and throughput characteristics and can quantify multiple proteins simultaneously, including low-abundance proteins in precious samples such as pancreatic islets. In this study, a new method for the absolute quantification of three proteases involved in insulin maturation, namely PC1/3, PC2 and CPE, was developed by coupling a stable isotope dimethyl labeling strategy for internal standard peptide preparation with SID-MRM-MS quantitative technology. This method offers a new and effective approach for deep understanding of the functional status of pancreatic β cells and pathogenesis in diabetes.

Isotopic insights into microbial sulfur cycling in oil reservoirs

PubMed Central

Hubbard, Christopher G.; Cheng, Yiwei; Engelbrekston, Anna; Druhan, Jennifer L.; Li, Li; Ajo-Franklin, Jonathan B.; Coates, John D.; Conrad, Mark E.

2014-01-01

Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures. PMID:25285094

Application of stable isotope ratio analysis for biodegradation monitoring in groundwater

USGS Publications Warehouse

Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

2013-01-01

Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions.

CONTROL SYSTEM FOR ISOTOPE SEPARATING APPARATUS

DOEpatents

Barnes, S.W.

1960-01-26

A method is described for controlling the position of the ion beams in a calutron used for isotope separation. The U/sup 238/ beams is centered over the U/sup 235/ receiving pocket, the operator monitoring the beam until a maximum reading is achieved on the meter connected to that pocket. Then both beams are simultaneously shifted by a preselected amount to move the U/sup 235/ beam over the U/sup 235/ pocket. A slotted door is placed over the entrance to that pocket during the U/sup 238/ beam centering to reduce the contamination to the pocket, while allowing enough beam to pass for monitoring purposes.

Stable isotopes in barnacles as a tool to understand green sea turtle (Chelonia mydas) regional movement patterns

NASA Astrophysics Data System (ADS)

Detjen, M.; Sterling, E.; Gómez, A.

2015-12-01

Sea turtles are migratory animals that travel long distances between their feeding and breeding grounds. Traditional methods for researching sea turtle migratory behavior have important disadvantages, and the development of alternatives would enhance our ability to monitor and manage these globally endangered species. Here we report on the isotope signatures in green sea-turtle (Chelonia mydas) barnacles (Platylepas sp.) and discuss their potential relevance as tools with which to study green sea turtle migration and habitat use patterns. We analyzed oxygen (δ18O) and carbon (δ13C) isotope ratios in barnacle calcite layers from specimens collected from green turtles captured at the Palmyra Atoll National Wildlife Refuge (PANWR) in the central Pacific. Carbon isotopes were not informative in this study. However, the oxygen isotope results suggest likely regional movement patterns when mapped onto a predictive oxygen isotope map of the Pacific. Barnacle proxies could therefore complement other methods in understanding regional movement patterns, informing more effective conservation policy that takes into account connectivity between populations.

Stable isotopes in barnacles as a tool to understand green sea turtle (Chelonia mydas) regional movement patterns

NASA Astrophysics Data System (ADS)

Detjen, M.; Sterling, E.; Gómez, A.

2015-03-01

Sea turtles are migratory animals that travel long distances between their feeding and breeding grounds. Traditional methods for researching sea turtle migratory behavior have important disadvantages, and the development of alternatives would enhance our ability to monitor and manage these globally endangered species. Here we report on the isotope signatures in green sea turtle (Chelonia mydas) barnacles (Platylepas sp.) and discuss their potential relevance as tools with which to study green sea turtle migration and habitat use patterns. We analyzed oxygen (δ18O) and carbon (δ13C) isotope ratios in barnacle calcite layers from specimens collected from green turtles captured at the Palmyra Atoll National Wildlife Refuge (PANWR) in the Central Pacific. Carbon isotopes were not informative in this study. However, the oxygen isotope results suggest likely regional movement patterns when mapped onto a predictive oxygen isotope map of the Pacific. Barnacle proxies could therefore complement other methods in understanding regional movement patterns, informing more effective conservation policy that takes into account connectivity between populations.

Imprint of CO2 emission in atmosphere and biosphere on the basis of 14C and 13C measurements

NASA Astrophysics Data System (ADS)

Pazdur, Anna; Gabryś, Alicja; Kuc, Tadeusz; Pawełczyk, Sławomira; Piotrowska, Natalia; Rakowski, Andrzej; Różański, Kazimierz; Sensuła, Barbara

2015-04-01

As is shown in the IPCC (Intergovernmental Panel on Climate Change) report, the observed climate changes are caused, among others, by human activity. Mainly emission of CO2 to the atmosphere coming from the burning of fossil fuels, can have dire consequences for life on Earth and development of humankind. The report uses, among others, data obtained from isotopic measurements in the biosphere. Measurements of 14C and 13C concentration in modern atmospheric carbon dioxide and biosphere allow the determination of the decrease of the concentration of this isotope. Furthermore, the magnitude of emission to the atmosphere of carbon dioxide not containing the isotope 14C can be estimated on this basis. Such emission stems from fossil fuel combustion - petroleum, natural gas and black coal. A sensitive bioindicator of the emission are annual tree rings. The measurements of 14C concentration in tree ring material using AMS allow to see its seasonal changes. Trees, treated as an archive of changes in conjunction with information about the isotopic composition of carbon can be used for monitoring of environment as sensitive bioindicators on local, as well as on the global scale. Regular investigations of isotopic composition of carbon in trees have been carried out in the GADAM Centre for the urban areas of both Poland and worldwide. This method can be applied in the study of the emission of CO2 to the atmosphere and its spatial and temporal distribution connected with the production of energy by power plants based on fossil fuel combustion for the area of southern Poland. Modelling of CO2 emission using both 14C and 13C carbon isotopes measured in pine tree rings on the background of climatic changes will be presented. The national ecological policy in the era of global warming requires the manufacturers of energy to get involved in the development of methods suitable for monitoring the state of the environment. Hence, the interest in the area of monitoring the fossil fuel component in CO2 in our region is rising. The measurements of 14C (by AMS method) and 13C isotopes have been carried out in atmospheric CO2 and plants in the Gliwice city centre. A high decrease of both isotopes contents and their short-term seasonal changes during the year caused by human impact during the year are observed.

Monitoring the bio-stimulation of hydrocarbon-contaminated soils by measurements of soil electrical properties, and CO2 content and its 13C/12C isotopic signature

NASA Astrophysics Data System (ADS)

Noel, C.; Gourry, J.; Ignatiadis, I.; Colombano, S.; Dictor, M.; Guimbaud, C.; Chartier, M.; Dumestre, A.; Dehez, S.; Naudet, V.

2013-12-01

Hydrocarbon contaminated soils represent an environmental issue as it impacts on ecosystems and aquifers. Where significant subsurface heterogeneity exists, conventional intrusive investigations and groundwater sampling can be insufficient to obtain a robust monitoring of hydrocarbon contaminants, as the information they provide is restricted to vertical profiles at discrete locations, with no information between sampling points. In order to obtain wider information in space volume on subsurface modifications, complementary methods can be used like geophysics. Among geophysical methods, geoelectrical techniques such as electrical resistivity (ER) and induced polarization (IP) seem the more promising, especially to study the effects of biodegradation processes. Laboratory and field geoelectrical experiments to characterize soils contaminated by oil products have shown that mature hydrocarbon-contaminated soils are characterized by enhanced electrical conductivity although hydrocarbons are electrically resistive. This high bulk conductivity is due to bacterial impacts on geological media, resulting in changes in the chemical and physical properties and thus, to the geophysical properties of the ground. Moreover, microbial activity induced CO2 production and isotopic deviation of carbon. Indeed, produced CO2 will reflect the pollutant isotopic signature. Thus, the ratio δ13C(CO2) will come closer to δ13C(hydrocarbon). BIOPHY, project supported by the French National Research Agency (ANR), proposes to use electrical methods and gas analyses to develop an operational and non-destructive method for monitoring in situ biodegradation of hydrocarbons in order to optimize soil treatment. Demonstration field is located in the South of Paris (France), where liquid fuels (gasoline and diesel) leaked from some tanks in 1997. In order to stimulate biodegradation, a trench has been dug to supply oxygen to the water table and thus stimulate aerobic metabolic bioprocesses. ER and IP surveys are performed regularly to monitor the stimulated biodegradation and progress of remediation until soil cleanup. Microbial activity is characterized by CO2 production increase and δ13C isotopic deviation, in the produced CO2 measured by infrared laser spectroscopy, and by an evolution of electrical conductivity and IP responses in correlation with microbiological and chemical analyses.

Apparatus and method for detecting gamma radiation

DOEpatents

Sigg, Raymond A.

1994-01-01

A high efficiency radiation detector for measuring X-ray and gamma radiation from small-volume, low-activity liquid samples with an overall uncertainty better than 0.7% (one sigma SD). The radiation detector includes a hyperpure germanium well detector, a collimator, and a reference source. The well detector monitors gamma radiation emitted by the reference source and a radioactive isotope or isotopes in a sample source. The radiation from the reference source is collimated to avoid attenuation of reference source gamma radiation by the sample. Signals from the well detector are processed and stored, and the stored data is analyzed to determine the radioactive isotope(s) content of the sample. Minor self-attenuation corrections are calculated from chemical composition data.

Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking

USGS Publications Warehouse

Vander Zanden, Hannah B.; Tucker, Anton D.; Hart, Kristen M.; Lamont, Margaret M.; Fujisaki, Ikuko; Addison, David S.; Mansfield, Katherine L.; Phillips, Katrina F.; Wunder, Michael B.; Bowen, Gabriel J.; Pajuelo, Mariela; Bolten, Alan B.; Bjorndal, Karen A.

2015-01-01

Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: 1) a nominal approach through discriminant analysis and 2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively determine geographic origin for large numbers of untracked individuals. Regular monitoring of sea turtle nesting aggregations with stable isotope sampling can be used to fill critical data gaps regarding habitat use and migration patterns. Probabilistic assignment to origin with isoscapes has not been previously used in the marine environment, but the methods presented here could also be applied to other migratory marine species.

Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking.

PubMed

Zanden, Hannah B Vander; Tucker, Anton D; Hart, Kristen M; Lamont, Margaret M; Fuisaki, Ikuko; Addison, David; Mansfield, Katherine L; Phillips, Katrina F; Wunder, Michael B; Bowen, Gabriel J; Pajuelo, Mariela; Bolten, Alan B; Bjorndal, Karen A

2015-03-01

Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: (1) a nominal approach through discriminant analysis and (2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively determine geographic origin for large numbers of untracked individuals. Regular monitoring of sea turtle nesting aggregations with stable isotope sampling can be used to fill critical data gaps regarding habitat use and migration patterns. Probabilistic assignment to origin with isoscapes has not been previously used in the marine environment, but the methods presented here could also be applied to other migratory marine species.

Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

NASA Astrophysics Data System (ADS)

Noone, D.; Galewsky, J.; Sharp, Z.; Worden, J.

2008-12-01

The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link the water sources to regional sinks, and thus proves useful in understanding the large scale humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and monitored as climate changes.

Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

NASA Astrophysics Data System (ADS)

Galewsky, J.; Noone, D.; Sharp, Z.; Worden, J.

2009-04-01

The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link water sources to regional sinks, and thus proves useful in understanding large scale atmospheric humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and monitored as climate changes.

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-permeable polypropylene tubing and a cavity ring-down laser absorption spectrometer. By analyzing water vapor δ2H and δ18O sampled with the tubing from a fine sand for temperatures ranging between 8-24° C, we demonstrate that (i) our new method is capable of monitoring δ2H and δ18O in soils online with high precision and, after calibration, also with high accuracy, (ii) our sampling protocol enabled detecting changes of δ2H and δ18O following non-fractionating addition and removal of liquid water and water vapor of different isotopic compositions, and (iii) the time needed for the tubing to monitor these changes is compatible with the observed variations of δ2H and δ18O in soils under natural conditions.

Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method.

PubMed

Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

2018-04-01

Isotope ratio monitoring by 13 C NMR spectrometry (irm- 13 C NMR) provides the complete 13 C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13 C natural abundance values (50‰), irm- 13 C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13 C NMR. Until now, the conventional strategy to determine the position-specific abundance x i relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13 C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13 C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1 H NMR pulse sequence (named DWET) with a 13 C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T 1 , which forms a serious limitation for irm- 13 C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T 1 variations. Their performance is evaluated on the determination of the 13 C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm- 13 C NMR since it is now possible to perform isotopic analysis with high relaxing agent concentrations, leading to a strong reduction of the overall experiment time. Copyright © 2018 Elsevier Inc. All rights reserved.

Real-time isotope monitoring network at the Biosphere 2 Landscape Evolution Observatory resolves meter-to-catchment scale flow dynamics

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Van Haren, J. L. M.; Kim, M.; Harman, C. J.; Pangle, L.; Meredith, L. K.; Troch, P. A.

2017-12-01

Stable isotope analysis is a powerful tool for tracking flow pathways, residence times, and the partitioning of water resources through catchments. However, the capacity of stable isotopes to characterize catchment hydrological dynamics has not been fully exploited as commonly used methodologies constrain the frequency and extent at which isotopic data is available across hydrologically-relevant compartments (e.g. soil, plants, atmosphere, streams). Here, building upon significant recent developments in laser spectroscopy and sampling techniques, we present a fully automated monitoring network for tracing water isotopes through the three model catchments of the Landscape Evolution Observatory (LEO) at the Biosphere 2, University of Arizona. The network implements state-of-the-art techniques for monitoring in great spatiotemporal detail the stable isotope composition of water in the subsurface soil, the discharge outflow, and the atmosphere above the bare soil surface of each of the 330-m2 catchments. The extensive valving and probing systems facilitate repeated isotope measurements from a total of more than five-hundred locations across the LEO domain, complementing an already dense array of hydrometric and other sensors installed on, within, and above each catchment. The isotope monitoring network is operational and was leveraged during several months of experimentation with deuterium-labelled rain pulse applications. Data obtained during the experiments demonstrate the capacity of the monitoring network to resolve sub-meter to whole-catchment scale flow and transport dynamics in continuous time. Over the years to come, the isotope monitoring network is expected to serve as an essential tool for collaborative interdisciplinary Earth science at LEO, allowing us to disentangle changes in hydrological behavior as the model catchments evolve in time through weathering and colonization by plant communities.

One Year of Monthly N and O Isotope Measurements in Nitrate from 18 Streamwater Monitoring Stations Within the Predominantly Pastoral Upper Manawatu Catchment, New Zealand

NASA Astrophysics Data System (ADS)

Baisden, W. T.; Douence, C.

2010-12-01

New Zealand's intensive pastoral agricultural systems have a significant impact on water quality due to nitrogen loading in rivers. A research programme has been designed to develop indicators of the sources and denitrification losses of nitrate in streamwater. This work describes the results of one year of monthly measurements at ~18 monitoring locations in the 1260 square km upper Manawatu River catchment. The catchment was chosen for study because it is among the most pastoral catchments in New Zealand, with little non-pastoral agriculture and limited forest area outside of the Tararua mountain range on the west side of the catchment. The use of N and O isotope ratios in nitrate has considerable potential to elucidate the sources and fate of nitrate with greater precision than in most other nations due to the lack of nitrate in atmospheric deposition and the lack of nitrates used as fertilizer. We measured N and O isotope ratios in nitrate plus nitrite using cadmium and azide chemical denitrification method, and refer to the results as nitrate for brevity due to low nitrite concentrations. When examined as annual averages at each monitoring site, we found the lowest N and O isotope ratios in our only site draining native forest. All agricultural monitoring sites sit approximately on a 1:1 line, enriched in N-15 and O-18 by 2-6 per mil relative to the native forest subcatchment. The three main effluent point sources in the catchment demonstrated unexpected variability in isotope ratios. Two modern sewage treatment ponds had N and O isotope ratios close to those found in agricultural catchments, while a closed meat freezing factory effluent pond had isotope ratios strongly enriched in N-15 and O-18. The lack of summer low flows during monitoring period, combined with the variability in isotope ratios from point source, appeared to be responsible for our inability to clearly detect the effect of point sources in the isotope data from stations upstream and downstream of the point source inputs. Month-to-month variation in some catchments sat near the 1:1 line expected for denitrification as the primary driver of variability in isotope ratios, but the data from many stations including river's main stem was more complex. Overall, we are hopeful about the potential for the development of isotope indicators as planned. Specifically, our results tentatively support the use of the O isotope composition of soil water as a function of elevation and irrigation, and N isotope composition of soil N as a function of agricultural intensity driving the use of N and O isotopes to identify sources. While diffusion processes appear to suppress the isotope effect associated with denitrification, it may be observable and consistent in smaller and more uniform subcatchments. These smaller subcatchments will therefore become an increasing focus of our study. If successful, the indicators we intend to develop have the potential to work within a nitrogen cap and trade scheme for the catchment, providing an important efficiency tool to enable agriculture intensification in areas of effective N removal while targeting areas of poor nitrogen removal for decreased agricultural intensity or alternate land uses.

Apparatus and method for detecting gamma radiation

DOEpatents

Sigg, R.A.

1994-12-13

A high efficiency radiation detector is disclosed for measuring X-ray and gamma radiation from small-volume, low-activity liquid samples with an overall uncertainty better than 0.7% (one sigma SD). The radiation detector includes a hyperpure germanium well detector, a collimator, and a reference source. The well detector monitors gamma radiation emitted by the reference source and a radioactive isotope or isotopes in a sample source. The radiation from the reference source is collimated to avoid attenuation of reference source gamma radiation by the sample. Signals from the well detector are processed and stored, and the stored data is analyzed to determine the radioactive isotope(s) content of the sample. Minor self-attenuation corrections are calculated from chemical composition data. 4 figures.

Tracing Sources of Organic Matter and Nitrate in the San Francisco Bay-Delta-River Ecosystem Using Isotopic Techniques: Comparison of Insights Gained from Fixed-site, Synoptic, and Diel Sampling Strategies

NASA Astrophysics Data System (ADS)

Kendall, C.; Silva, S. R.; Doctor, D. H.; Wankel, S. D.; Chang, C. C.; Bergamaschi, B. A.; Kratzer, C. R.; Dahlgren, R. A.; Fleenor, W. E.

2005-12-01

Understanding the sources and sinks for organics and nitrate is critical for devising effective strategies to reduce their loads in ecosystems and mitigate local problems of low dissolved oxygen levels and/or production of disinfection byproducts during water treatment. Since isotopic techniques are effective methods for quantifying the sources and sinks of organics and nutrients, we have analyzed particulate organic matter (POM), nitrate, dissolved inorganic and organic carbon (DIC, DOC), and water isotope samples from selected sites since 2000. Our studies indicate that isotope data are a useful adjunct to traditional methods for assessing and monitoring sources of organics and nutrients. The original sampling in 2000-2001 used the classical fixed-site and fixed-time interval sampling approach, where sites on the San Joaquin River and its major tributaries were sampled bimonthly from July to October for chemistry and isotopes (Kratzer et al., 2004: see URL below). Subsequently, samples were collected during 4 transects along the San Joaquin River (10/02, 3/03, 9/03, and 7/04); the first and last of these transects extended through the Delta to the Bay. Several sites were sampled during diel studies in 8/04 and 7/05. Although fixed-site sampling is the norm in watershed studies, we have found that isotope and chemical data collected during longitudinal transects of the river and diel sampling of several sites along short river reaches have been more useful in convincing colleagues that isotope measurements are extremely useful adjuncts to traditional methods for assessing and monitoring sources of organics and nutrients during ecosystem restoration programs. Furthermore, we have concluded that while the obvious value of isotopes for water resources management is to tell us things about water resources that we didn't know before, what convinces the skeptic is when the isotopes tell us things about water resources that contradict what we thought we knew before. This work will highlight these and other insights developed using varied sampling strategies, and suggest guidelines for how to approach future studies in biologically active and human impacted rivers like the San Joaquin River system.

Rapid measurement of plasma free fatty acid concentration and isotopic enrichment using LC/MS

PubMed Central

Persson, Xuan-Mai T.; Błachnio-Zabielska, Agnieszka Urszula; Jensen, Michael D.

2010-01-01

Measurements of plasma free fatty acids (FFA) concentration and isotopic enrichment are commonly used to evaluate FFA metabolism. Until now, gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) was the best method to measure isotopic enrichment in the methyl derivatives of 13C-labeled fatty acids. Although IRMS is excellent for analyzing enrichment, it requires time-consuming derivatization steps and is not optimal for measuring FFA concentrations. We developed a new, rapid, and reliable method for simultaneous quantification of 13C-labeled fatty acids in plasma using high-performance liquid chromatography-mass spectrometry (HPLC/MS). This method involves a very quick Dole extraction procedure and direct injection of the samples on the HPLC system. After chromatographic separation, the samples are directed to the mass spectrometer for electrospray ionization (ESI) and analysis in the negative mode using single ion monitoring. By employing equipment with two columns connected parallel to a mass spectrometer, we can double the throughput to the mass spectrometer, reducing the analysis time per sample to 5 min. Palmitate flux measured using this approach agreed well with the GC/C/IRMS method. This HPLC/MS method provides accurate and precise measures of FFA concentration and enrichment. PMID:20526002

Tritium monitor

DOEpatents

Chastagner, Philippe

1994-01-01

A system for continuously monitoring the concentration of tritium in an aqueous stream. The system pumps a sample of the stream to magnesium-filled combustion tube which reduces the sample to extract hydrogen gas. The hydrogen gas is then sent to an isotope separation device where it is separated into two groups of isotopes: a first group of isotopes containing concentrations of deuterium and tritium, and a second group of isotopes having substantially no deuterium and tritium. The first group of isotopes containing concentrations of deuterium and tritium is then passed through a tritium detector that produces an output proportional to the concentration of tritium detected. Preferably, the detection system also includes the necessary automation and data collection equipment and instrumentation for continuously monitoring an aqueous stream.

Tritium monitor

DOEpatents

Chastagner, P.

1994-06-14

A system is described for continuously monitoring the concentration of tritium in an aqueous stream. The system pumps a sample of the stream to magnesium-filled combustion tube which reduces the sample to extract hydrogen gas. The hydrogen gas is then sent to an isotope separation device where it is separated into two groups of isotopes: a first group of isotopes containing concentrations of deuterium and tritium, and a second group of isotopes having substantially no deuterium and tritium. The first group of isotopes containing concentrations of deuterium and tritium is then passed through a tritium detector that produces an output proportional to the concentration of tritium detected. Preferably, the detection system also includes the necessary automation and data collection equipment and instrumentation for continuously monitoring an aqueous stream. 1 fig.

On-target labeling of intracellular metabolites combined with chemical mapping of individual hyphae revealing cytoplasmic relocation of isotopologues.

PubMed

Hu, Jie-Bi; Chen, Yu-Chie; Urban, Pawel L

2012-06-05

A microscale analytical platform integrating microbial cell culture, isotopic labeling, along with visual and mass spectrometric imaging with single-cell resolution has been developed and applied in the monitoring of cellular metabolism in fungal mycelium. The method implements open chips with a two-dimensional surface pattern composed of hydrophobic and hydrophilic zones. Two hydrophilic islands are used as medium reservoirs, while the hydrophobic area constitutes the support for the growing aerial hyphae, which do not have direct contact with the medium. The first island, containing (12)C(6)-glucose medium, was initially inoculated with the mycelium (Neurospora crassa), and following the initial incubation period, the hyphae progressed toward the second medium island, containing an isotopically labeled substrate ((13)C(6)-glucose). The (13)C atoms were gradually incorporated into cellular metabolites, which was revealed by MALDI-MS. The fate of the chitin-biosynthesis precursor, uridine diphosphate N-acetylglucosamine (UDP-GlcNAc), was monitored by recording mass spectra with characteristic isotopic patterns, which indicated the presence of various (12)C/(13)C isotopologues. The method enabled mapping the (13)C-labeled UDP-GlcNAc in fungal mycelium and recording its redistribution in hyphae, directly on the chip.

Maximum reasonable radioxenon releases from medical isotope production facilities and their effect on monitoring nuclear explosions.

PubMed

Bowyer, Theodore W; Kephart, Rosara; Eslinger, Paul W; Friese, Judah I; Miley, Harry S; Saey, Paul R J

2013-01-01

Fission gases such as (133)Xe are used extensively for monitoring the world for signs of nuclear testing in systems such as the International Monitoring System (IMS). These gases are also produced by nuclear reactors and by fission production of (99)Mo for medical use. Recently, medical isotope production facilities have been identified as the major contributor to the background of radioactive xenon isotopes (radioxenon) in the atmosphere (Stocki et al., 2005; Saey, 2009). These releases pose a potential future problem for monitoring nuclear explosions if not addressed. As a starting point, a maximum acceptable daily xenon emission rate was calculated, that is both scientifically defendable as not adversely affecting the IMS, but also consistent with what is possible to achieve in an operational environment. This study concludes that an emission of 5 × 10(9) Bq/day from a medical isotope production facility would be both an acceptable upper limit from the perspective of minimal impact to monitoring stations, but also appears to be an achievable limit for large isotope producers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Broad-spectrum monitoring strategies for predicting occult precipitation contribution to water balance in a coastal watershed in California: Ground-truthing, areal monitoring and isotopic analysis of fog in the San Francisco Bay region

NASA Astrophysics Data System (ADS)

Koohafkan, M.; Thompson, S. E.; Leonardson, R.; Dufour, A.

2013-12-01

We showcase a fog monitoring study designed to quantitatively estimate the contribution of summer fog events to the water balance of a coastal watershed managed by the San Francisco Public Utilities Commission. Two decades of research now clearly show that fog and occult precipitation can be major contributors to the water balance of watersheds worldwide. Monitoring, understanding and predicting occult precipitation is therefore as hydrologically compelling as forecasting precipitation or evaporation, particularly in the face of climate variability. We combine ground-based monitoring and collection strategies with remote sensing technologies, time-lapse imagery, and isotope analysis to trace the ';signature' of fog in physical and ecological processes. Spatial coverage and duration of fog events in the watershed is monitored using time-lapse cameras and leaf wetness sensors strategically positioned to provide estimates of the fog bank extent and cloud base elevation, and this fine-scale data is used to estimate transpiration suppression by fog and is examined in the context of regional climate through the use of satellite imagery. Soil moisture sensors, throughfall collectors and advective fog collectors deployed throughout the watershed provide quantitative estimates of fog drip contribution to soil moisture and plants. Fog incidence records and streamflow monitoring provide daily estimates of fog contribution to streamflow. Isotope analysis of soil water, fog drip, stream water and vegetation samples are used to probe for evidence of direct root and leaf uptake of fog drip by plants. Using this diversity of fog monitoring methods, we develop an empirical framework for the inclusion of fog processes in water balance models.

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.

Isotope-dilution gas chromatography-mass spectrometry method for the analysis of hydroxyurea.

PubMed

Garg, Uttam; Scott, David; Frazee, Clint; Kearns, Gregory; Neville, Kathleen

2015-06-01

Hydroxyurea is used in the treatment of various malignancies and sickle cell disease. There are limited studies on the pharmacokinetics of hydroxyurea, particularly in pediatric patients. An accurate, precise, and sensitive method is needed to support such studies and to monitor therapeutic adherence. We describe a novel gas chromatography-mass spectrometry (GC-MS) method for the determination of hydroxyurea concentration in plasma using stable labeled hydroxyurea C N2 as an internal standard. The method involved an organic extraction followed by the preparation of trimethylsilyl (TMS) derivatives of hydroxyurea for GC-MS selected ion-monitoring analysis. The following mass-to-charge (m/z) ratio ions for silated hydroxyurea and hydroxyurea C N2 were monitored: hydroxyurea-quantitative ion 277, qualifier ions 292 and 249; hydroxyurea C N2-quantitative ion 280, qualifier ion 295. This method was evaluated for reportable range, accuracy, within-run and between-run imprecisions, and limits of quantification. The reportable range for the method was 0.1-100 mcg/mL. All results were accurate within an allowable error of 15%. Within-run and between-run imprecisions were <15%. Samples were stable for at least 4 hours at room temperature, 2 months at -20°C, and 6 months at -70°C, and after 3 freeze/thaw cycles. Extraction efficiency for 1-, 5-, 10-, and 50-mcg/mL samples averaged 2.2%, 1.8%, 1.6%, and 1.4%, respectively. The isotope-dilution GC-MS method for analysis of hydroxyurea described here is accurate, sensitive, precise, and robust. Its characteristics make the method suitable for supporting pharmacokinetic studies and/or clinical therapeutic monitoring.

Monitoring BTEX degradation by CSIA - chances and challenges

NASA Astrophysics Data System (ADS)

Vogt, Carsten; Dorer, Conrad; Kümmel, Steffen; Bombach, Petra; Fischer, Anko; Richnow, Hans Hermann

2014-05-01

Monitoring is crucial for evaluating the success of any geobiotechnological applications. Compound- specific stable isotope analysis (CSIA) has emerged as a key method for monitoring biogeochemical transformation processes. Isotope compositions of residual reactants may change during the first rate-limiting step in (bio)chemical reactions; measurement of these changes are the basis for CSIA. Caused by differences in the activation energy, light isotopologues often react slightly faster than heavy isotopologues, resulting in enrichment of heavy isotopes at the reactive site in the substrate or of light isotopes in the product. This is termed isotope fractionation. Upon multi-dimensional CSIA (2D-CSIA, 3D-CSIA), the isotope fractionation of two or more different elements within a molecule is determined, allowing highly resolved analyses of degradation processes as masking effects typically occurring in one-dimensional CSIA are cancelled. In the last years, 2D-CSIA making use of the ratio of stable carbon to hydrogen isotopes (13C/12C, 2H/1H), turned out to be an important tool for elucidating the environmental biodegradation pattern of BTEX compounds which are global notorious contaminants. This presentation aims to summarize the current knowledge on 2D-CSIA of BTEX, to point out the prospects and to indicate future perspectives upon monitoring in the field. Degradation experiments for determining carbon and hydrogen isotope fractionation factors were carried out using several pure and mixed cultures performing different BTEX-activating reactions. Various anaerobic key reactions showed pronounced hydrogen isotope fractionation: (i) fumarate addition to the methyl moiety of toluene, xylene isomers and probably ethylbenzene catalyzed by benzylsuccinate synthases, (ii) anaerobic hydroxylation of the ethyl side chain of ethylbenzene catalyzed by ethylbenzene dehydrogenase, and (iii) anaerobic activation of benzene by yet unknown biochemical mechanisms. Due to the high hydrogen isotope fractionation, the ratios of hydrogen vs. carbon isotope fractionation in two-dimensional plots (lambda values, Λ) were generally higher than 10 (in extreme cases > 100). Upon aerobic activation reactions at the aromatic ring catalyzed by mono- or dioxygenases, usually Λ values smaller than 10 were observed due to small, absent or inverse hydrogen isotope fractionation. An exception is the aerobic monooxygenation of methyl or methylene moieties which is linked to large hydrogen and carbon isotope fractionation. Since Λ values are highly indicative for specific transformation reactions, 2D-CSIA has a great potential for evaluating biodegradation processes of BTEX in the environment. Moreover, reactions catalyzed by benzylsuccinate synthases showed partially variable Λ values, indicating slightly different reaction mechanisms of isoenzymes, probably permitting the detection of specific isoenzymes by 2D-CSIA in field applications. In contrast, ethylbenzene dehydrogenase of three tested organisms showed similar, very characteristic isotope fractionation pattern even under different redox conditions. The major goal of future investigations is to use 2D-CSIA at contaminated field sites for elucidating specific degradation pathways. Single data for benzene are promising, demonstrating e.g., anaerobic benzene degradation by 2D-CSIA at a highly contaminated site. Nevertheless, 2D-CSIA field data for BTEX are yet lacking and need to be surveyed for a proper evaluation of the 2D-CSIA concept for BTEX.

Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

NASA Astrophysics Data System (ADS)

Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard

2014-05-01

Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such systematic knowledge of the extent of oxygen isotope fractionation between H2O and CO2 can help to reconstruct equilibration times, fluid-CO2 ratios as well as temperature and salinity conditions. Isotope results from systematic laboratory studies and the information they provide for assessing in situ reservoir conditions can be transferred to field applications concerning integrity of CO2 reservoirs. They can also apply to natural systems and other industrial uses that involve monitoring of gases in the subsurface under similar pressure and temperature conditions. Reference: Myrttinen, A., Becker, V., Barth, J.A.C., 2012. A review of methods used for equilibrium isotope fractionation investigations between dissolved inorganic carbon and CO2. Earth-Science Reviews, 115(3): 192-199.

What can one sample tell us? Stable isotopes can assess complex processes in national assessments of lakes, rivers and streams.

EPA Science Inventory

Stable isotopes can be very useful in large-scale monitoring programs because samples for isotopic analysis are easy to collect, and isotopes integrate information about complex processes such as evaporation from water isotopes and denitrification from nitrogen isotopes. Traditi...

Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

PubMed

Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

2010-01-01

In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

The Multi-Isotope Process (MIP) Monitor Project: FY13 Final Report

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

Meier, David E.; Coble, Jamie B.; Jordan, David V.

The Multi-Isotope Process (MIP) Monitor provides an efficient approach to monitoring the process conditions in reprocessing facilities in support of the goal of “… (minimization of) the risks of nuclear proliferation and terrorism.” The MIP Monitor measures the distribution of the radioactive isotopes in product and waste streams of a nuclear reprocessing facility. These isotopes are monitored online by gamma spectrometry and compared, in near-real-time, to spectral patterns representing “normal” process conditions using multivariate analysis and pattern recognition algorithms. The combination of multivariate analysis and gamma spectroscopy allows us to detect small changes in the gamma spectrum, which may indicatemore » changes in process conditions. By targeting multiple gamma-emitting indicator isotopes, the MIP Monitor approach is compatible with the use of small, portable, relatively high-resolution gamma detectors that may be easily deployed throughout an existing facility. The automated multivariate analysis can provide a level of data obscurity, giving a built-in information barrier to protect sensitive or proprietary operational data. Proof-of-concept simulations and experiments have been performed in previous years to demonstrate the validity of this tool in a laboratory setting for systems representing aqueous reprocessing facilities. However, pyroprocessing is emerging as an alternative to aqueous reprocessing techniques.« less

A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

NASA Astrophysics Data System (ADS)

Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

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 thousand were detected in the hair strands from UK residents whereas the traveler presented a variation of >5 per thousand. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies.

Use of phenyl/tetrazolyl-functionalized magnetic microspheres and stable isotope labeled internal standards for significant reduction of matrix effect in determination of nine fluoroquinolones by liquid chromatography-quadrupole linear ion trap mass spectrometry.

PubMed

Xu, Fei; Liu, Feng; Wang, Chaozhan; Wei, Yinmao

2018-02-01

In this study, the strategy of unique adsorbent combined with isotope labeled internal standards was used to significantly reduce the matrix effect for the enrichment and analysis of nine fluoroquinolones in a complex sample by liquid chromatography coupled to quadrupole linear ion trap mass spectrometry (LC-QqQ LIT -MS/MS). The adsorbent was prepared conveniently by functionalizing Fe 3 O 4 @SiO 2 microspheres with phenyl and tetrazolyl groups, which could adsorb fluoroquinolones selectively via hydrophobic, electrostatic, and π-π interactions. The established magnetic solid-phase extraction (MSPE) method as well as using stable isotope labeled internal standards in the next MS/MS detection was able to reduce the matrix effect significantly. In the process of LC-QqQ LIT -MS/MS analysis, the precursor and product ions of the analytes were monitored quantitatively and qualitatively on a QTrap system equipped simultaneously with the multiple reaction monitoring (MRM) and enhanced product ion (EPI) scan. Subsequently, the enrichment method combined with LC-QqQ LIT -MS/MS demonstrated good analytical features in terms of linearity (7.5-100.0 ng mL -1 , r > 0.9960), satisfactory recoveries (88.6%-118.3%) with RSDs < 12.0%, LODs = 0.5 μg kg -1 and LOQs = 1.5 μg kg -1 for all tested analytes. Finally, the developed MSPE-LC-QqQ LIT -MS/MS method had been successfully applied to real pork samples for food-safety risk monitoring in Ningxia Province, China. Graphical abstract Mechanism of reducing matrix effect through the as-prepared adsorbent.

Shot-noise Limited Faraday Rotation Spectroscopy for Detection of Nitric Oxide Isotopes in Breath, Urine, and Blood

PubMed Central

Wang, Yin; Nikodem, Michal; Zhang, Eric; Cikach, Frank; Barnes, Jarrod; Comhair, Suzy; Dweik, Raed A.; Kao, Christina; Wysocki, Gerard

2015-01-01

Measurement of NO and/or its metabolites in the various body compartments has transformed our understanding of biology. The inability of the current NO measurement methods to account for naturally occurring and experimental NO isotopes, however, has prevented the scientific community from fully understating NO metabolism in vivo. Here we present a mid-IR Faraday rotation spectrometer (FRS) for detection of NO isotopes. The instrument utilizes a novel dual modulation/demodulation (DM) FRS method which exhibits noise performance at only 2 times the fundamental quantum shot-noise level and provides the record sensitivity in its class. This is achieved with a system that is fully autonomous, robust, transportable, and does not require cryogenic cooling. The DM-FRS enables continuous monitoring of nitric oxide isotopes with the detection limits of 3.72 ppbv/Hz1/2 to14NO and 0.53 ppbv/Hz1/2 to15NO using only 45 cm active optical path. This DM-FRS measurement method can be used to improve the performance of conventional FRS sensors targeting other radical species. The feasibility of the instrument to perform measurements relevant to studies of NO metabolism in humans is demonstrated. PMID:25767064

Dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources

DOEpatents

Barty, Christopher P.J.

2013-02-05

A dual isotope notch observer for isotope identification, assay and imaging with mono-energetic gamma-ray sources includes a detector arrangement consists of three detectors downstream from the object under observation. The latter detector, which operates as a beam monitor, is an integrating detector that monitors the total beam power arriving at its surface. The first detector and the middle detector each include an integrating detector surrounding a foil. The foils of these two detectors are made of the same atomic material, but each foil is a different isotope, e.g., the first foil may comprise U235 and second foil may comprise U238. The integrating detectors surrounding these pieces of foil measure the total power scattered from the foil and can be similar in composition to the final beam monitor. Non-resonant photons will, after calibration, scatter equally from both foils.

Glycan reductive isotope labeling for quantitative glycomics.

PubMed

Xia, Baoyun; Feasley, Christa L; Sachdev, Goverdhan P; Smith, David F; Cummings, Richard D

2009-04-15

Many diseases and disorders are characterized by quantitative and/or qualitative changes in complex carbohydrates. Mass spectrometry methods show promise in monitoring and detecting these important biological changes. Here we report a new glycomics method, termed glycan reductive isotope labeling (GRIL), where free glycans are derivatized by reductive amination with the differentially coded stable isotope tags [(12)C(6)]aniline and [(13)C(6)]aniline. These dual-labeled aniline-tagged glycans can be recovered by reverse-phase chromatography and can be quantified based on ultraviolet (UV) absorbance and relative ion abundances. Unlike previously reported isotopically coded reagents for glycans, GRIL does not contain deuterium, which can be chromatographically resolved. Our method shows no chromatographic resolution of differentially labeled glycans. Mixtures of differentially tagged glycans can be directly compared and quantified using mass spectrometric techniques. We demonstrate the use of GRIL to determine relative differences in glycan amount and composition. We analyze free glycans and glycans enzymatically or chemically released from a variety of standard glycoproteins, as well as human and mouse serum glycoproteins, using this method. This technique allows linear relative quantitation of glycans over a 10-fold concentration range and can accurately quantify sub-picomole levels of released glycans, providing a needed advancement in the field of glycomics.

GLYCAN REDUCTIVE ISOTOPE LABELING (GRIL) FOR QUANTITATIVE GLYCOMICS

PubMed Central

Xia, Baoyun; Feasley, Christa L.; Sachdev, Goverdhan P.; Smith, David F.; Cummings, Richard D.

2009-01-01

Many diseases and disorders are characterized by quantitative and/or qualitative changes in complex carbohydrates. Mass spectrometry methods show promise in monitoring and detecting these important biological changes. Here we report a new glycomics method, termed Glycan Reductive Isotope Labeling (GRIL), where free glycans are derivatized by reductive amination with the differentially coded stable isotope tags [12C6]-aniline and [13C6]-aniline. These dual-labeled aniline-tagged glycans can be recovered by reversed-phase chromatography and quantified based on UV-absorbance and relative ion abundances. Unlike previously reported isotopically coded reagents for glycans, GRIL does not contain deuterium, which can be chromatographically resolved. Our method shows no chromatographic resolution of differentially labeled glycans. Mixtures of differentially tagged glycans can be directly compared and quantified using mass spectrometric techniques. We demonstrate the use of GRIL to determine relative differences in glycan amount and composition. We analyze free glycans and glycans enzymatically or chemically released from a variety of standard glycoproteins, as well as human and mouse serum glycoproteins using this method. This technique allows for linear, relative quantitation of glycans over a 10-fold concentration range and can accurately quantify sub-picomole levels of released glycans, providing a needed advancement in the field of Glycomics. PMID:19454239

Stable Isotopes Reveal Nitrogen Loading to Lake Tanganyika from Remote Shoreline Villages

NASA Astrophysics Data System (ADS)

Kelly, Brianne; Mtiti, Emmanuel; McIntyre, Peter B.; Vadeboncoeur, Yvonne

2017-02-01

Access to safe water is an ongoing challenge in rural areas in Tanzania where communities often lack access to improved sanitation. Methods to detect contamination of surface water bodies, such as monitoring nutrient concentrations and bacterial counts, are time consuming and results can be highly variable in space and time. On the northeast shore of Lake Tanganyika, Tanzania, the low population density coupled with the high potential for dilution in the lake necessitates the development of a sensitive method for detecting contamination in order to avoid human health concerns. We investigated the potential use of nitrogen and carbon stable isotopes of snail tissues to detect anthropogenic nutrient loading along the northeast shore of Lake Tanganyika. δ15N of snails was positively related to human population size in the nearest village, but only for villages with >4000 inhabitants. The areal footprint of villages within their watershed was also significantly correlated with snail δ15N, while agricultural land use and natural vegetation were not. Dissolved nutrient concentrations were not significantly different between village and reference sites. Our results indicate that nitrogen isotopes provide a sensitive index of local nutrient loading that can be used to monitor contamination of oligotrophic aquatic environments with low surrounding population densities.

The workshop on signatures of medical and industrial isotope production - WOSMIP; Strassoldo, Italy, 1-3 July 2009.

PubMed

Matthews, K M; Bowyer, T W; Saey, P R J; Payne, R F

2012-08-01

Radiopharmaceuticals make contributions of inestimable value to medical practice. With growing demand new technologies are being developed and applied worldwide. Most diagnostic procedures rely on (99m)Tc and the use of uranium targets in reactors is currently the favored method of production, with 95% of the necessary (99)Mo parent currently being produced by four major global suppliers. Coincidentally there are growing concerns for nuclear security and proliferation. New disarmament treaties such as the Comprehensive Nuclear-Test-Ban Treaty (CTBT) are coming into effect and treaty compliance-verification monitoring is gaining momentum. Radioxenon emissions (isotopes Xe-131, 133, 133m and 135) from radiopharmaceutical production facilities are of concern in this context because radioxenon is a highly sensitive tracer for detecting nuclear explosions. There exists, therefore, a potential for confusing source attribution, with emissions from radiopharmaceutical-production facilities regularly being detected in treaty compliance-verification networks. The CTBT radioxenon network currently under installation is highly sensitive with detection limits approaching 0.1 mBq/m³ and, depending on transport conditions and background, able to detect industrial release signatures from sites thousands of kilometers away. The method currently employed to distinguish between industrial and military radioxenon sources involves plots of isotope ratios (133m)Xe/(131m)Xe versus (135)Xe/(133)Xe, but source attribution can be ambiguous. Through the WOSMIP Workshop the environmental monitoring community is gaining a better understanding of the complexities of the processes at production facilities, and the production community is recognizing the impact their operations have on monitoring systems and their goal of nuclear non-proliferation. Further collaboration and discussion are needed, together with advances in Xe trapping technology and monitoring systems. Such initiatives will help in addressing the dichotomy which exists between expanding production and improving monitoring sensitivity, with the ultimate aim of enabling unambiguous distinction between different nuclide signatures. Copyright © 2012 Elsevier Ltd. All rights reserved.

New Isotopic Tracers for Shale Gas and Hydraulic Fracturing Fluids

EPA Pesticide Factsheets

The combined application of geochemistry, stable isotopes (δ18O, δ2H), strontium isotopes (87Sr/86Sr), boron isotopes (δ11B), and radium isotopes (228Ra/226Ra) provides a unique methodology for tracing and monitoring shale gas and fracking fluids in the environment.

Dynamic radioactive particle source

DOEpatents

Moore, Murray E; Gauss, Adam Benjamin; Justus, Alan Lawrence

2012-06-26

A method and apparatus for providing a timed, synchronized dynamic alpha or beta particle source for testing the response of continuous air monitors (CAMs) for airborne alpha or beta emitters is provided. The method includes providing a radioactive source; placing the radioactive source inside the detection volume of a CAM; and introducing an alpha or beta-emitting isotope while the CAM is in a normal functioning mode.

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring

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

Gulson, Brian, E-mail: brian.gulson@mq.edu.au; CSIRO Earth Science and Resource Engineering North Ryde, NSW 1670; Korsch, Michael

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments,more » air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. - Highlights: Black-Right-Pointing-Triangle Lead carbonate concentrate. Black-Right-Pointing-Triangle Successful use of Pb isotopes in identifying sources of Pb arising from transport and shipping. Black-Right-Pointing-Triangle Use of Pb isotopes in legal proceedings and their use in cleanup of residences. Black-Right-Pointing-Triangle Use of Pb isotopes in cleanup of a residual 9000 tonnes of Pb carbonate and in ongoing monitoring.« less

Radon isotope measurements as a monitoring tool for CO2 leakage in geological storage

NASA Astrophysics Data System (ADS)

Grandia, F.; Mazadiego, L. F.; de Elío, J.; Ortega, M.; Bruno, J.

2011-12-01

Early detection of the failure of the seal integrity is fundamental in the monitoring plan of a deep geological CO2 storage. A number of methods of leakage control are based on changes in fluid geochemistry (shallow water, soil gases) providing valuable indicators. Among them, the measurement of CO2 fluxes in the soil-atmosphere interface is commonly used since it can be easily done using portable infra-red analyzers (i.e., accumulation chambers). However, initial emission of CO2 from storage horizon could be masked by fluxes from biological activity, limiting its applicability as an early alarm system. The measurement of fluxes of trace gas (Rn, He, VOC) that are virtually absent in the pre-injection baseline turns out a promising complementary method. The measurement of radon isotopes has been long used for the observation of mass transport from deep reservoirs to surface despite the flux of 222Rn and 220Rn is usually very limited in sedimentary basins due to the short half-life of these isotopes. The enhanced transport of radon in CO2 fluxes has been reported from natural systems, resulting in concentration in air up to several thousands of Bq/m3. In the frame of the Compostilla pilot plant project in Spain, a number of methodologies to measure radon emission are being tested in natural systems to select of the most reliable and cost-effective method to be used in leakage control. These methods are (1) Scintillation detector EDA RD-200, (2) Track Etch °, (3) Ionization Chamber and (4) alpha spectroscopy SARAD RTM 200. Some of them are capable of measuring the isotopes separately (SARAD) whereas others just detect the bulk radon concentration. Also, these methods follow distinct procedures and acquisition times. The studied natural sites are located in central and NE Spain (Campo de Calatrava and La Selva basins), and in central Italy (Arezzo basin). Apparently, radon isotopes (up 200000 Bq/m3) are measured far from parent isotopes, and they are coupled to moderate to high CO2 fluxes (from 1×10-7 to 5×10-5 kg/m-2/s), along with other minor and trace gases (H2S, VOC, helium). The results in some sites show that not all Rn isotopes behave in the same way. In some cases, thoron (220Rn) does not flow with CO2 and 222Rn and, consequently, it appears to be a need to use methods capable of discriminating isotopes to avoid masking of unbounded radon to CO2 flux. The highest radon-thoron ratio is then related to CO2 flow. The behavior of radon isotopes could be caused by different rocks at depth. In addition, travel time for thoron could be too long compared to its very short half life (few hours). The methods tested provide similar radon data although some of them need further data refinement. SARAD alpha spectroscopy appears to be effective in the sites studied so far, which are characterized by high radon fluxes. Future work in the project is the testing of these techniques in areas with smaller radon fluxes and the determination of the gases that may interact with radon in some methods.

Development and Validation of a Rapid 13C6-Glucose Isotope Dilution UPLC-MRM Mass Spectrometry Method for Use in Determining System Accuracy and Performance of Blood Glucose Monitoring Devices

PubMed Central

Matsunami, Risë K.; Angelides, Kimon; Engler, David A.

2015-01-01

Background: There is currently considerable discussion about the accuracy of blood glucose concentrations determined by personal blood glucose monitoring systems (BGMS). To date, the FDA has allowed new BGMS to demonstrate accuracy in reference to other glucose measurement systems that use the same or similar enzymatic-based methods to determine glucose concentration. These types of reference measurement procedures are only comparative in nature and are subject to the same potential sources of error in measurement and system perturbations as the device under evaluation. It would be ideal to have a completely orthogonal primary method that could serve as a true standard reference measurement procedure for establishing the accuracy of new BGMS. Methods: An isotope-dilution liquid chromatography/mass spectrometry (ID-UPLC-MRM) assay was developed using 13C6-glucose as a stable isotope analogue to specifically measure glucose concentration in human plasma, and validated for use against NIST standard reference materials, and against fresh isolates of whole blood and plasma into which exogenous glucose had been spiked. Assay performance was quantified to NIST-traceable dry weight measures for both glucose and 13C6-glucose. Results: The newly developed assay method was shown to be rapid, highly specific, sensitive, accurate, and precise for measuring plasma glucose levels. The assay displayed sufficient dynamic range and linearity to measure across the range of both normal and diabetic blood glucose levels. Assay performance was measured to within the same uncertainty levels (<1%) as the NIST definitive method for glucose measurement in human serum. Conclusions: The newly developed ID UPLC-MRM assay can serve as a validated reference measurement procedure to which new BGMS can be assessed for glucose measurement performance. PMID:25986627

Data from a Thick Unsaturated Zone Underlying Two Artificial Recharge Sites along Oro Grande Wash in the Western Part of the Mojave Desert, near Victorville, San Bernardino County, California, 2001-2006

USGS Publications Warehouse

Clark, Dennis A.; Izbicki, John A.; Johnson, Russell D.; Land, Michael

2009-01-01

This report presents data on the physical and hydraulic properties of unsaturated alluvial deposits and on the chemical and isotopic composition of water collected at two recharge sites in the western part of the Mojave Desert, near Victorville, California, from 2001 to 2006. Unsaturated-zone monitoring sites were installed adjacent to the two recharge ponds using the ODEX air-hammer and air rotary method to depths of about 460 feet and 269 feet below land surface. Each of the two unsaturated-zone monitoring sites included a water-table well, matric-potential sensors, and suction-cup lysimeters installed in a single bore hole. Drilling procedures, lithologic and geophysical data, and site construction and instrumentation are described. Core material was analyzed for water content, bulk density, water potential, particle size, and water retention. The chemical composition of leachate from almost 400 samples of cores and cuttings was determined. Water from suction-cup lysimeters also was analyzed for chemical and isotopic composition. In addition, data on the chemical and isotopic composition of groundwater from the two water-table wells are reported along with chemical and isotopic composition of the surface water in the recharge ponds.

BIODEGRADATION OF FLUORANTHENE AS MONITORED USING STABLE CARBON ISOTOPES

EPA Science Inventory

The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

Real-time Stack Monitoring at the BaTek Medical Isotope Production Facility

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

McIntyre, Justin I.; Agusbudiman, A.; Cameron, Ian M.

2016-04-01

Radioxenon emissions from radiopharmaceutical production are a major source of background concentrations affecting the radioxenon detection systems of the International Monitoring System (IMS). Collection of real-time emissions data from production facilities makes it possible to screen out some medical isotope signatures from the IMS radioxenon data sets. This paper describes an effort to obtain and analyze real-time stack emissions data with the design, construction and installation of a small stack monitoring system developed by a joint CTBTO-IDC, BATAN, and PNNL team at the BaTek medical isotope production facility near Jakarta, Indonesia.

Radioxenon spiked air

DOE PAGES

Watrous, Matthew G.; Delmore, James E.; Hague, Robert K.; ...

2015-08-27

Four of the radioactive xenon isotopes ( 131mXe, 133mXe, 133Xe and 135Xe) with half-lives ranging from 9 h to 12 days are produced from nuclear fission and can be detected from days to weeks following their production and release. Being inert gases, they are readily transported through the atmosphere. Sources for release of radioactive xenon isotopes include operating nuclear reactors via leaks in fuel rods, medical isotope production facilities, and nuclear weapons' detonations. They are not normally released from fuel reprocessing due to the short half-lives. The Comprehensive Nuclear-Test-Ban Treaty has led to creation of the International Monitoring System. Themore » International Monitoring System, when fully implemented, will consist of one component with 40 stations monitoring radioactive xenon around the globe. Monitoring these radioactive xenon isotopes is important to the Comprehensive Nuclear-Test-Ban Treaty in determining whether a seismically detected event is or is not a nuclear detonation. A variety of radioactive xenon quality control check standards, quantitatively spiked into various gas matrices, could be used to demonstrate that these stations are operating on the same basis in order to bolster defensibility of data across the International Monitoring System. This study focuses on Idaho National Laboratory's capability to produce three of the xenon isotopes in pure form and the use of the four xenon isotopes in various combinations to produce radioactive xenon spiked air samples that could be subsequently distributed to participating facilities.« less

Radioxenon spiked air

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

Watrous, Matthew G.; Delmore, James E.; Hague, Robert K.

Four of the radioactive xenon isotopes ( 131mXe, 133mXe, 133Xe and 135Xe) with half-lives ranging from 9 h to 12 days are produced from nuclear fission and can be detected from days to weeks following their production and release. Being inert gases, they are readily transported through the atmosphere. Sources for release of radioactive xenon isotopes include operating nuclear reactors via leaks in fuel rods, medical isotope production facilities, and nuclear weapons' detonations. They are not normally released from fuel reprocessing due to the short half-lives. The Comprehensive Nuclear-Test-Ban Treaty has led to creation of the International Monitoring System. Themore » International Monitoring System, when fully implemented, will consist of one component with 40 stations monitoring radioactive xenon around the globe. Monitoring these radioactive xenon isotopes is important to the Comprehensive Nuclear-Test-Ban Treaty in determining whether a seismically detected event is or is not a nuclear detonation. A variety of radioactive xenon quality control check standards, quantitatively spiked into various gas matrices, could be used to demonstrate that these stations are operating on the same basis in order to bolster defensibility of data across the International Monitoring System. This study focuses on Idaho National Laboratory's capability to produce three of the xenon isotopes in pure form and the use of the four xenon isotopes in various combinations to produce radioactive xenon spiked air samples that could be subsequently distributed to participating facilities.« less

Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies

NASA Astrophysics Data System (ADS)

Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; Gross, Michael L.

2016-01-01

We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting.

Isotope-encoded Carboxyl Group Footprinting for Mass Spectrometry-based Protein Conformational Studies

PubMed Central

Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; Gross, Michael L.

2015-01-01

We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded “heavy” and “light” GEE are used to label separately the two states of the Orange Carotenoid Protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the “heavy” and “light” peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting. PMID:26384685

Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies

DOE PAGES

Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; ...

2015-09-18

Here, we report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded “heavy” and “light” GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the “heavy”more » and “light” peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting.« less

New stable isotope results for reservoir and above zone monitoring in CCS from the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; van Geldern, Robert; Myrttinen, Anssi; Veith, Becker; Zimmer, Martin; Barth, Johannes

2013-04-01

With rising atmospheric greenhouse gas concentrations, CCS technologies are a feasible option to diminish consequences of uncontrolled anthropogenic CO2 emissions and related climate change. However, application of CCS technologies requires appropriate and routine monitoring tools in order to ensure a safe and effective CO2 injection. Stable isotope techniques have proven as a useful geochemical monitoring tool at several CCS pilot projects worldwide. They can provide important information about gas - water - rock interactions, mass balances and CO2 migration in the reservoir and may serve as a tool to detect CO2 leakage in the subsurface and surface. Since the beginning of injection in 2008 at the Ketzin pilot site in Germany, more than 450 samples of fluids and gases have been analysed for their carbon and oxygen isotopic composition. Analytical advancements were achieved by modifying a conventional isotope ratio mass-spectrometer with a He dilution system. This allowed analyses of a larger number of CO2 gas samples from the injection well and observation wells. With this, a high-resolution monitoring program was established over a time period of one year. Results revealed that two isotopical distinct kinds of CO2 are injected at the Ketzin pilot site. The most commonly injected CO2 is so-called 'technical' CO2 with an average carbon isotopic value of about -31 ‰. Sporadically, natural source CO2 with an average δ13C value of -3 ‰ was injected. The injection of natural source CO2 generated a distinct isotope signal at the injection well that can be used as an ideal tracer. CO2 isotope values analysed at the observation wells indicate a highly dispersive migration of the supercritical CO2 that results in mixing of the two kinds of CO2 within the reservoir. Above-reservoir monitoring includes the first overlying aquifer above the cap rock. An observation well within this zone comprises an U-tube sampling device that allows frequent sampling of unaltered brine. The fluids were analysed among others for their carbon isotopic compositions of dissolved inorganic carbon (DIC). δ13CDIC values allowed to assess impacts of the carbonate-based drilling fluid during well development and helped to monitor successive geochemical re-equilibration processes of the brine. Based on the determined δ13C baseline values of the aquifer fluid, first concepts indicate the scale of change of the δ13CDIC values that would be necessary to detect CO2 leakage from the underlying storage reservoir. Recent efforts aim at applications of new laser-based isotope sensors that allow online measurements in the field. These devices are applied for CO2 gas tracer experiments as well as for monitoring of isotope composition of soil gases in the vicinity of the pilot site. This new development will allow much better temporal and spatial resolution of measurements at a lower price. Therefore, stable isotope analyses can become a strong and promising tool for subsurface as well as surface monitoring at future CCS sites.

Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

NASA Technical Reports Server (NTRS)

Morgan, Leah; Tappa, Mike; Ellam, Rob; Mark, Darren; Higgins, John; Simon, Justin I.

2013-01-01

Knowledge of the isotopic ratios of standards, spikes, and reference materials is fundamental to the accuracy of many geochronological methods. For example, the 238U/235U ratio relevant to U-Pb geochronology was recently re-determined [1] and shown to differ significantly from the previously accepted value employed during age determinations. These underlying values are fundamental to accurate age calculations in many isotopic systems, and uncertainty in these values can represent a significant (and often unrecognized) portion of the uncertainty budget for determined ages. The potassium isotopic composition of mineral standards, or neutron flux monitors, is a critical, but often overlooked component in the calculation of K-Ar and 40Ar/39Ar ages. It is currently assumed that all terrestrial materials have abundances indistinguishable from that of NIST SRM 985 [2]; this is apparently a reasonable assumption at the 0.25per mille level (1s) [3]. The 40Ar/39Ar method further relies on the assumption that standards and samples (including primary and secondary standards) have indistinguishable 40K/39K values. We will present data establishing the potassium isotopic compositions of NIST isotopic K SRM 985, elemental K SRM 999b, and 40Ar/39Ar biotite mineral standard GA1550 (sample MD-2). Stable isotopic compositions (41K/39K) were measured by the peak shoulder method with high resolution MC-ICP-MS (Thermo Scientific NEPTUNE Plus), using the accepted value of NIST isotopic SRM 985 [2] for fractionation [4] corrections [5]. 40K abundances were measured by TIMS (Thermo Scientific TRITON), using 41K/39K values from ICP-MS measurements (or, for SRM 985, values from [2]) for internal fractionation corrections. Collectively these data represent an important step towards a metrologically traceable calibration of 40K concentrations in primary 40Ar/39Ar mineral standards and improve uncertainties by ca. an order of magnitude in the potassium isotopic compositions of standards.

Monitoring Subsurface Fluid Flow Using Perfluorocarbon Tracers: Another Tool Potentially Available for Subsurface Fluid Flow Assessments

EPA Pesticide Factsheets

Perfluorocarbon Tracers (PFTs) Complement stable Isotopes and Geochemistry for Verifying, Assessing or Modeling Fluid Flow. Geochemistry, Isotopes and PFT’s complement Geophysics to monitor and verify plume movement, leakage to shallow aquifers or surface

In-line assay monitor for uranium hexafluoride

DOEpatents

Wallace, Steven A.

1981-01-01

An in-line assay monitor for determining the content of uranium-235 in a uranium hexafluoride gas isotopic separation system is provided which removes the necessity of complete access to the operating parameters of the system for determining the uranium-235 content. The monitor is intended for uses such as safeguard applications to assure that weapons grade uranium is not being produced in an enrichment cascade. The method and monitor for carrying out the method involve cooling of a radiation pervious chamber connected in fluid communication with the selected point in the system to withdraw a specimen and solidify the specimen in the chamber. The specimen is irradiated by means of an ionizing radiation source of energy different from that of the 185 keV gamma emissions from the uranium-235 present in the specimen. Simultaneously, the gamma emissions from the uranium-235 of the specimen and the source emissions transmitted through the sample are counted and stored in a multiple channel analyzer. The uranium-235 content of the specimen is determined from the comparison of the accumulated 185 keV energy counts and the reference energy counts. The latter is used to measure the total uranium isotopic content of the specimen. The process eliminates the necessity of knowing the system operating conditions and yet obtains the necessary data without need for large scintillation crystals and sophisticated mechanical designs.

Development and Validation of a Rapid (13)C6-Glucose Isotope Dilution UPLC-MRM Mass Spectrometry Method for Use in Determining System Accuracy and Performance of Blood Glucose Monitoring Devices.

PubMed

Matsunami, Risë K; Angelides, Kimon; Engler, David A

2015-05-18

There is currently considerable discussion about the accuracy of blood glucose concentrations determined by personal blood glucose monitoring systems (BGMS). To date, the FDA has allowed new BGMS to demonstrate accuracy in reference to other glucose measurement systems that use the same or similar enzymatic-based methods to determine glucose concentration. These types of reference measurement procedures are only comparative in nature and are subject to the same potential sources of error in measurement and system perturbations as the device under evaluation. It would be ideal to have a completely orthogonal primary method that could serve as a true standard reference measurement procedure for establishing the accuracy of new BGMS. An isotope-dilution liquid chromatography/mass spectrometry (ID-UPLC-MRM) assay was developed using (13)C6-glucose as a stable isotope analogue to specifically measure glucose concentration in human plasma, and validated for use against NIST standard reference materials, and against fresh isolates of whole blood and plasma into which exogenous glucose had been spiked. Assay performance was quantified to NIST-traceable dry weight measures for both glucose and (13)C6-glucose. The newly developed assay method was shown to be rapid, highly specific, sensitive, accurate, and precise for measuring plasma glucose levels. The assay displayed sufficient dynamic range and linearity to measure across the range of both normal and diabetic blood glucose levels. Assay performance was measured to within the same uncertainty levels (<1%) as the NIST definitive method for glucose measurement in human serum. The newly developed ID UPLC-MRM assay can serve as a validated reference measurement procedure to which new BGMS can be assessed for glucose measurement performance. © 2015 Diabetes Technology Society.

[Interest and limits of inductively coupled plasma mass spectrometry (ICP-MS) for urinary diagnosis of radionuclide internal contamination].

PubMed

Lecompte, Yannick; Bohand, Sandra; Laroche, Pierre; Cazoulat, Alain

2013-01-01

After a review of radiometric reference methods used in radiotoxicology, analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the workplace urinary diagnosis of internal contamination by radionuclides are evaluated. A literature review (covering the period from 2000 to 2012) is performed to identify the different applications of ICP-MS in radiotoxicology for urine analysis. The limits of detection are compared to the recommendations of the International commission on radiological protection (ICRP 78: "Individual monitoring for internal exposure of workers"). Except one publication describing the determination of strontium-90 (β emitter), all methods using ICP-MS reported in the literature concern actinides (α emitters). For radionuclides with a radioactive period higher than 10(4) years, limits of detection are most often in compliance with ICRP publication 78 and frequently lower than radiometric methods. ICP-MS allows the specific determination of plutonium-239 + 240 isotopes which cannot be discriminated by α spectrometry. High resolution ICP-MS can also measure uranium isotopic ratios in urine for total uranium concentrations lower than 20 ng/L. The interest of ICP-MS in radiotoxicology concerns essentially the urinary measurement of long radioactive period actinides, particularly for uranium isotope ratio determination and 239 and 240 plutonium isotopes discrimination. Radiometric methods remain the most efficient for the majority of other radionuclides.

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

NASA Technical Reports Server (NTRS)

Merritt, D. A.; Brand, W. A.; Hayes, J. M.

1994-01-01

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

Development and validation of a liquid chromatography-isotope dilution tandem mass spectrometry for determination of olanzapine in human plasma and its application to bioavailability study.

PubMed

Zhang, Meng-Qi; Jia, Jing-Ying; Lu, Chuan; Liu, Gang-Yi; Yu, Cheng-Yin; Gui, Yu-Zhou; Liu, Yun; Liu, Yan-Mei; Wang, Wei; Li, Shui-Jun; Yu, Chen

2010-06-01

A simple, reliable and sensitive liquid chromatography-isotope dilution mass spectrometry (LC-ID/MS) was developed and validated for quantification of olanzapine in human plasma. Plasma samples (50 microL) were extracted with tert-butyl methyl ether and isotope-labeled internal standard (olanzapine-D3) was used. The chromatographic separation was performed on XBridge Shield RP 18 (100 mm x 2.1 mm, 3.5 microm, Waters). An isocratic program was used at a flow rate of 0.4 m x min(-1) with mobile phase consisting of acetonitrile and ammonium buffer (pH 8). The protonated ions of analytes were detected in positive ionization by multiple reactions monitoring (MRM) mode. The plasma method, with a lower limit of quantification (LLOQ) of 0.1 ng x mL(-1), demonstrated good linearity over a range of 0.1 - 30 ng x mL(-1) of olanzapine. Specificity, linearity, accuracy, precision, recovery, matrix effect and stability were evaluated during method validation. The validated method was successfully applied to analyzing human plasma samples in bioavailability study.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats.

PubMed

Nakata, Hokuto; Nakayama, Shouta M M; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-10

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown ( Rattus norvegicus , n = 43) and black ( R. rattus , n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed.

Monitoring Lead (Pb) Pollution and Identifying Pb Pollution Sources in Japan Using Stable Pb Isotope Analysis with Kidneys of Wild Rats

PubMed Central

Nakata, Hokuto; Nakayama, Shouta M. M.; Oroszlany, Balazs; Ikenaka, Yoshinori; Mizukawa, Hazuki; Tanaka, Kazuyuki; Harunari, Tsunehito; Tanikawa, Tsutomu; Darwish, Wageh Sobhy; Yohannes, Yared B.; Saengtienchai, Aksorn; Ishizuka, Mayumi

2017-01-01

Although Japan has been considered to have little lead (Pb) pollution in modern times, the actual pollution situation is unclear. The present study aims to investigate the extent of Pb pollution and to identify the pollution sources in Japan using stable Pb isotope analysis with kidneys of wild rats. Wild brown (Rattus norvegicus, n = 43) and black (R. rattus, n = 98) rats were trapped from various sites in Japan. Mean Pb concentrations in the kidneys of rats from Okinawa (15.58 mg/kg, dry weight), Aichi (10.83), Niigata (10.62), Fukuoka (8.09), Ibaraki (5.06), Kyoto (4.58), Osaka (4.57), Kanagawa (3.42), and Tokyo (3.40) were above the threshold (2.50) for histological kidney changes. Similarly, compared with the previous report, it was regarded that even structural and functional kidney damage as well as neurotoxicity have spread among rats in Japan. Additionally, the possibility of human exposure to a high level of Pb was assumed. In regard to stable Pb isotope analysis, distinctive values of stable Pb isotope ratios (Pb-IRs) were detected in some kidney samples with Pb levels above 5.0 mg/kg. This result indicated that composite factors are involved in Pb pollution. However, the identification of a concrete pollution source has not been accomplished due to limited differences among previously reported values of Pb isotope composition in circulating Pb products. Namely, the current study established the limit of Pb isotope analysis for source identification. Further detailed research about monitoring Pb pollution in Japan and the demonstration of a novel method to identify Pb sources are needed. PMID:28075384

A novel reductive amination method with isotopic formaldehydes for the preparation of internal standard and standards for determining organosulfur compounds in garlic.

PubMed

Tsai, De-Cheng; Liu, Meng-Chieh; Lin, Yi-Reng; Huang, Mei-Fang; Liang, Shih-Shin

2016-04-15

Garlic (Allium sativum) is a long-cultivated plant that is widely utilized in cooking and has been employed as a medicine for over 4000 years. In this study, we fabricated standards and internal standards (ISs) for absolute quantification via reductive amination with isotopic formaldehydes. Garlic has four abundant organosulfur compounds (OSCs): S-allylcysteine, S-allylcysteinine sulfoxide, S-methylcysteine, and S-ethylcysteine are abundant in garlic. OSCs with primary amine groups were reacted with isotopic formaldehydes to synthesize ISs and standards. Cooked and uncooked garlic samples were compared, and we utilized tandem mass spectrometry equipped with a selective reaction monitoring technique to absolutely quantify the four organosulfur compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method for radioactivity monitoring

DOEpatents

Umbarger, C. John; Cowder, Leo R.

1976-10-26

The disclosure relates to a method for analyzing uranium and/or thorium contents of liquid effluents preferably utilizing a sample containing counting chamber. Basically, 185.7-keV gamma rays following .sup.235 U alpha decay to .sup.231 Th which indicate .sup.235 U content and a 63-keV gamma ray doublet found in the nucleus of .sup.234 Pa, a granddaughter of .sup.238 U, are monitored and the ratio thereof taken to derive uranium content and isotopic enrichment .sup.235 U/.sup.235 U + .sup.238 U) in the liquid effluent. Thorium content is determined by monitoring the intensity of 238-keV gamma rays from the nucleus of .sup.212 Bi in the decay chain of .sup.232 Th.

Recommendations for the generation, quantification, storage and handling of peptides used for mass spectrometry-based assays

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

Hoofnagle, Andrew N.; Whiteaker, Jeffrey R.; Carr, Steven A.

2015-12-30

The Clinical Proteomic Tumor Analysis Consortium (1) (CPTAC) of the National Cancer Institute (NCI) is a comprehensive and coordinated effort to accelerate the understanding of the molecular basis of cancer through the application of robust technologies and workflows for the quantitative measurements of proteins. The Assay Development Working Group of the CPTAC Program aims to foster broad uptake of targeted mass spectrometry-based assays employing isotopically labeled peptides for confident assignment and quantification, including multiple reaction monitoring (MRM; also referred to as Selected Reaction Monitoring), parallel reaction monitoring (PRM), and other targeted methods.

Multiplexed MRM-Based Protein Quantitation Using Two Different Stable Isotope-Labeled Peptide Isotopologues for Calibration.

PubMed

LeBlanc, André; Michaud, Sarah A; Percy, Andrew J; Hardie, Darryl B; Yang, Juncong; Sinclair, Nicholas J; Proudfoot, Jillaine I; Pistawka, Adam; Smith, Derek S; Borchers, Christoph H

2017-07-07

When quantifying endogenous plasma proteins for fundamental and biomedical research - as well as for clinical applications - precise, reproducible, and robust assays are required. Targeted detection of peptides in a bottom-up strategy is the most common and precise mass spectrometry-based quantitation approach when combined with the use of stable isotope-labeled peptides. However, when measuring protein in plasma, the unknown endogenous levels prevent the implementation of the best calibration strategies, since no blank matrix is available. Consequently, several alternative calibration strategies are employed by different laboratories. In this study, these methods were compared to a new approach using two different stable isotope-labeled standard (SIS) peptide isotopologues for each endogenous peptide to be quantified, enabling an external calibration curve as well as the quality control samples to be prepared in pooled human plasma without interference from endogenous peptides. This strategy improves the analytical performance of the assay and enables the accuracy of the assay to be monitored, which can also facilitate method development and validation.

Laser-based measurements of δ13 C and δ2 H methane isotope signatures: precisions competitive with mass spectrometry methods

NASA Astrophysics Data System (ADS)

Yacovitch, Tara; Shorter, Joanne; Nelson, David; Herndon, Scott; Agnese, Mike; McManus, Barry; Zahniser, Mark

2017-04-01

In order to understand how and why methane (CH4 ) concentrations change over time, it is necessary to understand their sources and sinks. Stable isotope measurements of 13 CH4 :12 CH4 and CH3 D:12 CH4 ratios constrain the inventory of these sinks and sources. Current measurements often depend on Isotope Ratio Mass Spectrometry (IRMS), which requires extensive sample preparation including cryogenic separation of methane from air and subsequent conversion to either CO2 or H2 . Here, we detail improvements to a direct-absorption laser spectrometer that enable fast and precise measurements of methane isotope ratios (δ13 C and δ2 H ) of ambient air samples, without such sample preparation. The measurement system consists of a laser-based direct absorption spectrometer configured with a sample manifold for measurement of discrete samples (as opposed to flow-through measurements). Samples are trapped in the instrument using a rapid sample switching technique that compares each flask sample against a monitor tank sample. This approach reduces instrument drift and results in excellent precision. Precisions of 0.054 o/oo for δ13 C and 1.4 o/oo for δ2 H have been achieved (Allan-Werle deviations). These results are obtained in 20 minutes using 4 replicate comparisons to a monitor tank.

Understanding the role of fog in forest hydrology: Stable isotopes as tools for determining input and partitioning of cloud water in montane forests

USGS Publications Warehouse

Scholl, M.; Eugster, W.; Burkard, R.

2011-01-01

Understanding the hydrology of tropical montane cloud forests (TMCF) has become essential as deforestation of mountain areas proceeds at an increased rate worldwide. Passive and active cloud-water collectors, throughfall and stemflow collectors, visibility or droplet size measurements, and micrometeorological sensors are typically used to measure the fog water inputs to ecosystems. In addition, stable isotopes may be used as a natural tracer for fog and rain. Previous studies have shown that the isotopic signature of fog tends to be more enriched in the heavier isotopes 2H and 18O than that of rain, due to differences in condensation temperature and history. Differences between fog and rain isotopes are largest when rain is from synoptic-scale storms, and fog or orographic cloud water is generated locally. Smaller isotopic differences have been observed between rain and fog on mountains with orographic clouds, but only a few studies have been conducted. Quantifying fog deposition using isotope methods is more difficult in forests receiving mixed precipitation, because of limitations in the ability of sampling equipment to separate fog from rain, and because fog and rain may, under some conditions, have similar isotopic composition. This article describes the various types of fog most relevant to montane cloud forests and the importance of fog water deposition in the hydrologic budget. A brief overview of isotope hydrology provides the background needed to understand isotope applications in cloud forests. A summary of previous work explains isotopic differences between rain and fog in different environments, and how monitoring the isotopic signature of surface water, soil water and tree xylem water can yield estimates of the contribution of fog water to streamflow, groundwater recharge and transpiration. Next, instrumentation to measure fog and rain, and methods to determine isotopic concentrations in plant and soil water are discussed. The article concludes with the identification of some of the more pressing research questions in this field and offers various suggestions for future research. ?? 2010 This article is a US Government work and is in the public domain in the USA.

A new, simple and precise method for measuring cyclotron proton beam energies using the activity vs. depth profile of zinc-65 in a thick target of stacked copper foils.

PubMed

Asad, A H; Chan, S; Cryer, D; Burrage, J W; Siddiqui, S A; Price, R I

2015-11-01

The proton beam energy of an isochronous 18MeV cyclotron was determined using a novel version of the stacked copper-foils technique. This simple method used stacked foils of natural copper forming 'thick' targets to produce Zn radioisotopes by the well-documented (p,x) monitor-reactions. Primary beam energy was calculated using the (65)Zn activity vs. depth profile in the target, with the results obtained using (62)Zn and (63)Zn (as comparators) in close agreement. Results from separate measurements using foil thicknesses of 100, 75, 50 or 25µm to form the stacks also concurred closely. Energy was determined by iterative least-squares comparison of the normalized measured activity profile in a target-stack with the equivalent calculated normalized profile, using 'energy' as the regression variable. The technique exploits the uniqueness of the shape of the activity vs. depth profile of the monitor isotope in the target stack for a specified incident energy. The energy using (65)Zn activity profiles and 50-μm foils alone was 18.03±0.02 [SD] MeV (95%CI=17.98-18.08), and 18.06±0.12MeV (95%CI=18.02-18.10; NS) when combining results from all isotopes and foil thicknesses. When the beam energy was re-measured using (65)Zn and 50-μm foils only, following a major upgrade of the ion sources and nonmagnetic beam controls the results were 18.11±0.05MeV (95%CI=18.00-18.23; NS compared with 'before'). Since measurement of only one Zn monitor isotope is required to determine the normalized activity profile this indirect yet precise technique does not require a direct beam-current measurement or a gamma-spectroscopy efficiency calibrated with standard sources, though a characteristic photopeak must be identified. It has some advantages over published methods using the ratio of cross sections of monitor reactions, including the ability to determine energies across a broader range and without need for customized beam degraders. Copyright © 2015 Elsevier Ltd. All rights reserved.

Well-based stable carbon isotope leakage monitoring of an aquifer overlying the CO2 storage reservoir at the Ketzin pilot site, Germany

NASA Astrophysics Data System (ADS)

Nowak, Martin; Myrttinen, Anssi; Zimmer, Martin; van Geldern, Robert; Barth, Johannes A. C.

2014-05-01

At the pilot site for CO2 storage in Ketzin, a new well-based leakage-monitoring concept was established, comprising geochemical and hydraulic observations of the aquifer directly above the CO2 reservoir (Wiese et al., 2013, Nowak et al. 2013). Its purpose was to allow early detection of un-trapped CO2. Within this monitoring concept, we established a stable carbon isotope monitoring of dissolved inorganic carbon (DIC). If baseline isotope values of aquifer DIC (δ13CDIC) and reservoir CO2 (δ13CCO2) are known and distinct from each other, the δ13CDIC has the potential to serve as an an early indicator for an impact of leaked CO2 on the aquifer brine. The observation well of the overlying aquifer was equipped with an U-tube sampling system that allowed sampling of unaltered brine. The high alkaline drilling mud that was used during well drilling masked δ13CDIC values at the beginning of the monitoring campaign. However, subsequent monitoring allowed observing on-going re-equilibration of the brine, indicated by changing δ13CDIC and other geochemical values, until values ranging around -23 ‰ were reached. The latter were close to baseline values before drilling. Baselineδ13CDIC and δ13CCO2 values were used to derive a geochemical and isotope model that predicts evolution of δ13CDIC, if CO2 from the reservoir would leak into the aquifer. The model shows that equilibrium isotope fractionation would have to be considered if CO2 dissolves in the brine. The model suggests that stable carbon isotope monitoring is a suitable tool to assess the impact of injected CO2 in overlying groundwater aquifers. However, more data are required to close gaps of knowledge about fractionation behaviour within the CO2(g) - DIC system under elevated pressures and temperatures. Nowak, M., Myrttinen, A., Zimmer, M., Wiese, B., van Geldern, R., Barth, J.A.C., 2013. Well-based, Geochemical Leakage Monitoring of an Aquifer Immediately Above a CO2 Storage Reservoir by Stable Carbon Isotopes at the Ketzin Pilot Site, Germany. Energy Procedia 40, 346-354. Wiese, B., Zimmer, M., Nowak, M., Pellizzari, L., Pilz, P., 2013. Well-based hydraulic and geochemical monitoring of the above zone of the CO2 reservoir at Ketzin, Germany. Environmental Earth Sciences, 1-18.

In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems [Urban ecohydrologic dynamics revealed by in situ monitoring of H and O stable isotopes in soil water

DOE PAGES

Oerter, Erik J.; Bowen, Gabriel

2017-04-12

The water cycle in urban and hydrologically managed settings is subject to perturbations that are dynamic on small spatial and temporal scales; the effects of which may be especially profound in soils. We deploy a membrane inlet-based laser spectroscopy system in conjunction with soil moisture and temperature sensors to monitor soil water dynamics and H and O stable isotope ratios (δ 2H and δ 18O values) in a seasonally irrigated urban-landscaped garden soil over the course of 9 months between the cessation of irrigation in the autumn and the onset of irrigation through the summer. Here, we find that soilmore » water δ 2H and δ 18O values predominately reflect seasonal precipitation and irrigation inputs. A comparison of total soil water by cryogenic extraction and mobile soil water measured by in situ water vapor probes reveals that initial infiltration events after long periods of soil drying (the autumn season in this case) emplace water into the soil matrix that is not easily replaced by, or mixed with, successive pulses of infiltrating soil water. Tree stem xylem water H and O stable isotope composition did not match that of available water sources. Our findings suggest that partitioning of soil water into mobile and immobile “pools” and resulting ecohydrologic separation may occur in engineered and hydrologically managed soils and not be limited to natural settings. Furthermore, the laser spectroscopy method detailed here has potential to yield insights in a variety of critical zone and vadose zone studies, potential that is heightened by the simplicity and portability of the system.« less

In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems [Urban ecohydrologic dynamics revealed by in situ monitoring of H and O stable isotopes in soil water

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

Oerter, Erik J.; Bowen, Gabriel

The water cycle in urban and hydrologically managed settings is subject to perturbations that are dynamic on small spatial and temporal scales; the effects of which may be especially profound in soils. We deploy a membrane inlet-based laser spectroscopy system in conjunction with soil moisture and temperature sensors to monitor soil water dynamics and H and O stable isotope ratios (δ 2H and δ 18O values) in a seasonally irrigated urban-landscaped garden soil over the course of 9 months between the cessation of irrigation in the autumn and the onset of irrigation through the summer. Here, we find that soilmore » water δ 2H and δ 18O values predominately reflect seasonal precipitation and irrigation inputs. A comparison of total soil water by cryogenic extraction and mobile soil water measured by in situ water vapor probes reveals that initial infiltration events after long periods of soil drying (the autumn season in this case) emplace water into the soil matrix that is not easily replaced by, or mixed with, successive pulses of infiltrating soil water. Tree stem xylem water H and O stable isotope composition did not match that of available water sources. Our findings suggest that partitioning of soil water into mobile and immobile “pools” and resulting ecohydrologic separation may occur in engineered and hydrologically managed soils and not be limited to natural settings. Furthermore, the laser spectroscopy method detailed here has potential to yield insights in a variety of critical zone and vadose zone studies, potential that is heightened by the simplicity and portability of the system.« less

Rapid quantification of free cholesterol in tears using direct insertion/electron ionization-mass spectrometry.

PubMed

Wei, Xiaojia Eric; Korth, John; Brown, Simon H J; Mitchell, Todd W; Truscott, Roger J W; Blanksby, Stephen J; Willcox, Mark D P; Zhao, Zhenjun

2013-12-09

To establish a simple and rapid analytical method, based on direct insertion/electron ionization-mass spectrometry (DI/EI-MS), for measuring free cholesterol in tears from humans and rabbits. A stable-isotope dilution protocol employing DI/EI-MS in selected ion monitoring mode was developed and validated. It was used to quantify the free cholesterol content in human and rabbit tear extracts. Tears were collected from adult humans (n = 15) and rabbits (n = 10) and lipids extracted. Screening, full-scan (m/z 40-600) DI/EI-MS analysis of crude tear extracts showed that diagnostic ions located in the mass range m/z 350 to 400 were those derived from free cholesterol, with no contribution from cholesterol esters. DI/EI-MS data acquired using selected ion monitoring (SIM) were analyzed for the abundance ratios of diagnostic ions with their stable isotope-labeled analogues arising from the D6-cholesterol internal standard. Standard curves of good linearity were produced and an on-probe limit of detection of 3 ng (at 3:1 signal to noise) and limit of quantification of 8 ng (at 10:1 signal to noise). The concentration of free cholesterol in human tears was 15 ± 6 μg/g, which was higher than in rabbit tears (10 ± 5 μg/g). A stable-isotope dilution DI/EI-SIM method for free cholesterol quantification without prior chromatographic separation was established. Using this method demonstrated that humans have higher free cholesterol levels in their tears than rabbits. This is in agreement with previous reports. This paper provides a rapid and reliable method to measure free cholesterol in small-volume clinical samples.

A radon-thoron isotope pair as a reliable earthquake precursor

PubMed Central

Hwa Oh, Yong; Kim, Guebuem

2015-01-01

Abnormal increases in radon (222Rn, half-life = 3.82 days) activity have occasionally been observed in underground environments before major earthquakes. However, 222Rn alone could not be used to forecast earthquakes since it can also be increased due to diffusive inputs over its lifetime. Here, we show that a very short-lived isotope, thoron (220Rn, half-life = 55.6 s; mean life = 80 s), in a cave can record earthquake signals without interference from other environmental effects. We monitored 220Rn together with 222Rn in air of a limestone-cave in Korea for one year. Unusually large 220Rn peaks were observed only in February 2011, preceding the 2011 M9.0 Tohoku-Oki Earthquake, Japan, while large 222Rn peaks were observed in both February 2011 and the summer. Based on our analyses, we suggest that the anomalous peaks of 222Rn and 220Rn activities observed in February were precursory signals related to the Tohoku-Oki Earthquake. Thus, the 220Rn-222Rn combined isotope pair method can present new opportunities for earthquake forecasting if the technique is extensively employed in earthquake monitoring networks around the world. PMID:26269105

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

PubMed

Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

2017-05-01

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

Abatement of Xenon and Iodine Emissions from Medical Isotope Production Facilities

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

Doll, Charles G.; Sorensen, Christina M.; Bowyer, Ted W.

2014-04-01

The capability of the International Monitoring System (IMS) to detect xenon from underground nuclear explosions is dependent on the radioactive xenon background. Adding to the background, medical isotope production (MIP) by fission releases several important xenon isotopes including xenon-133 and iodine-133 that decays to xenon-133. The amount of xenon released from these facilities may be equivalent to or exceed that released from an underground nuclear explosion. Thus the release of gaseous fission products within days of irradiation makes it difficult to distinguish MIP emissions from a nuclear explosion. In addition, recent shortages in molybdenum-99 have created interest and investment opportunitiesmore » to design and build new MIP facilities in the United States and throughout the world. Due to the potential increase in the number of MIP facilities, a discussion of abatement technologies provides insight into how the problem of emission control from MIP facilities can be tackled. A review of practices is provided to delineate methods useful for abatement of medical isotopes.« less

International challenge to predict the impact of radioxenon releases from medical isotope production on a comprehensive nuclear test ban treaty sampling station.

PubMed

Eslinger, Paul W; Bowyer, Ted W; Achim, Pascal; Chai, Tianfeng; Deconninck, Benoit; Freeman, Katie; Generoso, Sylvia; Hayes, Philip; Heidmann, Verena; Hoffman, Ian; Kijima, Yuichi; Krysta, Monika; Malo, Alain; Maurer, Christian; Ngan, Fantine; Robins, Peter; Ross, J Ole; Saunier, Olivier; Schlosser, Clemens; Schöppner, Michael; Schrom, Brian T; Seibert, Petra; Stein, Ariel F; Ungar, Kurt; Yi, Jing

2016-06-01

The International Monitoring System (IMS) is part of the verification regime for the Comprehensive Nuclear-Test-Ban-Treaty Organization (CTBTO). At entry-into-force, half of the 80 radionuclide stations will be able to measure concentrations of several radioactive xenon isotopes produced in nuclear explosions, and then the full network may be populated with xenon monitoring afterward. An understanding of natural and man-made radionuclide backgrounds can be used in accordance with the provisions of the treaty (such as event screening criteria in Annex 2 to the Protocol of the Treaty) for the effective implementation of the verification regime. Fission-based production of (99)Mo for medical purposes also generates nuisance radioxenon isotopes that are usually vented to the atmosphere. One of the ways to account for the effect emissions from medical isotope production has on radionuclide samples from the IMS is to use stack monitoring data, if they are available, and atmospheric transport modeling. Recently, individuals from seven nations participated in a challenge exercise that used atmospheric transport modeling to predict the time-history of (133)Xe concentration measurements at the IMS radionuclide station in Germany using stack monitoring data from a medical isotope production facility in Belgium. Participants received only stack monitoring data and used the atmospheric transport model and meteorological data of their choice. Some of the models predicted the highest measured concentrations quite well. A model comparison rank and ensemble analysis suggests that combining multiple models may provide more accurate predicted concentrations than any single model. None of the submissions based only on the stack monitoring data predicted the small measured concentrations very well. Modeling of sources by other nuclear facilities with smaller releases than medical isotope production facilities may be important in understanding how to discriminate those releases from releases from a nuclear explosion. Published by Elsevier Ltd.

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring.

PubMed

Gulson, Brian; Korsch, Michael; Winchester, Wayne; Devenish, Matthew; Hobbs, Thad; Main, Cleve; Smith, Gerard; Rosman, Kevin; Howearth, Lynette; Burn-Nunes, Laurie; Seow, Jimmy; Oxford, Cameron; Yun, Gracie; Gillam, Lindsay; Crisp, Michelle

2012-01-01

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments, air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

Determination of human-use pharmaceuticals in filtered water by direct aqueous injection: high-performance liquid chromatography/tandem mass spectrometry

USGS Publications Warehouse

Furlong, Edward T.; Noriega, Mary C.; Kanagy, Christopher J.; Kanagy, Leslie K.; Coffey, Laura J.; Burkhardt, Mark R.

2014-01-01

This report describes a method for the determination of 110 human-use pharmaceuticals using a 100-microliter aliquot of a filtered water sample directly injected into a high-performance liquid chromatograph coupled to a triple-quadrupole tandem mass spectrometer using an electrospray ionization source operated in the positive ion mode. The pharmaceuticals were separated by using a reversed-phase gradient of formic acid/ammonium formate-modified water and methanol. Multiple reaction monitoring of two fragmentations of the protonated molecular ion of each pharmaceutical to two unique product ions was used to identify each pharmaceutical qualitatively. The primary multiple reaction monitoring precursor-product ion transition was quantified for each pharmaceutical relative to the primary multiple reaction monitoring precursor-product transition of one of 19 isotope-dilution standard pharmaceuticals or the pesticide atrazine, using an exact stable isotope analogue where possible. Each isotope-dilution standard was selected, when possible, for its chemical similarity to the unlabeled pharmaceutical of interest, and added to the sample after filtration but prior to analysis. Method performance for each pharmaceutical was determined for reagent water, groundwater, treated drinking water, surface water, treated wastewater effluent, and wastewater influent sample matrixes that this method will likely be applied to. Each matrix was evaluated in order of increasing complexity to demonstrate (1) the sensitivity of the method in different water matrixes and (2) the effect of sample matrix, particularly matrix enhancement or suppression of the precursor ion signal, on the quantitative determination of pharmaceutical concentrations. Recovery of water samples spiked (fortified) with the suite of pharmaceuticals determined by this method typically was greater than 90 percent in reagent water, groundwater, drinking water, and surface water. Correction for ambient environmental concentrations of pharmaceuticals hampered the determination of absolute recoveries and method sensitivity of some compounds in some water types, particularly for wastewater effluent and influent samples. The method detection limit of each pharmaceutical was determined from analysis of pharmaceuticals fortified at multiple concentrations in reagent water. The calibration range for each compound typically spanned three orders of magnitude of concentration. Absolute sensitivity for some compounds, using isotope-dilution quantitation, ranged from 0.45 to 94.1 nanograms per liter, primarily as a result of the inherent ionization efficiency of each pharmaceutical in the electrospray ionization process. Holding-time studies indicate that acceptable recoveries of pharmaceuticals can be obtained from filtered water samples held at 4 °C for as long as 9 days after sample collection. Freezing samples to provide for storage for longer periods currently (2014) is under evaluation by the National Water Quality Laboratory.

Stable isotope labeling tandem mass spectrometry (SILT) to quantify protein production and clearance rates

PubMed Central

Bateman, Randall J.; Munsell, Ling Y.; Chen, Xianghong; Holtzman, David M.; Yarasheski, Kevin E.

2007-01-01

In all biological systems, protein amount is a function of the rate of production and clearance. The speed of a response to a disturbance in protein homeostasis is determined by turnover rate. Quantifying alterations in protein synthesis and clearance rates is vital to understanding disease pathogenesis (e.g., aging, inflammation). No methods exist for quantifying production and clearance rates of low abundance (femtomole) proteins in vivo. We describe a novel, mass spectrometry-based method for quantitating low abundance protein synthesis and clearance rates in vitro and in vivo in animals and humans. The utility of this method is demonstrated with amyloid-beta (Aß), an important low abundance protein involved in Alzheimer's disease pathogenesis. We used in vivo stable isotope labeling, immunoprecipitation of Aß from cerebrospinal fluid, and quantitative liquid chromatography electrospray-ionization tandem mass spectrometry (LC-ESI-tandem MS) to quantify human Aß protein production and clearance rates. The method is sensitive and specific for stable isotope labeled amino acid incorporation into CNS (± 1% accuracy). This in vivo method can be used to identify pathophysiologic changes in protein metabolism; and may serve as a biomarker for monitoring disease risk, progression, or response to novel therapeutic agents. The technique is adaptable to other macromolecules, such as carbohydrates or lipids. PMID:17383190

Analysis and application of heavy isotopes in the environment

NASA Astrophysics Data System (ADS)

Steier, Peter; Dellinger, Franz; Forstner, Oliver; Golser, Robin; Knie, Klaus; Kutschera, Walter; Priller, Alfred; Quinto, Francesca; Srncik, Michaela; Terrasi, Filippo; Vockenhuber, Christof; Wallner, Anton; Wallner, Gabriele; Wild, Eva Maria

2010-04-01

A growing number of AMS laboratories are pursuing applications of actinides. We discuss the basic requirements of the AMS technique of heavy (i.e., above ˜150 amu) isotopes, present the setup at the Vienna Environmental Research Accelerator (VERA) which is especially well suited for the isotope 236U, and give a comparison with other AMS facilities. Special emphasis will be put on elaborating the effective detection limits for environmental samples with respect to other mass spectrometric methods. At VERA, we have carried out measurements for radiation protection and environmental monitoring ( 236U, 239,240,241,242,244Pu), astrophysics ( 182Hf, 236U, 244Pu, 247Cm), nuclear physics, and a search for long-lived super-heavy elements ( Z > 100). We are pursuing the environmental distribution of 236U, as a basis for geological applications of natural 236U.

An LC-MRM method for measuring intestinal triglyceride assembly using an oral stable isotope-labeled fat challenge.

PubMed

Li, Xiaofang; Parks, Elizabeth J; McLaren, David G; Lambert, Jennifer E; Cardasis, Helene L; Chappell, Derek L; McAvoy, Thomas; Salituro, Gino; Alon, Achilles; Dennie, Justin; Chakravarthy, Manu; Shankar, Sudha S; Laterza, Omar F; Lassman, Michael E

2016-06-01

A traditional oral fatty acid challenge assesses absorption of triacylglycerol (TG) into the periphery through the intestines, but cannot distinguish the composition or source of fatty acid in the TG. Stable isotope-labeled tracers combined with LC-MRM can be used to identify and distinguish TG synthesized with dietary and stored fatty acids. Concentrations of three abundant TGs (52:2, 54:3 and 54:4) were monitored for incorporation of one or two (2)H11-oleate molecules per TG. This method was subjected to routine assay validation and meets typical requirements for an assay to be used to support clinical studies. Calculations for the fractional appearance rate of TG in plasma are presented along with the intracellular enterocyte precursor pool for 12 study participants.

Nursing benefits of using an automated injection system for ictal brain single photon emission computed tomography.

PubMed

Vonhofen, Geraldine; Evangelista, Tonya; Lordeon, Patricia

2012-04-01

The traditional method of administering radioactive isotopes to pediatric patients undergoing ictal brain single photon emission computed tomography testing has been by manual injections. This method presents certain challenges for nursing, including time requirements and safety risks. This quality improvement project discusses the implementation of an automated injection system for isotope administration and its impact on staffing, safety, and nursing satisfaction. It was conducted in an epilepsy monitoring unit at a large urban pediatric facility. Results of this project showed a decrease in the number of nurses exposed to radiation and improved nursing satisfaction with the use of the automated injection system. In addition, there was a decrease in the number of nursing hours required during ictal brain single photon emission computed tomography testing.

Stable isotopic labeling-based quantitative targeted glycomics (i-QTaG).

PubMed

Kim, Kyoung-Jin; Kim, Yoon-Woo; Kim, Yun-Gon; Park, Hae-Min; Jin, Jang Mi; Hwan Kim, Young; Yang, Yung-Hun; Kyu Lee, Jun; Chung, Junho; Lee, Sun-Gu; Saghatelian, Alan

2015-01-01

Mass spectrometry (MS) analysis combined with stable isotopic labeling is a promising method for the relative quantification of aberrant glycosylation in diseases and disorders. We developed a stable isotopic labeling-based quantitative targeted glycomics (i-QTaG) technique for the comparative and quantitative analysis of total N-glycans using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). We established the analytical procedure with the chemical derivatizations (i.e., sialic acid neutralization and stable isotopic labeling) of N-glycans using a model glycoprotein (bovine fetuin). Moreover, the i-QTaG using MALDI-TOF MS was evaluated with various molar ratios (1:1, 1:2, 1:5) of (13) C6 /(12) C6 -2-aminobenzoic acid-labeled glycans from normal human serum. Finally, this method was applied to direct comparison of the total N-glycan profiles between normal human sera (n = 8) and prostate cancer patient sera (n = 17). The intensities of the N-glycan peaks from i-QTaG method showed a good linearity (R(2) > 0.99) with the amount of the bovine fetuin glycoproteins. The ratios of relative intensity between the isotopically 2-AA labeled N-glycans were close to the theoretical molar ratios (1:1, 1:2, 1:5). We also demonstrated that the up-regulation of the Lewis antigen (~82%) in sera from prostate cancer patients. In this proof-of-concept study, we demonstrated that the i-QTaG method, which enables to achieve a reliable comparative quantitation of total N-glycans via MALDI-TOF MS analysis, has the potential to diagnose and monitor alterations in glycosylation associated with disease states or biotherapeutics. © 2015 American Institute of Chemical Engineers.

Analysis of acrylamide in coffee and cocoa by isotope dilution liquid chromatography-tandem mass spectrometry.

PubMed

Aguas, Patricia C; Fitzhenry, Matthew J; Giannikopoulos, Georgina; Varelis, Peter

2006-08-01

An accurate and precise method for the quantification of acrylamide using stable isotope dilution liquid chromatography-tandem mass spectrometry was developed and used to measure acrylamide in coffee and cocoa samples. The sample preparation involved extraction of the analyte and its internal standard, 13C3-acrylamide, into water and subsequent defatting of the aqueous extract with dichloromethane. An aliquot of the resulting aqueous extract was then azeotropically dried under reduced pressure and subsequently purified using an aminopropyl-bonded silica cartridge. The purified extracts were then chromatographed on a 5-microm 2.1 x 150 mm Hypercarb column, the effluent of which was monitored for the analyte and its internal standard using positive-ion APCI-selected reaction monitoring. The intra-laboratory reproducibility of the method, expressed as a relative coefficient of variation (%, n=5), was determined at four levels of concentration (12.3, 42.3, 139.3 and 464.8 microg kg(-1)) and was found to vary between 0.6-2.5%. The accuracy of the method was assessed using a reference sample of coffee. The average result obtained using our method differed from the assigned value of the reference material by less than 1%. An analysis of a cocoa sample revealed that the method is capable of precisely estimating acrylamide in challenging matrices down to a level of at least 12.3 microg kg(-1).

Investigating the Mechanism of Heteroaromatic Decarboxylation Using Solvent Kinetic Isotope Effects and Eyring Transition-State Theory

ERIC Educational Resources Information Center

Mundle, Scott O. C.; Opinska, Liliana Guevara; Kluger, Ronald; Dicks, Andrew P.

2011-01-01

An upper-level mechanistic organic experiment is outlined where undergraduates measure kinetic rate constants for decarboxylation of pyrrole-2-carboxylic acid by the initial-rates method. UV spectroscopy is used to monitor reactant disappearance in both hydrochloric acid and deuterium chloride at different temperatures. Individual data are pooled…

Development and evaluation of a suite of isotope reference gases for methane in air

NASA Astrophysics Data System (ADS)

Sperlich, Peter; Uitslag, Nelly A. M.; Richter, Jürgen M.; Rothe, Michael; Geilmann, Heike; van der Veen, Carina; Röckmann, Thomas; Blunier, Thomas; Brand, Willi A.

2016-08-01

Measurements from multiple laboratories have to be related to unifying and traceable reference material in order to be comparable. However, such fundamental reference materials are not available for isotope ratios in atmospheric methane, which led to misinterpretations of combined data sets in the past. We developed a method to produce a suite of synthetic CH4-in-air standard gases that can be used to unify methane isotope ratio measurements of laboratories in the atmospheric monitoring community. Therefore, we calibrated a suite of pure methane gases of different methanogenic origin against international referencing materials that define the VSMOW (Vienna Standard Mean Ocean Water) and VPDB (Vienna Pee Dee Belemnite) isotope scales. The isotope ratios of our pure methane gases range between -320 and +40 ‰ for δ2H-CH4 and between -70 and -40 ‰ for δ13C-CH4, enveloping the isotope ratios of tropospheric methane (about -85 and -47 ‰ for δ2H-CH4 and δ13C-CH4 respectively). Estimated uncertainties, including the full traceability chain, are < 1.5 ‰ and < 0.2 ‰ for δ2H and δ13C calibrations respectively. Aliquots of the calibrated pure methane gases have been diluted with methane-free air to atmospheric methane levels and filled into 5 L glass flasks. The synthetic CH4-in-air standards comprise atmospheric oxygen/nitrogen ratios as well as argon, krypton and nitrous oxide mole fractions to prevent gas-specific measurement artefacts. The resulting synthetic CH4-in-air standards are referred to as JRAS-M16 (Jena Reference Air Set - Methane 2016) and will be available to the atmospheric monitoring community. JRAS-M16 may be used as unifying isotope scale anchor for isotope ratio measurements in atmospheric methane, so that data sets can be merged into a consistent global data frame.

Carbon Stable Isotopes as Indicators of Coastal Eutrophication

EPA Science Inventory

Coastal ecologists and managers have frequently used nitrogen stable isotopes (δ15N) to trace and monitor anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of δ15N data can often be challenging, if not confounding, as the isotope values fractionate su...

Isotopic signature of atmospheric xenon released from light water reactors.

PubMed

Kalinowski, Martin B; Pistner, Christoph

2006-01-01

A global monitoring system for atmospheric xenon radioactivity is being established as part of the International Monitoring System to verify compliance with the Comprehensive Nuclear-Test-Ban Treaty (CTBT). The isotopic activity ratios of (135)Xe, (133m)Xe, (133)Xe and (131m)Xe are of interest for distinguishing nuclear explosion sources from civilian releases. Simulations of light water reactor (LWR) fuel burn-up through three operational reactor power cycles are conducted to explore the possible xenon isotopic signature of nuclear reactor releases under different operational conditions. It is studied how ratio changes are related to various parameters including the neutron flux, uranium enrichment and fuel burn-up. Further, the impact of diffusion and mixing on the isotopic activity ratio variability are explored. The simulations are validated with reported reactor emissions. In addition, activity ratios are calculated for xenon isotopes released from nuclear explosions and these are compared to the reactor ratios in order to determine whether the discrimination of explosion releases from reactor effluents is possible based on isotopic activity ratios.

Selected reaction monitoring (SRM) mass spectrometry without isotope labeling can be used for rapid protein quantification

PubMed Central

Zhi, Wenbo; Wang, Meiyao

2014-01-01

The validation of putative biomarker candidates has become the major bottle-neck in protein biomarker development. Conventional immunoaffinity methods are limited by the availability of antibodies and kits. Here we demonstrated the feasibility of using the selected reaction monitoring (SRM) without isotope labeling to achieve fast and reproducible quantification of serum proteins. The SRM/MRM assays for three standard serum proteins, including ceruloplasmin (CP), serum aymloid A (SAA) and sex hormone binding globulin (SHBG) have good linear ranges, generally 103 – 104. There are almost perfect correlations between SRM intensities and the loaded peptide amounts (R2 is usually ~0.99). Our data suggest that SRM/MRM is able to quantify proteins at 0.2 – 2 fmol level, which are comparable to the commercial ELISA/LUMINEX kits for these proteins. Excellent correlations between SRM/MRM and ELISA/LUMINEX assays were observed for SAA and SHBG (R2 = 0.928 and 0.851 respectively). The correlation between SRM/MRM and ELISA for CP is less desirable (R2 = 0.565). The reproducibility for SRM/MRM assays is generally very good but may depend on the proteins/peptides (R2 = 0.931 and 0.882 for SAA and SHBG, and 0.723 for CP). SRM/MRM assay without isotope labeling is a rapid and useful method for protein biomarker validation in a modest number of samples and is especially useful when other assays such as ELISA or Luminex beads are not available. PMID:21594933

Rapid and precise measurement of serum branched-chain and aromatic amino acids by isotope dilution liquid chromatography tandem mass spectrometry.

PubMed

Yang, Ruiyue; Dong, Jun; Guo, Hanbang; Li, Hongxia; Wang, Shu; Zhao, Haijian; Zhou, Weiyan; Yu, Songlin; Wang, Mo; Chen, Wenxiang

2013-01-01

Serum branched-chain and aromatic amino acids (BCAAs and AAAs) have emerged as predictors for the future development of diabetes and may aid in diabetes risk assessment. However, the current methods for the analysis of such amino acids in biological samples are time consuming. An isotope dilution liquid chromatography tandem mass spectrometry (ID-LC/MS/MS) method for serum BCAAs and AAAs was developed. The serum was mixed with isotope-labeled BCAA and AAA internal standards and the amino acids were extracted with acetonitrile, followed by analysis using LC/MS/MS. The LC separation was performed on a reversed-phase C18 column, and the MS/MS detection was performed via the positive electronic spray ionization in multiple reaction monitoring mode. Specific analysis of the amino acids was achieved within 2 min. Intra-run and total CVs for the amino acids were less than 2% and 4%, respectively, and the analytical recoveries ranged from 99.6 to 103.6%. A rapid and precise method for the measurement of serum BCAAs and AAAs was developed and may serve as a quick tool for screening serum BCAAs and AAAs in studies assessing diabetes risk.

Advantages of isotopic depletion of proteins for hydrogen/deuterium exchange experiments monitored by mass spectrometry.

PubMed

Bou-Assaf, George M; Chamoun, Jean E; Emmett, Mark R; Fajer, Piotr G; Marshall, Alan G

2010-04-15

Solution-phase hydrogen/deuterium exchange (HDX) monitored by mass spectrometry is an excellent tool to study protein-protein interactions and conformational changes in biological systems, especially when traditional methods such as X-ray crystallography or nuclear magnetic resonance are not feasible. Peak overlap among the dozens of proteolytic fragments (including those from autolysis of the protease) can be severe, due to high protein molecular weight(s) and the broad isotopic distributions due to multiple deuterations of many peptides. In addition, different subunits of a protein complex can yield isomeric proteolytic fragments. Here, we show that depletion of (13)C and/or (15)N for one or more protein subunits of a complex can greatly simplify the mass spectra, increase the signal-to-noise ratio of the depleted fragment ions, and remove ambiguity in assignment of the m/z values to the correct isomeric peptides. Specifically, it becomes possible to monitor the exchange progress for two isobaric fragments originating from two or more different subunits within the complex, without having to resort to tandem mass spectrometry techniques that can lead to deuterium scrambling in the gas phase. Finally, because the isotopic distribution for a small to medium-size peptide is essentially just the monoisotopic species ((12)C(c)(1)H(h)(14)N(n)(16)O(o)(32)S(s)), it is not necessary to deconvolve the natural abundance distribution for each partially deuterated peptide during HDX data reduction.

Overcoming interference with the detection of a stable isotopically labeled microtracer in the evaluation of beclabuvir absolute bioavailability using a concomitant microtracer approach.

PubMed

Jiang, Hao; Titsch, Craig; Zeng, Jianing; Jones, Barry; Joyce, Philip; Gandhi, Yash; Turley, Wesley; Burrell, Richard; Aubry, Anne F; Arnold, Mark E

2017-09-05

The oral absolute bioavailability of beclabuvir in healthy subjects was determined using a microdose (100μg) of the stable isotopically labeled tracer via intravenous (IV) infusion started after oral dosing of beclabuvir (150mg). To simultaneously analyze the concentrations of the IV microtracer ([ 13 C 6 ]beclabuvir) and beclabuvir in plasma samples, a liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) method was initially developed. Surprisingly beclabuvir significantly interfered with the IV microtracer detection when using the selected reaction monitoring (SRM) in the assay. An interfering component from the drug substance was observed using a high resolution mass spectrometer (HRMS). The mass-to-charge (m/z) of the interfering component was -32ppm different from the nominal value for the IV microtracer and thus could not be differentiated in the SRM assay by the unit mass resolution. To overcome this interference, we evaluated two approaches by either monitoring an alternative product ion using the SRM assay or isolating the interfering component using the parallel reaction monitoring (PRM) assay on the HRMS. This case study has demonstrated two practical approaches for overcoming interferences with the detection of stable isotopically labeled IV microtracers in the evaluation of absolute bioavailability, which provides users the flexibility in using either LC-MS/MS or HRMS to mitigate unpredicted interferences in the assay to support microtracer absolute bioavailability studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

PubMed

Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

2017-02-15

High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of 29 Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O 2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO + and SiO 2 + ion species was performed, and we found that SiO + ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO 3 ). For SiO 2 + , no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. 28 Si 16 O 18 O + , 30 Si 16 O 16 O + ). The developed method was validated by measuring a series of reference solutions with different 29 Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0.2%, <0.5% and <0.6%, respectively. These performances meet the requirements of the studies of nuclear glasses alteration and open up possibilities to use this method for precise determination of silicon content in natural samples by Isotope Dilution. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of Dilution, Filtration, and Microwave Digestion Sample Pretreatments in Elemental Profiling of Wine by ICP-MS.

PubMed

Godshaw, Joshua; Hopfer, Helene; Nelson, Jenny; Ebeler, Susan E

2017-09-25

Wine elemental composition varies by cultivar, geographic origin, viticultural and enological practices, and is often used for authenticity validation. Elemental analysis of wine by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is challenging due to the potential for non-spectral interferences and plasma instability arising from organic matrix components. Sample preparation mitigates these interferences, however, conflicting recommendations of best practices in ICP-MS analysis of wine have been reported. This study compared direct dilution, microwave-assisted acid digestion, and two filtration sample pretreatments, acidification prior to filtration and filtration followed by acidification, in elemental profiling of one white and three red table wines by ICP-MS. Of 43 monitored isotopes, 37 varied by sample preparation method, with significantly higher results of 17 isotopes in the microwave-digested samples. Both filtration treatments resulted in lower results for 11 isotopes compared to the other methods. Finally, isotope dilution determination of copper based on natural abundances and the 63 Cu: 65 Cu instrument response ratio agreed with external calibration and confirmed a significant sample preparation effect. Overall, microwave digestion did not compare favorably, and direct dilution was found to provide the best compromise between ease of use and result accuracy and precision, although all preparation strategies were able to differentiate the wines.

Predicting water quality changes from artificial recharge sources to nearby wellfields

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

Moran, J.E.

1998-01-23

Isotope tracer technologies have proven to be powerful tools for addressing questions related to surface water-ground water interactions. The Alameda County Water District artificially recharges tens of thousands of acre-ft of water annually, delivered from Alameda Creek in order to augment dwindling ground water supplies, and to maintain a barrier to seawater intrusion. The authors are using a suite of isotope tracers to track water movement, source characteristics and accompanying water quality changes from ACWD recharge facilities to nearby wells. The data gathered during the three year project will allow quantification of dilution by ambient basin ground water, subsurface travelmore » times, and several key water quality parameters, including degree of degradation of organic compounds, the fate of trace metals during recharge and subsurface transport, and sources and transport of major ions (salts). Reconnaissance work was carried out on naturally occurring isotopes in order to better understand the hydrogeology of the ground water basin. The basin is dissected by the Hayward Fault, and geologic conditions vary greatly on either side of the fault. Stable isotopes of oxygen, carbon, helium and other noble gases, along with radiocarbon and tritium were measured on water samples from production and monitoring wells. The goal of the reconnaissance work was to age date the water at various depths and distances from the recharge ponds, to examine the chemical evolution of the water with age, and to examine the water for source-related variations in isotope composition. Ground water ages were calculated by the tritium-helium method for three production wells in the Peralta-Tyson wellfield (in the Above Hayward Fault sub-basin), and for a monitoring well positioned between the recharge facilities and production wells, screened at three discreet intervals.« less

Comparing isotope signatures of prey fish: does gut removal affect δ13C or δ15N?

USGS Publications Warehouse

Chipps, Steven R.; Fincel, Mark J.; VanDeHey, Justin A.; Wuestewald, Andrew

2011-01-01

Stable isotope analysis is a quick and inexpensive method to monitor the effects of food web changes on aquatic communities. Traditionally, whole specimens have been used when determining isotope composition of prey fish or age-0 recreational fishes. However, gut contents of prey fish could potentially alter isotope composition of the specimen, especially when recent foraging has taken place or when the gut contains non-assimilated material that would normally pass through fishes undigested. To assess the impacts of gut content on prey fish isotope signatures, we examined the differences in isotopic variation of five prey fish species using whole fish, whole fish with the gut contents removed, and dorsal muscle only. We found significant differences in both δ15N and δ13C between the three tissue treatments. In most cases, muscle tissue was enriched compared to whole specimens or gut-removed specimens. Moreover, differences in mean δ15N within a species were up to 2‰ among treatments. This would result in a change of over half a trophic position (TP) based on a 3.4‰ increase per trophic level. However, there were no apparent relationships between tissue isotope values in fish with increased gut fullness (more prey tissue present). We suggest that muscle tissue should be used as the standard tissue for determining isotope composition of prey fish or age-0 recreational fishes, especially when determining enrichment for mixing models, calculating TP, or constructing aquatic food webs.

Stable isotope labeling by essential nutrients in cell culture for preparation of labeled coenzyme A and its thioesters.

PubMed

Basu, Sankha S; Mesaros, Clementina; Gelhaus, Stacy L; Blair, Ian A

2011-02-15

Stable isotope dilution mass spectrometry (MS) represents the gold standard for quantification of endogenously formed cellular metabolites. Although coenzyme A (CoA) and acyl-CoA thioester derivatives are central players in numerous metabolic pathways, the lack of a commercially available isotopically labeled CoA limits the development of rigorous MS-based methods. In this study, we adapted stable isotope labeling by amino acids in cell culture (SILAC) methodology to biosynthetically generate stable isotope labeled CoA and thioester analogues for use as internal standards in liquid chromatography/multiple reaction monitoring mass spectrometry (LC/MRM-MS) assays. This was accomplished by incubating murine hepatocytes (Hepa 1c1c7) in media in which pantothenate (a precursor of CoA) was replaced with [(13)C(3)(15)N(1)]-pantothenate. Efficient incorporation into various CoA species was optimized to >99% [(13)C(3)(15)N(1)]-pantothenate after three passages of the murine cells in culture. Charcoal-dextran-stripped fetal bovine serum (FBS) was found to be more efficient for serum supplementation than dialyzed or undialyzed FBS, due to lower contaminating unlabeled pantothenate content. Stable isotope labeled CoA species were extracted and utilized as internal standards for CoA thioester analysis in cell culture models. This methodology of stable isotope labeling by essential nutrients in cell culture (SILEC) can serve as a paradigm for using vitamins and other essential nutrients to generate stable isotope standards that cannot be readily synthesized.

Reductive amination derivatization for the quantification of garlic components by isotope dilution analysis.

PubMed

Lin, Yi-Reng; Huang, Mei-Fang; Wu, You-Ying; Liu, Meng-Chieh; Huang, Jing-Heng; Chen, Ziyu; Shiue, Yow-Ling; Wu, Chia-En; Liang, Shih-Shin

2017-09-01

In this work, we synthesized internal standards for four garlic organosulfur compounds (OSCs) by reductive amination with 13 C, D 2 -formaldehyde, and developed an isotope dilution analysis method to quantitate these organosulfur components in garlic samples. Internal standards were synthesized for internal absolute quantification of S-allylcysteine (SAC), S-allylcysteine sulfoxide (alliin), S-methylcysteine (SMC), and S-ethylcysteine (SEC). We used a multiple reaction monitoring (MRM) to detect 13 C, D 2 -formaldehyde-modified OSCs by ultrahigh-performance liquid phase chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and obtained MS spectra showing different ratios of 13 C, D 2 -formaldehyde-modified and H 2 -formaldehyde-modified compounds. The resulting labeled and unlabeled OSCs were exhibited correlation coefficient (R 2 ) ranged from 0.9989 to 0.9994, respectively. The average recoveries for four OSCs at three concentration levels ranged from 89% to 105%. By 13 C, D 2 -formaldehyde and sodium cyanoborohydride, the reductive amination-based method can be utilized to generate novel internal standard for isotope dilution and to extend the quantitative application. Copyright © 2017 Elsevier Ltd. All rights reserved.

Production of beta-gamma coincidence spectra of individual radioxenon isotopes for improved analysis of nuclear explosion monitoring data

NASA Astrophysics Data System (ADS)

Haas, Derek Anderson

Radioactive xenon gas is a fission product released in the detonation of nuclear devices that can be detected in atmospheric samples far from the detonation site. In order to improve the capabilities of radioxenon detection systems, this work produces beta-gamma coincidence spectra of individual isotopes of radioxenon. Previous methods of radioxenon production consisted of the removal of mixed isotope samples of radioxenon gas released from fission of contained fissile materials such as 235U. In order to produce individual samples of the gas, isotopically enriched stable xenon gas is irradiated with neutrons. The detection of the individual isotopes is also modeled using Monte Carlo simulations to produce spectra. The experiment shows that samples of 131mXe, 133 Xe, and 135Xe with a purity greater than 99% can be produced, and that a sample of 133mXe can be produced with a relatively low amount of 133Xe background. These spectra are compared to models and used as essential library data for the Spectral Deconvolution Analysis Tool (SDAT) to analyze atmospheric samples of radioxenon for evidence of nuclear events.

Uranium isotopes (U-234/U-238) in rivers of the Yukon Basin (Alaska and Canada) as an aid in identifying water sources, with implications for monitoring hydrologic change in arctic regions

USGS Publications Warehouse

Kraemer, Thomas F.; Brabets, Timothy P.

2012-01-01

The ability to detect hydrologic variation in large arctic river systems is of major importance in understanding and predicting effects of climate change in high-latitude environments. Monitoring uranium isotopes (234U and 238U) in river water of the Yukon River Basin of Alaska and northwestern Canada (2001–2005) has enhanced the ability to identify water sources to rivers, as well as detect flow changes that have occurred over the 5-year study. Uranium isotopic data for the Yukon River and major tributaries (the Porcupine and Tanana rivers) identify several sources that contribute to river flow, including: deep groundwater, seasonally frozen river-valley alluvium groundwater, and high-elevation glacial melt water. The main-stem Yukon River exhibits patterns of uranium isotopic variation at several locations that reflect input from ice melt and shallow groundwater in the spring, as well as a multi-year pattern of increased variability in timing and relative amount of water supplied from higher elevations within the basin. Results of this study demonstrate both the utility of uranium isotopes in revealing sources of water in large river systems and of incorporating uranium isotope analysis in long-term monitoring of arctic river systems that attempt to assess the effects of climate change.

Using Natural Stable Calcium Isotopes to Rapidly Assess Changes in Bone Mineral Balance Using a Bed Rest Model to Induce Bone Loss

NASA Technical Reports Server (NTRS)

Morgan, J. L. L.; Skulan, J. L.; Gordon, G. E.; Smith, Scott M.; Romaniello, S. J.; Anbar, A. D.

2012-01-01

Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 0.07% ( SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism.

Modeling and Measurement of Correlation between Blood and Interstitial Glucose Changes

PubMed Central

Shi, Ting; Li, Dachao; Li, Guoqing; Zhang, Yiming; Xu, Kexin; Lu, Luo

2016-01-01

One of the most effective methods for continuous blood glucose monitoring is to continuously measure glucose in the interstitial fluid (ISF). However, multiple physiological factors can modulate glucose concentrations and affect the lag phase between blood and ISF glucose changes. This study aims to develop a compensatory tool for measuring the delay in ISF glucose variations in reference to blood glucose changes. A theoretical model was developed based on biophysics and physiology of glucose transport in the microcirculation system. Blood and interstitial fluid glucose changes were measured in mice and rats by fluorescent and isotope methods, respectively. Computer simulation mimicked curves were fitted with data resulting from fluorescent measurements of mice and isotope measurements of rats, indicating that there were lag times for ISF glucose changes. It also showed that there was a required diffusion distance for glucose to travel from center of capillaries to interstitial space in both mouse and rat models. We conclude that it is feasible with the developed model to continuously monitor dynamic changes of blood glucose concentration through measuring glucose changes in ISF with high accuracy, which requires correct parameters for determining and compensating for the delay time of glucose changes in ISF. PMID:27239479

An assessment of the accuracy of stable Fe isotope ratio measurements on samples with organic and inorganic matrices by high-resolution multicollector ICP-MS

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2005-04-01

Multicollector ICP-MS-based stable isotope procedures provide the capability to determine small variations in metal isotope composition of materials, but they are prone to substantial bias introduced by inadequate sample preparation. Such a "cryptic" bias is not necessarily identifiable from the measured isotope ratios. The analytical protocol for Fe isotope analyses of organic and inorganic materials described here identifies and avoids such pitfalls. In medium-mass resolution mode of the ThermoFinnigan Neptune MC-ICP-MS, a 1-ppm Fe solution with an uptake rate of 50-70 [mu]L min-1 yielded 3 × 10-11 A on 56Fe for the ThermoFinnigan stable introduction system and 1.2-1.8 × 10-10 A for the ESI Apex-Q uptake system. Sensitivity was increased again 3-5-fold when using Finnigan X-cones instead of the standard H-cones. The combination of the ESI Apex-Q apparatus and X-cones allowed the determination of the isotope composition on as little as 50 ng of Fe. Fe isotope compositions were corrected for mass bias with both the standard-sample bracketing (SSB) method, and by using the 65Cu/63Cu ratio of added synthetic copper (Cu-doping) as internal monitor of mass discrimination. Both methods provide identical results on high-purity Fe solutions of either synthetic or natural samples. We prefer the SSB method because of its shorter analysis time and more straightforward correction of instrumental mass bias compared to Cu-doping. Strong error correlations of the data are observed in three isotope diagrams. Thus, we suggest that the quality assessment in such diagrams should be performed with error ellipses rather than error bars. Reproducibility of [delta]56Fe, [delta]57Fe and [delta]58Fe values of natural samples alone is not a sufficient criterion for accuracy. A set of tests is lined out that identify cryptic matrix effects and ensure a reproducible level of quality control. Using these criteria and the SSB correction method, we determined the external reproducibilities for [delta]56Fe, [delta]57Fe and [delta]58Fe at the 95% confidence interval from 318 measurements of 95 natural samples to be 0.049, 0.071 and 0.28[per mille sign], respectively.

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 evaporation, with unprecedentedly high temporal resolution. As the soil dried out, we could show for the first time the increasing influence of the depleted ambient water vapor on the enriched liquid water close to the soil surface. Finally, the obtained data was simulated using the fully coupled 1D isotope-enabled SVAT model SiSPAT-Isotope.

Isotopic Recorders of Pollution in Heterogeneous Urban Areas

NASA Astrophysics Data System (ADS)

Pataki, D. E.; Cobley, L.; Smith, R. M.; Ehleringer, J. R.; Chritz, K.

2017-12-01

A significant difficulty in quantifying urban pollution lies in the extreme spatial and temporal heterogeneity of cities. Dense sources of both point and non-point source pollution as well as the dynamic role of human activities, which vary over very short time scales and small spatial scales, complicate efforts to establish long-term urban monitoring networks that are relevant at neighborhood, municipal, and regional scales. Fortunately, the natural abundance of isotopes of carbon, nitrogen, and other elements provides a wealth of information about the sources and fate of urban atmospheric pollution. In particular, soils and plant material integrate pollution sources and cycling over space and time, and have the potential to provide long-term records of pollution dynamics that extend back before atmospheric monitoring data are available. Similarly, sampling organic material at high spatial resolution can provide "isoscapes" that shed light on the spatial heterogeneity of pollutants in different urban parcels and neighborhoods, along roads of varying traffic density, and across neighborhoods of varying affluence and sociodemographic composition. We have compiled numerous datasets of the isotopic composition of urban organic matter that illustrate the potential for isotopic monitoring of urban areas as a means of understanding hot spots and hot moments in urban atmospheric biogeochemistry. Findings to date already reveal the critical role of affluence, economic activity, demographic change, and land management practices in influencing urban pollution sources and sinks, and suggest an important role of stable isotope and radioisotope measurements in urban atmospheric and biogeochemical monitoring.

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.

Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

PubMed

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

2016-01-15

In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. Copyright © 2015 Elsevier B.V. All rights reserved.

Accurate Quantification of Cardiovascular Biomarkers in Serum Using Protein Standard Absolute Quantification (PSAQ™) and Selected Reaction Monitoring*

PubMed Central

Huillet, Céline; Adrait, Annie; Lebert, Dorothée; Picard, Guillaume; Trauchessec, Mathieu; Louwagie, Mathilde; Dupuis, Alain; Hittinger, Luc; Ghaleh, Bijan; Le Corvoisier, Philippe; Jaquinod, Michel; Garin, Jérôme; Bruley, Christophe; Brun, Virginie

2012-01-01

Development of new biomarkers needs to be significantly accelerated to improve diagnostic, prognostic, and toxicity monitoring as well as therapeutic follow-up. Biomarker evaluation is the main bottleneck in this development process. Selected Reaction Monitoring (SRM) combined with stable isotope dilution has emerged as a promising option to speed this step, particularly because of its multiplexing capacities. However, analytical variabilities because of upstream sample handling or incomplete trypsin digestion still need to be resolved. In 2007, we developed the PSAQ™ method (Protein Standard Absolute Quantification), which uses full-length isotope-labeled protein standards to quantify target proteins. In the present study we used clinically validated cardiovascular biomarkers (LDH-B, CKMB, myoglobin, and troponin I) to demonstrate that the combination of PSAQ and SRM (PSAQ-SRM) allows highly accurate biomarker quantification in serum samples. A multiplex PSAQ-SRM assay was used to quantify these biomarkers in clinical samples from myocardial infarction patients. Good correlation between PSAQ-SRM and ELISA assay results was found and demonstrated the consistency between these analytical approaches. Thus, PSAQ-SRM has the capacity to improve both accuracy and reproducibility in protein analysis. This will be a major contribution to efficient biomarker development strategies. PMID:22080464

Determination of Glyphosate, its Degradation Product Aminomethylphosphonic Acid, and Glufosinate, in Water by Isotope Dilution and Online Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry

USGS Publications Warehouse

Meyer, Michael T.; Loftin, Keith A.; Lee, Edward A.; Hinshaw, Gary H.; Dietze, Julie E.; Scribner, Elisabeth A.

2009-01-01

The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

Isotopic (d18O/d2H) integrity of water samples collected and stored by automatic samplers

USDA-ARS?s Scientific Manuscript database

Stable water isotopes are increasingly becoming part of routine monitoring programs that utilize automatic samplers. The objectives of this study were to quantify the uncertainty in isotope signatures due to the length of sample storage (1-24 d) inside autosamplers over a range of air temperatures (...

Watershed Scale Stable Isotope Distribution and Implications on Soil Organic Carbon Loss Monitoring under Hydrologic Uncertainty

NASA Astrophysics Data System (ADS)

Ahmed, I.; Karim, A.; Boutton, T. W.; Strom, K.; Fox, J.

2013-12-01

The thematic focus of this 3-year period multidisciplinary USDA-CBG collaborative applied research is integrated monitoring of soil organic carbon (SOC) loss from multi-use lands using state-of-the-art stable isotope science under uncertain hydrologic influences. In this study, SOC loss and water runoff are being monitored on a 150 square kilometer watershed in Houston, Texas, using natural rainfall events, and total organic carbon/nitrogen concentration (TOC/TN) and stable isotope ratio (δ13C, δ15N) measurements with different land-use types. The work presents the interdisciplinary research results to uncover statistically valid and scientifically sound ways to monitor SOC loss by (i) application of Bayesian Markov Chain Monte Carlo statistical models to assess the relationship between rainfall-runoff and SOC release during soil erosion in space and time, (ii) capturing the episodic nature of rainfall events and its role in the spatial distribution of SOC loss from water erosion, (iii) stable isotope composition guided fingerprinting (source and quantity) of SOC by considering various types of erosion processes common in a heterogeneous watershed, to be able to tell what percentage of SOC is lost from various land-use types (Fox and Papanicolaou, 2008), (iv) creating an integrated watershed scale statistical soil loss monitoring model driven by spatial and temporal correlation of flow and stable isotope composition (Ahmed et. al., 2013a,b), and (v) creation of an integrated decision support system (DSS) for sustainable management of SOC under hydrologic uncertainty to assist the end users. References: Ahmed, I., Karim, A., Boutton, T.W., and Strom, K.B. (2013a). 'Monitoring Soil Organic Carbon Loss from Erosion Using Stable Isotopes.' Proc., Soil Carbon Sequestration, International Conference, May 26-29, Reykjavik, Iceland. Ahmed, I, Bouttom, T.W., Strom, K. B., Karim, A., and Irvin-Smith, N. (2013b). 'Soil carbon distribution and loss monitoring in the urbanized Buffalo Bayou watershed, Houston, Texas.' Proc., 4th Annual All Investigators Meeting of the North American Carbon Program, February 4-7, Albuquerque, NM. Fox, J.F. and Papanicolaou, A.N. (2008). An un-mixing model to study watershed erosion processes. Advances in Water Resources, 31, 96-108. ______________________________ * Corresponding author';s e-mail: ifahmed@pvamu.edu

Soil Biogeochemical Properties and Erosion Source Prediction Model Summary for the Buffalo Bayou Watershed, Houston, Texas

NASA Astrophysics Data System (ADS)

Ahmed, I.

2015-12-01

We draw conclusions on the research output and findings from a 4-year multidisciplinary USDA-CBG collaborative program in sustainable integrated monitoring of soil organic carbon (SOC) loss prediction via erosion. The underlying method uses the state-of-the-art stable isotope science of sediment tracing under uncertain hydrologic influences. The research finds are rooted in the (i) application of Bayesian Markov Chain Monte Carlo statistical models to assess the relationship between rainfall-runoff and soil erosion in space and time, (ii) capture of the episodic nature of rainfall events and its role in the spatial distribution of SOC loss from water erosion, (iii) stable isotope composition guided fingerprinting (source and quantity) of eroded soil, and (iv) the creation of an integrated watershed scale statistical soil loss monitoring model driven by spatial and temporal correlation of flow and stable isotope composition. The research theme was successfully applied on the urbanized Buffalo Bayou Watershed in Houston, Texas. The application brought to light novel future research conceptual outlines which will also be discussed in this deliverable to the AGU meeting. These include but not limited to: regional rainfall cluster research, physics of muddy river-bank soil and suspended sediment interaction, and friction & mobility that together make up the plasticity of soil aggregates that control erosion processes and landscape changes in a riparian corridor. References: Ahmed, I., Karim, A., Boutton, T.W., and Strom, K.B. (2013a). "Monitoring Soil Organic Carbon Loss from Erosion Using Stable Isotopes." Proc., Soil Carbon Sequestration, International Conference, May 26-29, Reykjavik, Iceland. Ahmed, I, Bouttom, T.W., Strom, K. B., Karim, A., and Irvin-Smith, N. (2013b). "Soil carbon distribution and loss monitoring in the urbanized Buffalo Bayou watershed, Houston, Texas." Proc., 4th Annual All Investigators Meeting of the North American Carbon Program, February 4-7, Albuquerque, NM. Fox, J.F. and Papanicolaou, A.N. (2008). An un-mixing model to study watershed erosion processes. Advances in Water Resources, 31, 96-108.

Degradation of Perchloroethene by zero-valent iron evaluated by carbon isotope fractionation

NASA Astrophysics Data System (ADS)

Leitner, Simon; Watzinger, Andrea; Reichenauer, Thomas G.

2014-05-01

Perchloroethene (PCE) is a widely spread groundwater contaminant in formally used industrial sites. Zero valent iron (ZVI) is used for in situ chemical reduction (ISCR) of PCE contaminants in the groundwater. A key factor in the application of in situ remediation technologies is a proper monitoring of contaminant reduction. The measurement of the stable isotope ratio is a promising method that is already used for quantifying microbial degradation of chlorinated contaminants. The carbon isotope ratio of PCE, measured by - isotope ratio mass spectrometry coupled to a gas chromatograph via a combustion interface (GC-C-IRMS), increases during degradation of PCE and can be directly related to the degree of degradation. It can be used to directly quantify chemical degradation and thus serves as a useful monitoring tool for groundwater remediation. An experiment to determine the carbon isotopic fractionation factor was performed as a lab experiment using Nanofer Star (NANOIRON). Two different PCE concentrations (c1: 220mgL-1, c2: 110mgL-1) mixed with 0.5 g of ZVI were sealed under deoxygenated conditions in 250 ml glas bottles locked with mininert caps. The bottles were incubated on a shaker for 865 h. Samples were taken weekly to measure the change in the carbon isotopic ratio of PCE as well as its concentration. Results showed a strong increase in the carbon isotope ratio (δ-value) of PCE (start: -27 o end: -4 ), which indicates a significant dechlorination process of PCE. Beside PCE also one degradation product (Trichloroethylene - TCE) was measured. TCE was further dechlorinated as indicated by the δ-value change of TCE from -26 o to -4 oȦn unexpected intermediate value of -45 o for TCE was observed in the experiment. This fluctuation could be induced by the time depending concentration due to degradation and conversation processes. Furthermore, it seems that the progress of the δ-value is affected by the starting concentration of PCE (δ-value of c1 < c2) as there is a higher ratio of PCE to ZVI.

Important considerations in the use of carbon and hydrogen stable isotopes to determine the origin of hydrocarbons in groundwater – A case study from pre-shale gas Tioga County

EPA Pesticide Factsheets

stable carbon and hydrogen isotopic compositional ranges of methanes (δ13C and δ2H (D)) enable us to distinguish between microbial and thermogenic origin of natural gases. To identify stray gas origins, identify possible gas sources, create baseline, carry out site-specific monitoring, and monitor long-term changes

Linking the isotopic composition of monthly precipitation, cave drip water and tree ring cellulose - 15 years of monitoring and data-model comparison

NASA Astrophysics Data System (ADS)

Labuhn, Inga; Genty, Dominique; Daux, Valérie; Bourges, François; Hoffmann, Georg

2013-04-01

The isotopic composition of proxies used for palaeoclimate reconstruction, like tree ring cellulose or speleothem calcite, is controlled to a large extent by the isotopic composition of precipitation. In order to calibrate and interpret these proxies in terms of climate, it is necessary to study water isotopes in rainfall and their link with the proxies' source water. We present 10 to 15-year series of stable hydrogen and oxygen isotopes in monthly precipitation from three sites in the south of France, along with corresponding REMOiso model simulations, a monitoring of cave drip water from two of these sites (Villars cave in the south-west and Chauvet cave in the south-east), as well as measurements of oxygen isotopes in tree ring cellulose from oak trees growing in the same area. The isotopic composition of monthly precipitation at the three sites displays a typical annual cycle. At the south-west sites, under Atlantic influence, the interannual variability is much more pronounced during the winter months than during the summer, whereas the south-eastern Mediterranean site shows the same variability throughout the year. The model simulations are able to reproduce the annual cycle of monthly precipitation δ18O as well as the intra-seasonal variability. Compared to the data, however, the modelled average isotopic values and the seasonal amplitude are overestimated. Correlations between temperature and precipitation δ18O are generally weak at all our sites, on both the monthly and the annual scale, even when using temperature averages weighted by the amount of precipitation. Consequently, a proxy which is controlled by the δ18O of precipitation cannot be directly interpreted in terms of temperature in this region. The isotopic composition of cave drip water in both caves remains stable throughout the monitoring period. By calculating different weighted averages of precipitation δ18O for time periods ranging from months to years, we demonstrate that the cave drip water isotopic composition is the result of several years of rainfall mixing. The precipitation of every month must be considered in order to attain the drip water values, which means that rain water infiltrates throughout the year. There is no modification of the soil water isotopic composition by evaporation and no seasonal bias introduced by transpiring plants; they use water from reserves which represents several months or years of mixing. For the interpretation of tree ring cellulose δ18O, this implies that - at least for the monitoring period of 15 years - the source water signal is more or less constant. Therefore, the variability of cellulose δ18O must be mainly due to evaporation at the leaf level, which is strongly dependent on summer temperature. Insights on the variability and temperature correlations of stable isotopes in precipitation and on the origin and composition of cave drip water are important for the interpretation of proxies. Long-term monitoring is needed for model validation, and the locally validated and corrected model can provide longer time series for a reliable proxy calibration.

The U.S. Department of Veterans' Affairs depleted uranium exposed cohort at 25 Years: Longitudinal surveillance results

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

McDiarmid, Melissa A.; Gaitens, Joanna M.; Hines,

Background: A small group of Gulf War I veterans wounded in depleted uranium (DU) friendly-fire incidents have been monitored for health changes in a clinical surveillance program at the Veterans Affairs Medical Center, Baltimore since 1994. Methods: During the spring of 2015, an in-patient clinical surveillance protocol was performed on 36 members of the cohort, including exposure monitoring for total and isotopic uranium concentrations in urine and a comprehensive assessment of health outcomes. Results: On-going mobilization of U from embedded fragments is evidenced by elevated urine U concentrations. The DU isotopic signature is observed principally in participants possessing embedded fragments.more » Those with only an inhalation exposure have lower urine U concentration and a natural isotopic signature. Conclusions: At 25 years since first exposure to DU, an aging cohort of military veterans continues to show no U-related health effects in known target organs of U toxicity. As U body burden continues to accrue from in-situ mobilization from metal fragment depots, and increases with exposure duration, critical tissue-specific U concentration thresholds may be reached, thus recommending on-going surveillance of this veteran cohort. - Highlights: • Gulf War I veterans wounded with depleted uranium are monitored for health changes. • In 2015 in-patient clinical surveillance was performed on 36 members of the cohort. • Mobilization of U from embedded fragments is evidenced by elevated U in urine. • This cohort of continues to show no U-related health effects.« less

Using the Abitibi Greenstone Belt to Understand Martian Hydrothermal Systems and the Potential for Biosignature Preservation in High Temperature Aqueous Environments

NASA Technical Reports Server (NTRS)

Hurowitz, J.; Abelson, J.; Allwood, A.; Anderson, R.; Atkinson, B.; Beaty, D.; Bristow, T.; Ehlmann, B.; Eigenbrode, J.; Grotzinger, J.;

Global Xenon-133 Emission Inventory Caused by Medical Isotope Production and Derived from the Worldwide Technetium-99m Demand

NASA Astrophysics Data System (ADS)

Kalinowski, Martin B.; Grosch, Martina; Hebel, Simon

2014-03-01

Emissions from medical isotope production are the most important source of background for atmospheric radioxenon measurements, which are an essential part of nuclear explosion monitoring. This article presents a new approach for estimating the global annual radioxenon emission inventory caused by medical isotope production using the amount of Tc-99m applications in hospitals as the basis. Tc-99m is the most commonly used isotope in radiology and dominates the medical isotope production. This paper presents the first estimate of the global production of Tc-99m. Depending on the production and transport scenario, global xenon emissions of 11-45 PBq/year can be derived from the global isotope demand. The lower end of this estimate is in good agreement with other estimations which are making use of reported releases and realistic process simulations. This proves the validity of the complementary assessment method proposed in this paper. It may be of relevance for future emission scenarios and for estimating the contribution to the global source term from countries and operators that do not make sufficient radioxenon release information available. It depends on sound data on medical treatments with radio-pharmaceuticals and on technical information on the production process of the supplier. This might help in understanding the apparent underestimation of the global emission inventory that has been found by atmospheric transport modelling.

Using water stable isotopes to assess evaporation and water residence time of lakes in EPA’s National Lakes Assessment.

EPA Science Inventory

Stable isotopes of water (18O and 2H) can be very useful in large-scale monitoring programs because water samples are easy to collect and water isotopes integrate information about basic hydrological processes such as evaporation as a percentage of inflow (E/I), w...

Simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals using ultra-high-performance liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method.

PubMed

Pan, Xinglu; Dong, Fengshou; Xu, Jun; Liu, Xingang; Chen, Zenglong; Liu, Na; Chen, Xixi; Tao, Yan; Zhang, Hongjun; Zheng, Yongquan

2015-05-01

A reliable and sensitive isotope-labelled internal standard method for simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits (apple and grape), vegetables (cucumber and tomato) and cereals (rice and wheat) using ultra-high-performance liquid chromatography-tandem mass spectrometry was developed. Isotope-labelled internal standards were effective in compensating for the loss in the pretreatment and overcoming the matrix effect. The analytes were extracted with acetonitrile and cleaned up with different kinds of sorbents. The determination of the target compounds was achieved in less than 4 min using a T3 column combined with an electrospray ionization source in positive mode. The overall average relative recoveries in all matrices at three spiking levels (10, 20 and 50 μg kg(-1)) ranged from 95.5 to 106.2 %, with all relative standard deviations being less than 14.4 % for all analytes. The limits of detection did not exceed 0.085 μg kg(-1) and the limits of quantification were below 0.28 μg kg(-1) in all matrices. The method was demonstrated to be convenient and accurate for the routine monitoring of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals.

A method for screening of plant species for space use

NASA Technical Reports Server (NTRS)

Goeschl, J. D.; Sauer, R. L.; Scheld, H. W.

1986-01-01

A cost-effective methodology which monitors numerous dynamic aspects of carbon assimilation and allocation kinetics in live, intact plants is discussed. Analogous methods can apply to nitrogen uptake and allocation. This methodology capitalizes on the special properties of the short-lived, positron-gamma emitting isotope C-11 especially when applied as CO2-11 in a special extended square wave (ESW) pattern. The 20.4 minute half-life allows for repeated or continuous experiments on the same plant over periods of minutes, hours, days, or weeks. The steady-state isotope equilibrium approached during the ESW experiments, and the parameters which can be analyzed by this technique are also direct results of that short half-life. Additionally, the paired .511 MeV gamma rays penetrate any amount of tissue and their 180 deg opposite orientation provides good collimation and allows coincidence counting which nearly eliminates background.

Determination of gamma-aminobutyric acid in food matrices by isotope dilution hydrophilic interaction chromatography coupled to mass spectrometry.

PubMed

Zazzeroni, Raniero; Homan, Andrew; Thain, Emma

2009-08-01

The estimation of the dietary intake of gamma-aminobutyric acid (GABA) is dependent upon the knowledge of its concentration values in food matrices. To this end, an isotope dilution liquid chromatography-mass spectrometry method has been developed employing the hydrophilic interaction chromatography technique for analyte separation. This approach enabled accurate quantification of GABA in apple, potato, soybeans, and orange juice without the need of a pre- or post-column derivatization reaction. A selective and precise analytical measurement has been obtained with a triple quadrupole mass spectrometer operating in multiple reaction monitoring using the method of standard additions and GABA-d(6) as an internal standard. The concentrations of GABA found in the matrices tested are 7 microg/g of apple, 342 microg/g of potatoes, 211 microg/g of soybeans, and 344 microg/mL of orange juice.

Quantification of abscisic acid in grapevine leaf (Vitis vinifera) by isotope-dilution liquid chromatography-mass spectrometry.

PubMed

Vilaró, Francisca; Canela-Xandri, Anna; Canela, Ramon

2006-09-01

A specific, sensitive, precise, and accurate method for the determination of abscisic acid (ABA) in grapevine leaf tissues is described. The method employs high-performance liquid chromatography and electrospray ionization-mass spectrometry (LC-ESI-MS) in selected ion monitoring mode (SIM) to analyze ABA using a stable isotope-labeled ABA as an internal standard. Absolute recoveries ranged from 72% to 79% using methanol/water pH 5.5 (50:50 v/v) as an extraction solvent. The best efficiency was obtained when the chromatographic separation was carried out by using a porous graphitic carbon (PGC) column. The statistical evaluation of the method was satisfactory in the work range. A relative standard deviation (RDS) of < 5.5% and < 6.0% was obtained for intra-batch and inter-batch comparisons, respectively. As for accuracy, the relative error (%Er) was between -2.7 and 4.3%, and the relative recovery ranged from 95% to 107%.

Isotope dilution liquid chromatography - mass spectrometry methods for fat- and water-soluble vitamins in nutritional formulations.

PubMed

Phinney, Karen W; Rimmer, Catherine A; Thomas, Jeanice Brown; Sander, Lane C; Sharpless, Katherine E; Wise, Stephen A

2011-01-01

Vitamins are essential to human health, and dietary supplements containing vitamins are widely used by individuals hoping to ensure they have adequate intake of these important nutrients. Measurement of vitamins in nutritional formulations is necessary to monitor regulatory compliance and in studies examining the nutrient intake of specific populations. Liquid chromatographic methods, primarily with UV absorbance detection, are well established for both fat- and water-soluble measurements, but they do have limitations for certain analytes and may suffer from a lack of specificity in complex matrices. Liquid chromatography-mass spectrometry (LC-MS) provides both sensitivity and specificity for the determination of vitamins in these matrices, and simultaneous analysis of multiple vitamins in a single analysis is often possible. In this work, LC-MS methods were developed for both fat- and water-soluble vitamins and applied to the measurement of these analytes in two NIST Standard Reference Materials. When possible, stable isotope labeled internal standards were employed for quantification.

Rapid Surface Detection of CO2 Leaks from Geologic Sequestration Sites

NASA Astrophysics Data System (ADS)

Moriarty, D. M.; Krevor, S. C.; Benson, S. M.

2013-12-01

Carbon sequestration is becoming a viable option for global CO2 mitigation but effective monitoring methods are needed assure the carbon dioxide stays underground. Above surface monitoring using a mobile gas analyzer is one such method (e.g. Krevor et al., 2010). The Picarro gas analyzer uses wavelength-scanned cavity ring down spectroscopy to accurately identify concentrations of various atmospheric gases including their isotopic composition. These measurements can then be used for anomaly (leak) detection and source attribution. Leaks are detected by anomalous absolute concentration of CO2 and anomalous δ13C values. Source attribution is determined by the isotopic concentrations of the identified leaking gas. To distinguish between noise from ambient signals and leaks, a method based on mixing ratios has been developed. A newly acquired data set presented here has been collected from a 3.7km2 area with naturally occurring CO2 springs near Green River, Utah. All of the areas of known leakage were readily detected using this method along with several other areas that showed significant signs of leakage. In addition, testing on the Stanford campus has shown that this method is sensitive enough to distinguish between open fields and roadways. Another data set is being collected at Montana State University at the ZERT monitoring test site where an artificial leak has been created for the purpose of testing leak detection and quantification methods. Data collected from this site are being used for (1) assessing of detection levels and how they depend on environmental parameters such as wind speed, and acquisition variables such as sample rate and traverse speed, (2) optimizing acquisition parameters to increase detection levels and increase confidence in leak detection, (3) evaluating the potential for quantifying the magnitude of the leak and (4) spatial data analysis to identify the most probable leak locations.

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 lineshapes, as opposed to emission spectroscopy which requires higher plasma temperatures to be able to detect thermally excited emission. Improvements in laser and detection systems and spectroscopic techniques have allowed for isotopic measurements to be carried out at standoff distances under ambient atmospheric conditions, which have expanded the applicability of optical spectroscopy-based isotopic measurements to a variety of scientific fields. These technological advances offer an in-situ measurement capability that was previously not available. This review will focus on isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing knowledge/technological gaps identified from the current literature and suggestions for the future work.

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 applicability of our new non-destructive approach to field conditions.

Seasonal changes in background levels of deuterium and oxygen-18 prove water drinking by harp seals, which affects the use of the doubly labelled water method.

PubMed

Nordøy, Erling S; Lager, Anne R; Schots, Pauke C

2017-12-01

The aim of this study was to monitor seasonal changes in stable isotopes of pool freshwater and harp seal ( Phoca groenlandica ) body water, and to study whether these potential seasonal changes might bias results obtained using the doubly labelled water (DLW) method when measuring energy expenditure in animals with access to freshwater. Seasonal changes in the background levels of deuterium and oxygen-18 in the body water of four captive harp seals and in the freshwater pool in which they were kept were measured over a time period of 1 year. The seals were offered daily amounts of capelin and kept under a seasonal photoperiod of 69°N. Large seasonal variations of deuterium and oxygen-18 in the pool water were measured, and the isotope abundance in the body water showed similar seasonal changes to the pool water. This shows that the seals were continuously equilibrating with the surrounding water as a result of significant daily water drinking. Variations in background levels of deuterium and oxygen-18 in freshwater sources may be due to seasonal changes in physical processes such as precipitation and evaporation that cause fractionation of isotopes. Rapid and abrupt changes in the background levels of deuterium and oxygen-18 may complicate calculation of energy expenditure by use of the DLW method. It is therefore strongly recommended that analysis of seasonal changes in background levels of isotopes is performed before the DLW method is applied on (free-ranging) animals, and to use a control group in order to correct for changes in background levels. © 2017. Published by The Company of Biologists Ltd.

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates.

PubMed

Skulan, J; DePaolo, D J

1999-11-23

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the (44)Ca/(40)Ca isotopic ratio, the total range of variation observed is 5.5 per thousand, and as much as 4 per thousand variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers.

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates

PubMed Central

Skulan, Joseph; DePaolo, Donald J.

1999-01-01

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the 44Ca/40Ca isotopic ratio, the total range of variation observed is 5.5‰, and as much as 4‰ variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers. PMID:10570137

Anomaly Detection in Gamma-Ray Vehicle Spectra with Principal Components Analysis and Mahalanobis Distances

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

Tardiff, Mark F.; Runkle, Robert C.; Anderson, K. K.

2006-01-23

The goal of primary radiation monitoring in support of routine screening and emergency response is to detect characteristics in vehicle radiation signatures that indicate the presence of potential threats. Two conceptual approaches to analyzing gamma-ray spectra for threat detection are isotope identification and anomaly detection. While isotope identification is the time-honored method, an emerging technique is anomaly detection that uses benign vehicle gamma ray signatures to define an expectation of the radiation signature for vehicles that do not pose a threat. Newly acquired spectra are then compared to this expectation using statistical criteria that reflect acceptable false alarm rates andmore » probabilities of detection. The gamma-ray spectra analyzed here were collected at a U.S. land Port of Entry (POE) using a NaI-based radiation portal monitor (RPM). The raw data were analyzed to develop a benign vehicle expectation by decimating the original pulse-height channels to 35 energy bins, extracting composite variables via principal components analysis (PCA), and estimating statistically weighted distances from the mean vehicle spectrum with the mahalanobis distance (MD) metric. This paper reviews the methods used to establish the anomaly identification criteria and presents a systematic analysis of the response of the combined PCA and MD algorithm to modeled mono-energetic gamma-ray sources.« less

Multi-mycotoxin stable isotope dilution LC-MS/MS method for Fusarium toxins in beer.

PubMed

Habler, Katharina; Gotthardt, Marina; Schüler, Jan; Rychlik, Michael

2017-03-01

A stable isotope dilution LC-MS/MS multi-mycotoxin method was developed for 12 different Fusarium toxins including modified mycotoxins in beer (deoxynivalenol-3-glucoside, deoxynivalenol, 3-acetyldeoxynivalenol, 15-acetyl-deoxynivalenol, HT2-toxin, T2-toxin, enniatin B, B1, A1, A, beauvericin and zearalenone). As sample preparation and purification of beer a combined solid phase extraction for trichothecenes, enniatins, beauvericin and zearalenone was firstly developed. The validation of the new method gave satisfying results: intra-day and inter-day precision and recoveries were 1-5%, 2-8% and 72-117%, respectively. In total, 61 different organic and conventional beer samples from Germany and all over the world were analyzed by using the newly developed multi-mycotoxin method. In summary, deoxynivalenol, deoxynivalenol-3-glucoside, 3-acetyldeoxynivaleneol and enniatin B were quantified in rather low contents in the investigated beer samples. None of the other monitored Fusarium toxins like 15-acetyldeoxynivalenol, HT2- and T2-toxin, zearalenone, enniatin B1, A1, A or beauvericin were detectable. Copyright © 2016 Elsevier Ltd. All rights reserved.

Particular geoscientific perspectives on stable isotope analysis in the arboreal system

NASA Astrophysics Data System (ADS)

Helle, Gerhard; Balting, Daniel; Pauly, Maren; Slotta, Franziska

2017-04-01

In geosciences stable isotopes of carbon, oxygen and hydrogen from the tree ring archive have been used for several decades to trace the course of past environmental and climatological fluctuations. In contrast to ice cores, the tree ring archive is of biological nature (like many other terrestrial archives), but provides the opportunity to establish site networks with very high resolution in space and time. Many of the basic physical mechanisms of isotope shifts are known, but biologically mediated processes may lead to isotope effects that are poorly understood. This implies that the many processes within the arboreal system leading to archived isotope ratios in wood material are governed by a multitude of environmental variables that are not only tied to the isotopic composition of atmospheric source values (precipitation, CO2), but also to seasonally changing metabolic flux rates and pool sizes of photosynthates within the trees. Consequently, the extraction of climate and environmental information is particularly challenging and reconstructions are still of rather qualitative nature. Over the last 10 years or so, monitoring studies have been implemented to investigate stable isotope, climate and environmental signal transfer within the arboreal system to develop transfer or response functions that can translate the relevant isotope values extracted from tree rings into climate or other environmental variables. To what extent have these efforts lead to a better understanding that helps improving the meaningfulness of tree ring isotope signals? For example, do monitoring studies help deciphering the causes for age-related trends in tree ring stable isotope sequences that are published in a growing number of papers. Are existing monitoring studies going into detail enough or is it already too much effort for the outcome? Based on what we know already particularly in mesic habitats, tree ring stable isotopes are much better climate proxies than other tree ring parameters. However, millennial or multi-millennial high quality reconstructions from tree ring isotopes are still rare. This is because of i) methodological constraints related to mass spectrometric analyses and ii) the nature of tree-ring chronologies that are put together by many trees of various individual ages. In view of this: What is the state-of-the-art in high throughput tree ring stable isotope analyses? Is it necessary to advance existing methodologies further to conserve the annual time resolution provided by the tree-ring archive? Other terrestrial archives, like lake sediments and speleothems rarely provide annually resolved stable isotope data. Furthermore, certain tree species from tropical or sub-tropical regions cannot be dated properly by dendrochronology and hence demand specific stable isotope measuring strategies, etc.. Although the points raised here do specifically apply for the tree ring archive, some of them are important for all proxy archives of organic origin.

Temporal variations of methane concentration and isotopic composition in groundwater of the St. Lawrence Lowlands, eastern Canada

NASA Astrophysics Data System (ADS)

Rivard, Christine; Bordeleau, Geneviève; Lavoie, Denis; Lefebvre, René; Malet, Xavier

2018-03-01

Dissolved methane concentrations in shallow groundwater are known to vary both spatially and temporally. The extent of these variations is poorly documented although this knowledge is critical for distinguishing natural fluctuations from anthropogenic impacts stemming from oil and gas activities. This issue was addressed as part of a groundwater research project aiming to assess the risk of shale gas development for groundwater quality over a 500-km2 area in the St. Lawrence Lowlands (Quebec, Canada). A specific study was carried out to define the natural variability of methane concentrations and carbon and hydrogen isotope ratios in groundwater, as dissolved methane is naturally ubiquitous in aquifers of this area. Monitoring was carried out over a period of up to 2.5 years in seven monitoring wells. Results showed that for a given well, using the same sampling depth and technique, methane concentrations can vary over time from 2.5 to 6 times relative to the lowest recorded value. Methane isotopic composition, which is a useful tool to distinguish gas origin, was found to be stable for most wells, but varied significantly over time in the two wells where methane concentrations are the lowest. The use of concentration ratios, as well as isotopic composition of methane and dissolved inorganic carbon (DIC), helped unravel the processes responsible for these variations. This study indicates that both methane concentrations and isotopic composition, as well as DIC isotopes, should be regularly monitored over at least 1 year to establish their potential natural variations prior to hydrocarbon development.

First application of calorimetric low-temperature detectors in accelerator mass spectrometry

NASA Astrophysics Data System (ADS)

Kraft, S.; Andrianov, V.; Bleile, A.; Egelhof, P.; Golser, R.; Kiseleva, A.; Kiselev, O.; Kutschera, W.; Meier, J. P.; Priller, A.; Shrivastava, A.; Steier, P.; Vockenhuber, C.

2004-03-01

For the first time, calorimetric low-temperature detectors were applied in accelerator mass spectrometry, a well-known method for determination of very small isotope ratios with high sensitivity. The aim of the experiment was to determine with high accuracy the isotope ratio of 236U/238U for several samples of natural uranium, 236U being known as a sensitive monitor for neutron flux. Measurements were performed at the VERA tandem accelerator at Vienna, Austria. The detectors consist of sapphire absorbers and superconducting transition edge thermometers operated at T≈ 1.5 K. The relative energy resolution obtained for 17.39 MeV 238U is ΔE/E=4-9×10-3, depending on the experimental conditions. This performance enabled to substantially reduce background from neighbouring isotopes and to increase the detection efficiency. Due to the high sensitivity achieved, a value of 236U/238U=6.5×10-12 could be obtained, representing the smallest 236U/238U ratio measured until now.

Isotopenhydrologische Methoden (2H, 18O) zur Bestimmung der Grundwasserneubildung in Trockengebieten: Potenzial und Grenzen

NASA Astrophysics Data System (ADS)

Beyer, Matthias; Gaj, Marcel; Königer, Paul; Tulimeveva Hamutoko, Josefina; Wanke, Heike; Wallner, Markus; Himmelsbach, Thomas

2018-03-01

The estimation of groundwater recharge in water-limited environments is challenging due to climatic conditions, the occurrence of deep unsaturated zones, and specialized vegetation. We critically examined two methods based on stable isotopes of soil water: (i) the interpretation of natural isotope depth-profiles and subsequent approximation of recharge using empirical relationships and (ii) the use of deuterium-enriched water (2H2O) as tracer. Numerous depth-profiles were measured directly in the field in semiarid Namibia using a novel in-situ technique. Additionally, 2H2O was injected into the soil and its displacement over a complete rainy season monitored. Estimated recharge ranges between 0 and 29 mm/y for three rainy seasons experiencing seasonal rainfall of 660 mm (2013/14), 313 mm (2014/15) and 535 mm (2015/16). The results of this study fortify the suitability of water stable isotope-based approaches for recharge estimation and highlight enormous potential for future studies of water vapor transport and ecohydrological processes.

High mass accuracy assay for trimethylamine N-oxide using stable-isotope dilution with liquid chromatography coupled to orthogonal acceleration time of flight mass spectrometry with multiple reaction monitoring.

PubMed

Heaney, Liam M; Jones, Donald J L; Mbasu, Richard J; Ng, Leong L; Suzuki, Toru

2016-01-01

Trimethylamine N-oxide (TMAO) has attracted interest as circulating levels have reported prognostic value in patients with cardiovascular conditions, such as heart failure. With continual advances in accurate mass measurements, robust methods that can employ the capabilities of time of flight mass spectrometers would offer additional utility in the analysis of complex clinical samples. A Waters Acquity UPLC was coupled to a Waters Synapt G2-S high-resolution mass spectrometer. TMAO was measured in plasma by stable-isotope dilution-hydrophilic interaction liquid chromatography-time of flight mass spectrometry with multiple reaction monitoring (LC-ToF-MRM). Two transitions were monitored: m/z 76.1 to 58.066/59.073 and m/z 85.1 to 66.116/68.130. The method was assessed for linearity, lower limits of detection and quantitation, and reproducibility. A selected cohort of patients with systolic heart failure (SHF; n = 43) and healthy controls (n = 42) were measured to verify the assay is suitable for the analysis of clinical samples. Quantitative analysis of TMAO using LC-ToF-MRM enabled linearity to be established between 0.1 and 75 μmol/L, with a lower limit of detection of 0.05 μmol/L. Relative standard deviations reported an inter-day variation of ≤20.8% and an intra-day variation of ≤11.4% with an intra-study quality control variation of 2.7%. Run times were 2.5 min. Clinical application of the method reported that TMAO in SHF was elevated compared to that of healthy controls (p < 0.0005). LC-ToF-MRM offers a highly selective method for accurate mass measurement of TMAO with rapid and reproducible results. Applicability of the method was shown in a selected cohort of patient samples.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

Stable Carbon Isotope Evidence and Quantification of Reductive Dechlorination of Chlorinated Ethenes at Kelly AFB, TX

NASA Astrophysics Data System (ADS)

Morrill, P.; Lacrampe-Couloume, G.; Slater, G.; Sleep, B.; Edwards, E.; McMaster, M.; Major, D.; Sherwood Lollar, B.

2002-12-01

Cis-1, 2-dichloroethene (cDCE) was the primary volatile organic compound (VOC) after biostimulation of a perchloroethene (PCE) plume in a pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. A stable natural microbial consortium, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene was added in a pilot test area (PTA). After the addition of KB-1 stable carbon isotope values were measured for each chlorinated ethene to verify the occurrence of reductive dechlorination and quantify the extent of cDCE degradation. After bioaugmentation with KB-1, PCE, TCE and cDCE concentrations declined, while VC concentrations increased and subsequently decreased, as ethene became the dominant transformation product measured. Shifts in carbon isotopic values up to 2.7 permil, 6.4 permil, 10.9 permil and 10.6 permil were observed for PCE, TCE, cDCE and VC respectively. These isotopic shifts are consistent with the effects of biodegradation observed during laboratory and field studies. Most notably, isotopic enrichment trends characteristic of reductive dechlorination were detectable in the parent compounds before measurable concentrations of daughter products VC and ethene were produced. These results illustrate the advantage of using the more sensitive compound specific isotope analysis to confirm degradation in addition to the traditional method of monitoring the appearance of degradation products. Fractionation factors obtained from laboratory studies were used in conjunction with isotope data measured in the field to estimate the extent of cDCE degraded. It is estimated that within a 44 day period, 37 to 48 percent of the cDCE was reductively dechlorinated. Independent biodegradation estimates using data from a bromide tracer test, a groundwater flow model, and concentration analyses were all in good agreement with the isotope degradation estimate.

Method for production of an isotopically enriched compound

DOEpatents

Watrous, Matthew G.

2012-12-11

A method is presented for producing and isolating an isotopically enriched compound of a desired isotope from a parent radionuclide. The method includes forming, or placing, a precipitate containing a parent radionuclide of the desired daughter isotope in a first reaction zone and allowing sufficient time for the parent to decay into the desired gaseous daughter radioisotope. The method further contemplates collecting the desired daughter isotope as a solid in a second reaction zone through the application of temperatures below the freezing point of the desired isotope to a second reaction zone that is connected to the first reaction zone. Specifically, a method is presented for producing isotopically enriched compounds of xenon, including the radioactive isotope Xe-131m and the stable isotope Xe-131.

Stable isotope estimates of evaporation: inflow and water residence time for lakes across the United States as a tool for national lake water quality assessments

EPA Science Inventory

Stable isotope ratios of water (delta18O and delta2H) can be very useful in large-scale monitoring programs because water samples are easy to collect and isotope ratios integrate information about basic hydrologic processes such as evaporation as a percentage of inflow (E/I) and ...

Nuclear Explosion Monitoring Research and Development Roadmaps

DTIC Science & Technology

2010-09-01

environment, a radionuclide event is the release of radioactive atoms. Radionuclide sources include nuclear explosions, normal or anomalous reactor ...isotopes (e.g., potassium, uranium, and thorium and their decay products) and isotopes produced from the interactions of cosmic rays with the...and reactor emissions. For example, the IMS detected a pair of xenon isotopes at a Japanese station shortly after the 2009 DPRK event. The ratio of

Noble gas isotopes as low-budget exploration and monitoring tool for high- and low-temperature geothermal systems in extensional tectonic regimes

NASA Astrophysics Data System (ADS)

Kraml, Michael; Jodocy, Marco; Aeschbach, Werner; Kreuter, Horst

2017-04-01

Since viable geothermal systems in extensional settings are sparse compared to those situated in subduction zone environments, a specifically adapted exploration methodology of the former is currently not fully established. Standardized exploration methods applicable to geothermal systems related to subduction zones do not always deliver reliable or even deliver misleading results (e.g. Ochmann et al. 2010). The identification of promising prospects at the beginning of surface exploration studies is saving time and money of the project developer and investor. Noble gas isotope analyses can provide a low-budget tool for assessing the quality of the prospect in a very early exploration phase. Case studies of high- and low-temperature prospects situated in the East African Rift System and the Upper Rhine Graben, Germany will be presented and compared to other extensional areas like the Basin and Range Province, U.S.A. (Kraml et al. 2016a,b). Noble gas isotopes are also a versatile tool for monitoring of geothermal reservoirs during the production/exploitation phase. References Kraml, M., Jodocy, M., Reinecker, J., Leible, D., Freundt, F., Al Najem, S., Schmidt, G., Aeschbach, W., and Isenbeck-Schroeter, M. (2016a): TRACE: Detection of Permeable Deep-Reaching Fault Zone Sections in the Upper Rhine Graben, Germany, During Low-Budget Isotope-Geochemical Surface Exploration. Proceedings European Geothermal Congress 2016, Strasbourg, France, 19-24 Sept 2016 Kraml, M., Kaudse, T., Aeschbach, W. and Tanzanian Exploration Team (2016b): The search for volcanic heat sources in Tanzania: A helium isotope perspective. Proceedings 6th African Rift Geothermal Conference, Addis Ababa, Ethiopia, 2nd-4th November 2016 Ochmann, N., Kraml, M., Lindenfeld, M., Yakovlev, A., Rümpker, G., Babirye, P. (2010): Microearthquake Survey at the Buranga Geothermal Prospect (Western Uganda). Proceedings World Geothermal Congress, 25-29 April 2010, Bali, Indonesia (paper number 1126)

Determination of ultratrace levels of tributyltin in waters by isotope dilution and gas chromatography coupled to tandem mass spectrometry.

PubMed

Rodríguez-Cea, Andrés; Rodríguez-González, Pablo; Font Cardona, Nuria; Aranda Mares, José Luís; Ballester Nebot, Salomé; García Alonso, J Ignacio

2015-12-18

The current EU legislation lays down the Environmental Quality Standards (EQS) of 45 priority substances in surface water bodies. In particular, the concentration of tributyltin (TBT) must not exceed 0.2ngL(-1) and analytical methodologies with a Limit of Quantification (LOQ) equal or below 0.06ngL(-1) are urged to be developed. This work presents a procedure for the determination of ultratrace levels of TBT in water samples by Isotope Dilution and GC-MS/MS operating in Selected Reaction Monitoring (SRM) mode which meets current EU requirements. The method requires the monitorization of five consecutive transitions (287>175 to 291>179) for the sensitive and selective detection of TBT. The measured isotopic distribution of TBT fragment ions was in agreement with the theoretical values computed by a polynomial expansion algorithm. The combined use of Tandem Mass Spectrometry, a sample volume of 250mL, the preconcentration of 1mL of organic phase to 30μL and an injection volume of 25μL by Programmed Temperature Vaporization provided a LOQ of 0.0426ngL(-1) for TBT (calculated as ten times the standard deviation of nine independent blanks). The recovery for TBT calculated in Milli-Q water at the EQS level was 106.3±4%. A similar procedure was also developed for the quantification of dibutyltin (DBT) and monobutyltin (MBT) in water samples showing satisfactory results. The method was finally implemented in a routine testing laboratory to demonstrate its applicability to real samples obtaining quantitative recoveries for TBT at the EQS level in mineral water, river water and seawater. Copyright © 2015 Elsevier B.V. All rights reserved.

Stable isotope ratios of tap water in the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Ehleringer, James R.; Chesson, Lesley A.; Stange, Erik; Cerling, Thure E.

2007-03-01

Understanding links between water consumers and climatological (precipitation) sources is essential for developing strategies to ensure the long-term sustainability of water supplies. In pursing this understanding a need exists for tools to study and monitor complex human-hydrological systems that involve high levels of spatial connectivity and supply problems that are regional, rather than local, in nature. Here we report the first national-level survey of stable isotope ratios in tap water, including spatially and temporally explicit samples from a large number of cities and towns across the contiguous United States. We show that intra-annual ranges of tap water isotope ratios are relatively small (e.g., <10‰ for δ2H) at most sites. In contrast, spatial variation in tap water isotope ratios is very large, spanning ranges of 163‰ for δ2H and 23.6‰ for δ18O. The spatial distribution of tap water isotope ratios at the national level is similar to that of stable isotope ratios of precipitation. At the regional level, however, pervasive differences between tap water and precipitation isotope ratios can be attributed to hydrological factors in the water source to consumer chain. These patterns highlight the potential for monitoring of tap water isotope ratios to contribute to the study of regional water supply stability and provide warning signals for impending water resource changes. We present the first published maps of predicted tap water isotope ratios for the contiguous United States, which will be useful in guiding future research on human-hydrological systems and as a tool for applied forensics and traceability studies.

Method and apparatus for diagnosing breached fuel elements

DOEpatents

Gross, K.C.; Lambert, J.D.B.; Nomura, S.

1987-03-02

The invention provides an apparatus and method for diagnosing breached fuel elements in a nuclear reactor. A detection system measures the activity of isotopes from the cover gas in the reactor. A data acquisition and processing system monitors the detection system and corrects for the effects of the cover-gas clean up system on the measured activity and further calculates the derivative curve of the corrected activity as a function of time. A plotting system graphs the derivative curve, which represents the instantaneous release rate of fission gas from a breached fuel element. 8 figs.

Water balance model for mean annual hydrogen and oxygen isotope distributions in surface waters of the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Kennedy, Casey D.; Liu, Zhongfang; Stalker, Jeremy

2011-12-01

The stable H and O isotope composition of river and stream water records information on runoff sources and land-atmosphere water fluxes within the catchment and is a potentially powerful tool for network-based monitoring of ecohydrological systems. Process-based hydrological models, however, have thus far shown limited power to replicate observed large-scale variation in U.S. surface water isotope ratios. Here we develop a geographic information system-based model to predict long-term annual average surface water isotope ratios across the contiguous United States. We use elevation-explicit, gridded precipitation isotope maps as model input and data from a U.S. Geological Survey monitoring program for validation. We find that models incorporating monthly variation in precipitation-evapotranspiration (P-E) amounts account for the majority (>89%) of isotopic variation and have reduced regional bias relative to models that do not consider intra-annual P-E effects on catchment water balance. Residuals from the water balance model exhibit strong spatial patterning and correlations that suggest model residuals isolate additional hydrological signal. We use interpolated model residuals to generate optimized prediction maps for U.S. surface water δ2H and δ18O values. We show that the modeled surface water values represent a relatively accurate and unbiased proxy for drinking water isotope ratios across the United States, making these data products useful in ecological and criminal forensics applications that require estimates of the local environmental water isotope variation across large geographic regions.

Study report on a double isotope method of calcium absorption

NASA Technical Reports Server (NTRS)

1978-01-01

Some of the pros and cons of three methods to study gastrointestinal calcium absorption are briefly discussed. The methods are: (1) a balance study; (2) a single isotope method; and (3) a double isotope method. A procedure for the double isotope method is also included.

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

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

Wimmer, Bernhard, E-mail: bernhard.wimmer@ait.ac.at; Hrad, Marlies; Huber-Humer, Marion

Highlights: ► The isotopic signature of δ{sup 13}C-DIC of leachates is linked to the reactivity of MSW. ► Isotopic signatures of leachates depend on aerobic/anaerobic conditions in landfills. ► In situ aeration of landfills can be monitored by isotope analysis in leachate. ► The isotopic analysis of leachates can be used for assessing the stability of MSW. ► δ{sup 13}C-DIC of leachates helps to define the duration of landfill aftercare. - Abstract: Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated themore » isotopic signatures of δ{sup 13}C, δ{sup 2}H and δ{sup 18}O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ{sup 13}C-value of the dissolved inorganic carbon (δ{sup 13}C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ{sup 13}C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ{sup 13}C-DIC of −20‰ to −25‰. The production of methane under anaerobic conditions caused an increase in δ{sup 13}C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ{sup 13}C-DIC of about −20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.« less

Use of isotopically-tagged isolates of E. coli for tracking bacterial movement in karst environments

NASA Astrophysics Data System (ADS)

Bandy, A.; Fryar, A. E.; Macko, S. A.; Cook, K.

2014-12-01

Because of limited filtration and turbulent flow, karst aquifers are more susceptible to microbial contamination than clastic aquifers. Assessment of microbial transport in groundwater is complicated by the need to identify tracers that have a low detection limit, have minimal background concentrations, behave like the organisms of interest, and are non-pathogenic. We are assessing transport of two non-pathogenic isolates of Escherichia coli (E. coli) compared to traditional groundwater tracers in epikarst above Cave Springs Cavern near Bowling Green, KY, and in a karst conduit that emerges at Royal Spring in Georgetown, KY. The E. coli isolate exhibiting higher attachment efficiency in saturated granular columns contains the iha gene, while the isolate exhibiting lower attachment efficiency contains the kps gene. For the field experiments, bacteria are being grown on media enriched in 13C or 15N. Isotopically-tagged bacteria will be injected with rhodamine WT as a solute tracer and fluorescent microspheres as an abiotic particulate tracer. We will monitor breakthrough of the tracers in the cave and at the spring; based on a previous field test, we anticipate that particulate tracers may be remobilized during subsequent storm events. E. coli will be quantified by molecular methods (qPCR) and dual isotope analysis. Preliminary findings suggest that these two methods may be complementary, with each method having detection limitations.

Evaluation of analytical methodology for the detection of hormones and their attenuation during aquifer recharge and recovery cycles.

PubMed

de Lima Stebbins, Daniela; Docs, Jon; Lowe, Paula; Cohen, Jason; Lei, Hongxia

2016-05-18

The hormones listed in the screening survey list 2 of the Unregulated Contaminant Monitoring Rule 3 (estrone, 17-β-estradiol, 17-α-ethynylestradiol, 16-α-hydroxyestradiol (estriol), equilin, testosterone and 4-androstene-3,17-dione) were analyzed by liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Two analytical methods were compared: EPA method 539 and the isotope dilution method. EPA method 539 was successfully utilized in river and drinking water matrices with fortified recoveries of 98.9 to 108.5%. Samples from the Hillsborough River reflected levels below the method detection limit (MDL) for the majority of the analytes, except estrone (E1), which was detected at very low concentrations (<0.5 to 1 ng L(-1)) in the majority of samples. No hormones were detected in drinking water samples. The isotope dilution method was used to analyze reclaimed and aquifer storage and recovery (ASR) water samples as a result of strong matrix/solid phase extraction (SPE) losses observed in these more complex matrices. Most of the compounds were not detected or found at relatively low concentrations in the ASR samples. Attenuation of 50 to 99.1% was observed as a result of the ASR recharge/recovery cycles for most of the hormones, except for estriol (E3). Relatively stable concentrations of E3 were found, with only 10% attenuation at one of the sites and no measureable attenuation at another location. These results have substantiated that while EPA method 539 works well for most environmental samples, the isotope dilution method is more robust when dealing with complex matrices such as reclaimed and ASR samples.

Device and method for accurately measuring concentrations of airborne transuranic isotopes

DOEpatents

McIsaac, Charles V.; Killian, E. Wayne; Grafwallner, Ervin G.; Kynaston, Ronnie L.; Johnson, Larry O.; Randolph, Peter D.

1996-01-01

An alpha continuous air monitor (CAM) with two silicon alpha detectors and three sample collection filters is described. This alpha CAM design provides continuous sampling and also measures the cumulative transuranic (TRU), i.e., plutonium and americium, activity on the filter, and thus provides a more accurate measurement of airborne TRU concentrations than can be accomplished using a single fixed sample collection filter and a single silicon alpha detector.

Device and method for accurately measuring concentrations of airborne transuranic isotopes

DOEpatents

McIsaac, C.V.; Killian, E.W.; Grafwallner, E.G.; Kynaston, R.L.; Johnson, L.O.; Randolph, P.D.

1996-09-03

An alpha continuous air monitor (CAM) with two silicon alpha detectors and three sample collection filters is described. This alpha CAM design provides continuous sampling and also measures the cumulative transuranic (TRU), i.e., plutonium and americium, activity on the filter, and thus provides a more accurate measurement of airborne TRU concentrations than can be accomplished using a single fixed sample collection filter and a single silicon alpha detector. 7 figs.

Isotopic Discrimination During Leaf Litter Decomposition

NASA Astrophysics Data System (ADS)

Ngao, J.; Rubino, M.

2006-12-01

Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to implement an advanced laser spectrometry technology to measure the isotopic composition in respired CO2. The laser spectrometer will be used to investigate the isotopic discrimination during soil respiration, in laboratory and field studies.

Collaborative Study of Analysis of High Resolution Infrared Atmospheric Spectra Between NASA Langley Research Center and the University of Denver

NASA Technical Reports Server (NTRS)

Goldman, Aaron

1999-01-01

The Langley-D.U. collaboration on the analysis of high resolution infrared atmospheric spectra covered a number of important studies of trace gases identification and quantification from field spectra, and spectral line parameters analysis. The collaborative work included: Quantification and monitoring of trace gases from ground-based spectra available from various locations and seasons and from balloon flights. Studies toward identification and quantification of isotopic species, mostly oxygen and Sulfur isotopes. Search for new species on the available spectra. Update of spectroscopic line parameters, by combining laboratory and atmospheric spectra with theoretical spectroscopy methods. Study of trends of atmosphere trace constituents. Algorithms developments, retrievals intercomparisons and automatization of the analysis of NDSC spectra, for both column amounts and vertical profiles.

Uncertainty quantification for discrimination of nuclear events as violations of the comprehensive nuclear-test-ban treaty.

PubMed

Sloan, Jamison; Sun, Yunwei; Carrigan, Charles

2016-05-01

Enforcement of the Comprehensive Nuclear Test Ban Treaty (CTBT) will involve monitoring for radiologic indicators of underground nuclear explosions (UNEs). A UNE produces a variety of radioisotopes which then decay through connected radionuclide chains. A particular species of interest is xenon, namely the four isotopes (131m)Xe, (133m)Xe, (133)Xe, and (135)Xe. Due to their half lives, some of these isotopes can exist in the subsurface for more than 100 days. This convenient timescale, combined with modern detection capabilities, makes the xenon family a desirable candidate for UNE detection. Ratios of these isotopes as a function of time have been studied in the past for distinguishing nuclear explosions from civilian nuclear applications. However, the initial yields from UNEs have been treated as fixed values. In reality, these independent yields are uncertain to a large degree. This study quantifies the uncertainty in xenon ratios as a result of these uncertain initial conditions to better bound the values that xenon ratios can assume. We have successfully used a combination of analytical and sampling based statistical methods to reliably bound xenon isotopic ratios. We have also conducted a sensitivity analysis and found that xenon isotopic ratios are primarily sensitive to only a few of many uncertain initial conditions. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Phase II: Field Detector Development For Undeclared/Declared Nuclear Testing For Treaty Verfiation Monitoring

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

Kriz, M.; Hunter, D.; Riley, T.

2015-10-02

Radioactive xenon isotopes are a critical part of the Comprehensive Nuclear Test Ban Treaty (CTBT) for the detection or confirmation of nuclear weapons tests as well as on-site treaty verification monitoring. On-site monitoring is not currently conducted because there are no commercially available small/robust field detector devices to measure the radioactive xenon isotopes. Xenon is an ideal signature to detect clandestine nuclear events since they are difficult to contain and can diffuse and migrate through soils due to their inert nature. There are four key radioxenon isotopes used in monitoring: 135Xe (9 hour half-life), 133mXe (2 day half-life), 133Xe (5more » day half-life) and 131mXe (12 day half-life) that decay through beta emission and gamma emission. Savannah River National Laboratory (SRNL) is a leader in the field of gas collections and has developed highly selective molecular sieves that allow for the collection of xenon gas directly from air. Phase I assessed the development of a small, robust beta-gamma coincidence counting system, that combines collection and in situ detection methodologies. Phase II of the project began development of the custom electronics enabling 2D beta-gamma coincidence analysis in a field portable system. This will be a significant advancement for field detection/quantification of short-lived xenon isotopes that would not survive transport time for laboratory analysis.« less

Stable isotope views on ecosystem function: challenging or challenged?

PubMed

Resco, Víctor; Querejeta, José I; Ogle, Kiona; Voltas, Jordi; Sebastià, Maria-Teresa; Serrano-Ortiz, Penélope; Linares, Juan C; Moreno-Gutiérrez, Cristina; Herrero, Asier; Carreira, José A; Torres-Cañabate, Patricia; Valladares, Fernando

2010-06-23

Stable isotopes and their potential for detecting various and complex ecosystem processes are attracting an increasing number of scientists. Progress is challenging, particularly under global change scenarios, but some established views have been challenged. The IX meeting of the Spanish Association of Terrestrial Ecology (AAET, Ubeda, 18-22 October 2009) hosted a symposium on the ecology of stable isotopes where the linear mixing model approach of partitioning sinks and sources of carbon and water fluxes within an ecosystem was challenged, and new applications of stable isotopes for the study of plant interactions were evaluated. Discussion was also centred on the need for networks that monitor ecological processes using stable isotopes and key ideas for fostering future research with isotopes.

Stable isotope views on ecosystem function: challenging or challenged?

PubMed Central

Resco, Víctor; Querejeta, José I.; Ogle, Kiona; Voltas, Jordi; Sebastià, Maria-Teresa; Serrano-Ortiz, Penélope; Linares, Juan C.; Moreno-Gutiérrez, Cristina; Herrero, Asier; Carreira, José A.; Torres-Cañabate, Patricia; Valladares, Fernando

2010-01-01

Stable isotopes and their potential for detecting various and complex ecosystem processes are attracting an increasing number of scientists. Progress is challenging, particularly under global change scenarios, but some established views have been challenged. The IX meeting of the Spanish Association of Terrestrial Ecology (AAET, Úbeda, 18–22 October 2009) hosted a symposium on the ecology of stable isotopes where the linear mixing model approach of partitioning sinks and sources of carbon and water fluxes within an ecosystem was challenged, and new applications of stable isotopes for the study of plant interactions were evaluated. Discussion was also centred on the need for networks that monitor ecological processes using stable isotopes and key ideas for fostering future research with isotopes. PMID:20015858

UPLC-MS/MS method for therapeutic drug monitoring of 10 antibiotics used in intensive care units.

PubMed

El-Najjar, Nahed; Hösl, Julian; Holzmann, Thomas; Jantsch, Jonathan; Gessner, André

2018-03-01

A large variation in the levels of different ß-lactams and other antibiotics used in critically ill patients has been documented. The aim of this study is to establish and validate a fast, ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous analysis of ten antibiotics (Meropenem, Cefepime, Ceftazidime, Piperacillin, Benzylpenicillin, Ampicillin, Flucloxacillin, Linezolid, and Sulfamethoxazole/Trimethoprim) in human plasma according to European Medicines Agency (EMA) guidelines. Protein precipitation with ice-cold methanol containing 9 isotopically labeled internal standards was used for sample clean up. Antibiotics were detected, following a 4-minute gradient separation, in multiple reactions monitoring (MRM) using API 4000 instrument equipped with electrospray source operating in positive ion mode. The lower limit of quantification was 0.1 mg/L for Meropenem, Ceftazidime, Piperacillin, Ampicillin, Flucloxacillin, and Sulfamethoxazole; 0.05 mg/L for Cefepime, Benzylpenicillin, and Trimethoprim; and 0.02 mg/L for Linezolid. The method proved to be precise and accurate and applicable for therapeutic drug monitoring and other pharmacokinetic studies. Copyright © 2017 John Wiley & Sons, Ltd.

``Recycling'' Geophysics: Monitoring and Isotopic Analysis of Engineered Biological Systems

NASA Astrophysics Data System (ADS)

Doherty, R.; Singh, K. P.; Ogle, N.; Ntarlagiannis, D.

2010-12-01

The emerging sub discipline of biogeophysics has provoked debate on the mechanisms of microbial processes that may contribute to geophysical signatures. At field scales geophysical signatures are often non unique due to the many parameters (physical, chemical, and biological) that are involved. It may be easier to apply geophysical techniques such as electrodic potential (EP), self potential (SP) and induced polarization (IP) to engineered biological systems where there is a degree of control over the design of the physical and chemical domain. Here we present results of a column experiment that was designed to anaerobically biodegrade dissolved organic matter in landfill leachate. The column utilises a recycled porous media (concrete) to help sequester organic carbon. Electrodic potential, self potential and induced polarisation are used in conjunction with chemical and isotopic techniques to monitor the effectiveness of this approach. Preliminary carbon and oxygen isotopic analysis on concrete from the column in contact with leachate show isotopic enrichment suggesting abiotic precipitation of carbonates.

Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer-chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS).

PubMed

Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A; Schimmelmann, Arndt

2017-03-30

Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H 2 ) is responsible for non-quantitative H 2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer-Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems. The EA-Cr/HTC reactor was substantially modified for the conversion of halogen- and sulfur-bearing samples. The performance of the novel conversion setup for solid and liquid samples was monitored and optimized using a simultaneously operating dual-detection system of IRMS and ion trap MS. The method with several variants in the reactor, including the addition of manganese metal chips, was evaluated in three laboratories using EA-Cr/HTC-IRMS (on-line method) and compared with traditional uranium-reduction-based conversion combined with manual dual-inlet IRMS analysis (off-line method) in one laboratory. The modified EA-Cr/HTC reactor setup showed an overall H 2 -recovery of more than 96% for all halogen- and sulfur-bearing organic compounds. All results were successfully normalized via two-point calibration with VSMOW-SLAP reference waters. Precise and accurate hydrogen isotopic analysis was achieved for a variety of organics containing F-, Cl-, Br-, I-, and S-bearing heteroelements. The robust nature of the on-line EA-Cr/HTC technique was demonstrated by a series of 196 consecutive measurements with a single reactor filling. The optimized EA-Cr/HTC reactor design can be implemented in existing analytical equipment using commercially available material and is universally applicable for both heteroelement-bearing and heteroelement-free organic-compound classes. The sensitivity and simplicity of the on-line EA-Cr/HTC-IRMS technique provide a much needed tool for routine hydrogen-isotope source tracing of organic contaminants in the environment. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Habitat Use and Trophic Structure in a Highly Migratory Predatory Fish Identified with Geochemical Proxies in Scales

NASA Astrophysics Data System (ADS)

Seeley, M.; Walther, B. D.

2016-02-01

Atlantic tarpon, Megalops atlanticus, are highly migratory euryhaline predators that occupy different habitats throughout ontogeny. Specifically, Atlantic tarpon are known to inhabit oligohaline waters, although the frequency and duration of movements across estuarine gradients into these waters are relatively unknown. This species supports over a two billion dollar industry within the Gulf of Mexico and is currently listed as vulnerable under the International Union for the Conservation of Nature (IUCN). A new non-lethal method for reconstructing migrations across estuaries relies on trace element and stable isotope compositions of growth increments in scales. We analyzed Atlantic tarpon scales from the Texas coast to validate this method using inductively coupled plasma mass spectrometry (ICP-MS) for trace elements and isotope ratio mass spectrometry (IR-MS) for stable isotope ratios. Multiple scales were also taken from the same individual to confirm the consistency of elemental uptake within the same individual. Results show that scale Ba:Ca, Sr:Ca and δ13C are effective proxies for salinity, while enrichments in δ15N are consistent with known ontogenetic trophic shifts. In addition, chemical transects across multiple scales from the same individual were highly consistent, suggesting that any non-regenerated scale removed from a fish can provide equivalent time series. Continuous life history profiles of scales were obtained via laser ablation transects of scale cross-sections to quantify trace element concentrations from the core (youngest increments) to the edge (oldest increments). Stable isotope and trace element results together indicate that behavior is highly variable between individuals, with some but not all fish transiting estuarine gradients into oligohaline waters. Our findings will provide novel opportunities to investigate alternative non-lethal methods to monitor fish migrations across chemical gradients.

Novel isotopic N, N-Dimethyl Leucine (iDiLeu) Reagents Enable Absolute Quantification of Peptides and Proteins Using a Standard Curve Approach

NASA Astrophysics Data System (ADS)

Greer, Tyler; Lietz, Christopher B.; Xiang, Feng; Li, Lingjun

2015-01-01

Absolute quantification of protein targets using liquid chromatography-mass spectrometry (LC-MS) is a key component of candidate biomarker validation. One popular method combines multiple reaction monitoring (MRM) using a triple quadrupole instrument with stable isotope-labeled standards (SIS) for absolute quantification (AQUA). LC-MRM AQUA assays are sensitive and specific, but they are also expensive because of the cost of synthesizing stable isotope peptide standards. While the chemical modification approach using mass differential tags for relative and absolute quantification (mTRAQ) represents a more economical approach when quantifying large numbers of peptides, these reagents are costly and still suffer from lower throughput because only two concentration values per peptide can be obtained in a single LC-MS run. Here, we have developed and applied a set of five novel mass difference reagents, isotopic N, N-dimethyl leucine (iDiLeu). These labels contain an amine reactive group, triazine ester, are cost effective because of their synthetic simplicity, and have increased throughput compared with previous LC-MS quantification methods by allowing construction of a four-point standard curve in one run. iDiLeu-labeled peptides show remarkably similar retention time shifts, slightly lower energy thresholds for higher-energy collisional dissociation (HCD) fragmentation, and high quantification accuracy for trypsin-digested protein samples (median errors <15%). By spiking in an iDiLeu-labeled neuropeptide, allatostatin, into mouse urine matrix, two quantification methods are validated. The first uses one labeled peptide as an internal standard to normalize labeled peptide peak areas across runs (<19% error), whereas the second enables standard curve creation and analyte quantification in one run (<8% error).

Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry

USGS Publications Warehouse

Thurman, E.M.; Zimmerman, L.R.; Aga, D.S.; Gilliom, R.J.

2001-01-01

Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deutemted 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (<0.05 ??g/L) to 3.77 ??g/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

Potential impact of releases from a new Molybdenum-99 production facility on regional measurements of airborne xenon isotopes

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

Bowyer, Ted W.; Eslinger, Paul W.; Cameron, Ian M.

2014-03-01

The monitoring of the radioactive xenon isotopes 131mXe, 133Xe, 133mXe, and 135Xe is important for the detection of nuclear explosions. While backgrounds of the xenon isotopes are short-lived, they are constantly replenished from activities dominated by the fission-based production of 99Mo used for medical procedures. One of the most critical locations on earth for the monitoring of nuclear explosions is the Korean peninsula, where the Democratic Republic of North Korea (DPRK) has announced that it had conducted three nuclear tests between 2009 and 2013. This paper explores the backgrounds that would be caused by the medium to large scale productionmore » of 99Mo in the region of the Korean peninsula.« less

Development of a QuEChERS-Based Stable-Isotope Dilution LC-MS/MS Method To Quantitate Ferulic Acid and Its Main Microbial and Hepatic Metabolites in Milk.

PubMed

Waterstraat, Martin; Hildebrand, Andreas; Rosler, Margit; Bunzel, Mirko

2016-11-16

Forage plants of the Poaceae family are grown as pasturage or used for the production of hay, straw, corn stover, etc. Although ferulic acid contents of grasses are generally high, the amount of ingested ferulic acid differs depending on the type of forage, resulting in varying contents of ferulic acid and its microbial and hepatic metabolites in milk. Concentrations and patterns of these metabolites may be used as markers to track different forages in livestock feeding. Therefore, we developed a stable isotope dilution assay to quantitate ferulic acid, 12 ferulic acid-based metabolites, p-coumaric acid, and cinnamic acid in milk. Because most analytes were not commercially available as stable isotope labeled standard compounds, they were synthesized as 13 C- or deuterium-labeled standard compounds. A modification of the QuEChERS method, a Quick, Easy, Cheap, Effective, Rugged, and Safe approach usually applied to analyze pesticides in plant-based products, was used to extract the phenolic acids from milk. Determination was carried out by LC-ESI-MS/MS in scheduled multiple reaction monitoring modus. By using three different milk samples, the applicability of the validated approach was demonstrated.

Charge radii and electromagnetic moments of At-211195

NASA Astrophysics Data System (ADS)

Cubiss, J. G.; Barzakh, A. E.; Seliverstov, M. D.; Andreyev, A. N.; Andel, B.; Antalic, S.; Ascher, P.; Atanasov, D.; Beck, D.; Bieroń, J.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Derkx, X.; De Witte, H.; Elseviers, J.; Fedorov, D. V.; Fedosseev, V. N.; Fritzsche, S.; Gaffney, L. P.; George, S.; Ghys, L.; Heßberger, F. P.; Huyse, M.; Imai, N.; Kalaninová, Z.; Kisler, D.; Köster, U.; Kowalska, M.; Kreim, S.; Lane, J. F. W.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Marsh, B. A.; Mitsuoka, S.; Molkanov, P. L.; Nagame, Y.; Neidherr, D.; Nishio, K.; Ota, S.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Revill, J. P.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Sandhu, K.; Schweikhard, L.; Sels, S.; Truesdale, V. L.; Van Beveren, C.; Van den Bergh, P.; Wakabayashi, Y.; Van Duppen, P.; Wendt, K. D. A.; Wienholtz, F.; Whitmore, B. W.; Wilson, G. L.; Wolf, R. N.; Zuber, K.

2018-05-01

Hyperfine-structure parameters and isotope shifts of At-211195 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α -decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At,199197, for which a significant difference in the charge radii for ground (9 /2- ) and isomeric (1 /2+ ) states has been observed.

Monitoring in situ biodegradation of benzene and toluene by stable carbon isotope fractionation.

PubMed

Vieth, Andrea; Kästner, Matthias; Schirmer, Mario; Weiss, Holger; Gödeke, Stefan; Meckenstock, Rainer U; Richnow, Hans H

2005-01-01

Intrinsic biodegradation of benzene and toluene in a heavily contaminated aquifer at the site of a former hydrogenation plant was investigated by means of isotope fractionation processes. The carbon isotope compositions of benzene and toluene were monitored in two campaigns within a time period of 12 months to assess the extent of the in situ biodegradation and the stability of the plume over time. The Rayleigh model, applied to calculate the extent of biodegradation and residual theoretical concentrations of toluene, showed that in situ biodegradation was a relevant attenuation process. The biodegradation rate constant for toluene was estimated to be k = 5.7+/-0.5 microM/d in the groundwater flow path downstream of the source area. The spatial distribution of the carbon isotope composition of benzene indicated that in situ biodegradation occurred at marginal zones of the plume where concentrations were lower than 30 mg/L. The vertical structure of the benzene plume provided evidence for in situ degradation processes at the upper and lower fringes of the plume. The results show that isotope fractionation can be used to quantify the extent of microbial in situ degradation in contaminated aquifers and to develop conceptual models for natural attenuation approaches.

Ionization enhancement in atmospheric pressure chemical ionization and suppression in electrospray ionization between target drugs and stable-isotope-labeled internal standards in quantitative liquid chromatography/tandem mass spectrometry.

PubMed

Liang, H R; Foltz, R L; Meng, M; Bennett, P

2003-01-01

The phenomena of ionization suppression in electrospray ionization (ESI) and enhancement in atmospheric pressure chemical ionization (APCI) were investigated in selected-ion monitoring and selected-reaction monitoring modes for nine drugs and their corresponding stable-isotope-labeled internal standards (IS). The results showed that all investigated target drugs and their co-eluting isotope-labeled IS suppress each other's ionization responses in ESI. The factors affecting the extent of suppression in ESI were investigated, including structures and concentrations of drugs, matrix effects, and flow rate. In contrast to the ESI results, APCI caused seven of the nine investigated target drugs and their co-eluting isotope-labeled IS to enhance each other's ionization responses. The mutual ionization suppression or enhancement between drugs and their isotope-labeled IS could possibly influence assay sensitivity, reproducibility, accuracy and linearity in quantitative liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, calibration curves were linear if an appropriate IS concentration was selected for a desired calibration range to keep the response factors constant. Copyright 2003 John Wiley & Sons, Ltd.

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/1H ratios in CH4. Here, based on HIGHGAS project results, we present OTSs for atmospheric CO2 and CO measurements. The results delivered by the OTSs are in excellent agreement with gravimetric values of metrological "primary" static gas standards. The repeatabilities of the OTS results are matching the compatibility goals stated by WMO for atmospheric CO2 and CO measurements. In addition, we present OIRS measurement methods and procedures to demonstrate their applicability and validation. The requirements on, e.g. absorption line data quality and temperature sensitivity of isotope ratio, are discussed. Uncertainty budgets are presented and the traceability of the results is addressed. The current limitations in our measurements are discussed and steps taken to address these limitations are presented. 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] EMRP project ENV52-HIGHGAS, available at: http://www.euramet.org/ [2] Prosenjit Ghosh, Willi A. Brand, International Journal of Mass Spectrometry 228, 1-33 (2003).

Estrogens in seminal plasma of human and animal species: identification and quantitative estimation by gas chromatography-mass spectrometry associated with stable isotope dilution.

PubMed

Reiffsteck, A; Dehennin, L; Scholler, R

1982-11-01

Estrone, 2-methoxyestrone and estradiol-17 beta have been definitely identified in seminal plasma of man, bull, boar and stallion by high resolution gas chromatography associated with selective monitoring of characteristic ions of suitable derivatives. Quantitative estimations were performed by isotope dilution with deuterated analogues and by monitoring molecular ions of trimethylsilyl ethers of labelled and unlabelled compounds. Concentrations of unconjugated and total estrogens are reported together with the statistical evaluation of accuracy and precision.

Monitoring of tritium

DOEpatents

Corbett, James A.; Meacham, Sterling A.

1981-01-01

The fluid from a breeder nuclear reactor, which may be the sodium cooling fluid or the helium reactor-cover-gas, or the helium coolant of a gas-cooled reactor passes over the portion of the enclosure of a gaseous discharge device which is permeable to hydrogen and its isotopes. The tritium diffused into the discharge device is radioactive producing beta rays which ionize the gas (argon) in the discharge device. The tritium is monitored by measuring the ionization current produced when the sodium phase and the gas phase of the hydrogen isotopes within the enclosure are in equilibrium.

Operation and reactivity measurements of an accelerator driven subcritical TRIGA reactor

NASA Astrophysics Data System (ADS)

O'Kelly, David Sean

Experiments were performed at the Nuclear Engineering Teaching Laboratory (NETL) in 2005 and 2006 in which a 20 MeV linear electron accelerator operating as a photoneutron source was coupled to the TRIGA (Training, Research, Isotope production, General Atomics) Mark II research reactor at the University of Texas at Austin (UT) to simulate the operation and characteristics of a full-scale accelerator driven subcritical system (ADSS). The experimental program provided a relatively low-cost substitute for the higher power and complexity of internationally proposed systems utilizing proton accelerators and spallation neutron sources for an advanced ADSS that may be used for the burning of high-level radioactive waste. Various instrumentation methods that permitted ADSS neutron flux monitoring in high gamma radiation fields were successfully explored and the data was used to evaluate the Stochastic Pulsed Feynman method for reactivity monitoring.

Simultaneous determination of nine neonicotinoids in human urine using isotope-dilution ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Zhang, Quan; Wang, Ximing; Li, Zhe; Jin, Hangbiao; Lu, Zhengbiao; Yu, Chang; Huang, Yu-Fang; Zhao, Meirong

2018-05-14

Neonicotinoids (neonics), a class of systemic insecticides, have been frequently detected in pollen, vegetables, and fruits. Recently, an increasing concern has been aroused for human exposure to neonics. However, biological monitoring for quantifying body burden of neonics has rarely been reported. In this study, we developed an isotope-dilution ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) method to simultaneously quantify nine neonics, including acetamiprid (ACE), thiamethoxam (THIAM), imidacloprid (IMIP), clothianidin (CLO), flonicamid (FLO), thiacloprid (THIAC), dinotefuran (DIN), nitenpyram (NIT), and imidaclothiz (IMIT) in urine. The limits of quantification were 0.1 μg/L for ACE, FLO, DIN, NIT and IMIT, and 0.2 μg/L for THIAM, IMIP, CLO, and THIAC. The overall recoveries were 80.8-103%, 81.5-91.7% and 83.0-92.3% for QA/QC samples fortifying at 1, 25, and 100 μg/L levels, respectively. UPLC/MS/MS method was used to analyze urine samples obtained from 10 children in Hangzhou, China. The detection frequencies were 80% for ACE and IMIP, 70% for THIAM and CLO, 20% for DIN and IMIT and 10% for THIAC. FLO and NIT were not detected in those urine samples. The data provided here will be helpful for conducting biological monitoring of neonics exposure in the future. Copyright © 2018 Elsevier Ltd. All rights reserved.

Natural calcium isotonic composition of urine as a marker of bone mineral balance

USGS Publications Warehouse

Skulan, J.; Bullen, T.; Anbar, A.D.; Puzas, J.E.; Shackelford, L.; LeBlanc, A.; Smith, S.M.

2007-01-01

Background: We investigated whether changes in the natural isotopic composition of calcium in human urine track changes in net bone mineral balance, as predicted by a model of calcium isotopic behavior in vertebrates. If so, isotopic analysis of natural urine or blood calcium could be used to monitor short-term changes in bone mineral balance that cannot be detected with other techniques. Methods: Calcium isotopic compositions are expressed as ??44Ca, or the difference in parts per thousand between the 44Ca/40Ca of a sample and the 44Ca/ 40Ca of a standard reference material. ??44Ca was measured in urine samples from 10 persons who participated in a study of the effectiveness of countermeasures to bone loss in spaceflight, in which 17 weeks of bed rest was used to induce bone loss. Study participants were assigned to 1 of 3 treatment groups: controls received no treatment, one treatment group received alendronate, and another group performed resistive exercise. Measurements were made on urine samples collected before, at 2 or 3 points during, and after bed rest. Results: Urine ??44Ca values during bed rest were lower in controls than in individuals treated with alendronate (P <0.05, ANOVA) or exercise (P <0.05), and lower than the control group baseline (P <0.05, Mest). Results were consistent with the model and with biochemical and bone mineral density data. Conclusion: Results confirm the predicted relationship between bone mineral balance and calcium isotopes, suggesting that calcium isotopic analysis of urine might be refined into a clinical and research tool. ?? 2007 American Association for Clinical Chemistry.

222Rn+220Rn monitoring by alpha spectrometry.

PubMed

Buompane, R; Roca, V; Sabbarese, C; Pugliese, M; Quarto, M; Mattone, C

2014-07-01

Controlled 222Rn+220Rn mixed atmospheres have been realised introducing calibrated sources in a stainless steel chamber. An electrostatic alpha monitor internal to the chamber has been used for an accurate discrimination of alpha peaks due to the products of the two isotopes. In the chamber, different specific activities are achieved in order to test the response of the internal reference instrument and to evaluate the possible interferences due to contemporary presence of both radon isotopes. Results show that: (i) the atmospheres are very stable, (ii) the monitor is adequate for their control because the various alpha lines are well evaluated and (iii) using Tyvek® filter, the efficiency of monitor is stable and constant vs. activity. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

MONITORING FOOD WEB CHANGES IN TIDE-RESTORED SALT MARSHES: A CARBON STABLE ISOTOPE APPROACH

EPA Science Inventory

Primary producer (angiosperms, macroalgae, submerged aquatic vegetation), suspended particulate matter, and Fundulus heteroclitus isotope values (d13C , d15N, d34S) were examined to assess their use as an indicator for changes in food web support functions in tidally-restored sal...

APPLICATION OF STABLE CARBON AND HYDROGEN ISOTOPIC TECHNIQUES FOR MONITORING BIODEGRADATION OF MTBE IN THE FIELD

EPA Science Inventory

A significant challenge in environmental studies is to determine the onset and extent of MTBE bioremediation at an affected site, which may involve indirect approaches such as microcosm verification of microbial activities at a given site. Stable isotopic fractionation is cha...

Measurement of stable isotopic enrichment and concentration of long-chain fatty acyl-carnitines in tissue by HPLC-MS.

PubMed

Sun, Dayong; Cree, Melanie G; Zhang, Xiao-Jun; Bøersheim, Elisabet; Wolfe, Robert R

2006-02-01

We have developed a new method for the simultaneous measurements of stable isotopic tracer enrichments and concentrations of individual long-chain fatty acyl-carnitines in muscle tissue using ion-pairing high-performance liquid chromatography-electrospray ionization quadrupole mass spectrometry in the selected ion monitoring (SIM) mode. Long-chain fatty acyl-carnitines were extracted from frozen muscle tissue samples by acetonitrile/methanol. Baseline separation was achieved by reverse-phase HPLC in the presence of the volatile ion-pairing reagent heptafluorobutyric acid. The SIM capability of a single quadrupole mass analyzer allows further separation of the ions of interest from the sample matrixes, providing very clean total and selected ion chromatograms that can be used to calculate the stable isotopic tracer enrichment and concentration of long-chain fatty acyl-carnitines in a single analysis. The combination of these two separation techniques greatly simplifies the sample preparation procedure and increases the detection sensitivity. Applying this protocol to biological muscle samples proves it to be a very sensitive, accurate, and precise analytical tool.

Monitoring the hydrothermal system in Long Valley caldera, California

USGS Publications Warehouse

Farrar, C.D.; Sorey, M.L.

1985-01-01

An ongoing program to monitor the hydrothermal system in Long Valley for changes caused by volcanic or tectonic processes has produced considerable data on the water chemistry and discharge of springs and fluid temperatures and pressures in wells. Chemical and isotopic data collected under this program have greatly expanded the knowledge of chemical variability both in space and time. Although no chemical or isotopic changes in hot spring waters can be attributed directly to volcanic or tectonic processes, changes in hot spring chemistry that have been recorded probably relate to interactions between and variations in the quantity of liquid and gas discharged. Stable carbon isotope data are consistent with a carbon source either perform the mantle or from metamorphosed carbonate rocks. Continuous and periodic measurements of hot spring discharge at several sites show significant co seismic and a seismic changes since 1980.

Method for enriching a middle isotope using vibration-vibration pumping

DOEpatents

Rich, Joseph W.; Homicz, Gregory F.; Bergman, Richard C.

1989-01-01

Method for producing isotopically enriched material by vibration-vibration excitation of gaseous molecules wherein a middle mass isotope of an isotopic mixture including lighter and heavier mass isotopes preferentially populates a higher vibrational mode and chemically reacts to provide a product in which it is enriched. The method can be used for vibration-vibration enrichment of .sup.17 O in a CO reactant mixture.

Study of medical isotope production facility stack emissions and noble gas isotopic signature using automatic gamma-spectra analysis platform

NASA Astrophysics Data System (ADS)

Zhang, Weihua; Hoffmann, Emmy; Ungar, Kurt; Dolinar, George; Miley, Harry; Mekarski, Pawel; Schrom, Brian; Hoffman, Ian; Lawrie, Ryan; Loosz, Tom

2013-04-01

The nuclear industry emissions of the four CTBT (Comprehensive Nuclear-Test-Ban Treaty) relevant radioxenon isotopes are unavoidably detected by the IMS along with possible treaty violations. Another civil source of radioxenon emissions which contributes to the global background is radiopharmaceutical production companies. To better understand the source terms of these background emissions, a joint project between HC, ANSTO, PNNL and CRL was formed to install real-time detection systems to support 135Xe, 133Xe, 131mXe and 133mXe measurements at the ANSTO and CRL 99Mo production facility stacks as well as the CANDU (CANada Deuterium Uranium) primary coolant monitoring system at CRL. At each site, high resolution gamma spectra were collected every 15 minutes using a HPGe detector to continuously monitor a bypass feed from the stack or CANDU primary coolant system as it passed through a sampling cell. HC also conducted atmospheric monitoring for radioxenon at approximately 200 km distant from CRL. A program was written to transfer each spectrum into a text file format suitable for the automatic gamma-spectra analysis platform and then email the file to a server. Once the email was received by the server, it was automatically analysed with the gamma-spectrum software UniSampo/Shaman to perform radionuclide identification and activity calculation for a large number of gamma-spectra in a short period of time (less than 10 seconds per spectrum). The results of nuclide activity together with other spectrum parameters were saved into the Linssi database. This database contains a large amount of radionuclide information which is a valuable resource for the analysis of radionuclide distribution within the noble gas fission product emissions. The results could be useful to identify the specific mechanisms of the activity release. The isotopic signatures of the various radioxenon species can be determined as a function of release time. Comparison of 133mXe and 133Xe activity ratios showed distinct differences between the closed CANDU primary coolant system and radiopharmaceutical production releases. According to the concept proposed by Kalinowski and Pistner (2006), the relationship between different isotopic activity ratios based on three or four radioxenon isotopes was plotted in a log-log diagram for source characterisation (civil vs. nuclear test). The multiple isotopic activity ratios were distributed in three distinct areas: HC atmospheric monitoring ratios extended to far left; the CANDU primary coolant system ratios lay in the middle; and 99Mo stack monitoring ratios for ANSTO and CRL were located on the right. The closed CANDU primary coolant has the lowest logarithmic mean ratio that represents the nuclear power reactor operation. The HC atmospheric monitoring exhibited a broad range of ratios spreading over several orders of magnitude. In contrast, the ANSTO and CRL stack emissions showed the smallest range of ratios but the results indicate at least two processes involved in the 99Mo productions. Overall, most measurements were found to be shifted towards the reactor domain. The hypothesis is that this is due to an accumulation of the isotope 131mXe in the stack or atmospheric background as it has the longest half-life and extra 131mXe emissions from the decay of 131I. The contribution of older 131mXe to a fresh release shifts the ratio of 133mXe/131mXe to the left. It was also very interesting to note that there were some situations where isotopic ratios from 99Mo production emissions fell within the nuclear test domain. This is due to operational variability, such as shorter target irradiation times. Martin B. Kalinowski and Christoph Pistner, (2006), Isotopic signature of atmospheric xenon released from light water reactors, Journal of Environmental Radioactivity, 88, 215-235.

Detecting the leakage source of a reservoir using isotopes.

PubMed

Yi, Peng; Yang, Jing; Wang, Yongdong; Mugwanezal, Vincent de Paul; Chen, Li; Aldahan, Ala

2018-07-01

A good monitoring method is vital for understanding the sources of a water reservoir leakage and planning for effective restoring. Here we present a combination of several tracers ( 222 Rn, oxygen and hydrogen isotopes, anions and temperature) for identification of water leakage sources in the Pushihe pumped storage power station which is in the Liaoning province, China. The results show an average 222 Rn activity of 6843 Bq/m 3 in the leakage water, 3034 Bq/m 3 in the reservoir water, and 41,759 Bq/m 3 in the groundwater. Considering that 222 Rn activity in surface water is typically less than 5000 Bq/m 3 , the low level average 222 Rn activity in the leakage water suggests the reservoir water as the main source of water. Results of the oxygen and hydrogen isotopes show comparable ranges and values in the reservoir and the leakage water samples. However, important contribution of the groundwater (up to 36%) was present in some samples from the bottom and upper parts of the underground powerhouse, while the leakage water from some other parts indicate the reservoir water as the dominant source. The isotopic finding suggests that the reservoir water is the main source of the leakage water which is confirmed by the analysis of anions (nitrate, sulfate, and chloride) in the water samples. The combination of these tracer methods for studying dam water leakage improves the accuracy of identifying the source of leaks and provide a scientific reference for engineering solutions to ensure the dam safety. Copyright © 2018 Elsevier Ltd. All rights reserved.

A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

NASA Astrophysics Data System (ADS)

Ghosh, S.; Odom, A. L.

2007-12-01

Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg ratio of 1.11 is predicted by isotope fractionation due to the Magnetic Isotope Effect (MIE), because 1.11 is the ratio of the magnetic moments of the two odd-N isotopes. A plot of Δ199Hg versus Δ201Hg values obtained reveals a striking pattern. All samples plot well within analytical uncertainly along a straight line passing through zero and having a slope of 1.11. Based on thermodynamic principles, some have argued that nuclear spin effects are quite insignificant in producing isotopic fractionation. However the MIE is a kinetic one in which those isotopes with non-zero magnetic moments effect the rates of recombination of free radical pairs by nuclear-electron hyperfine interaction and can become enriched or depleted in either reactants or products. In the samples studied here, the nuclear spin is far more important than either nuclear mass or nuclear volume in effecting isotopic fractionation of Mercury.

Automatic identification approach for high-performance liquid chromatography-multiple reaction monitoring fatty acid global profiling.

PubMed

Tie, Cai; Hu, Ting; Jia, Zhi-Xin; Zhang, Jin-Lan

2015-08-18

Fatty acids (FAs) are a group of lipid molecules that are essential to organisms. As potential biomarkers for different diseases, FAs have attracted increasing attention from both biological researchers and the pharmaceutical industry. A sensitive and accurate method for globally profiling and identifying FAs is required for biomarker discovery. The high selectivity and sensitivity of high-performance liquid chromatography-multiple reaction monitoring (HPLC-MRM) gives it great potential to fulfill the need to identify FAs from complicated matrices. This paper developed a new approach for global FA profiling and identification for HPLC-MRM FA data mining. Mathematical models for identifying FAs were simulated using the isotope-induced retention time (RT) shift (IRS) and peak area ratios between parallel isotope peaks for a series of FA standards. The FA structures were predicated using another model based on the RT and molecular weight. Fully automated FA identification software was coded using the Qt platform based on these mathematical models. Different samples were used to verify the software. A high identification efficiency (greater than 75%) was observed when 96 FA species were identified in plasma. This FAs identification strategy promises to accelerate FA research and applications.

Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

NASA Astrophysics Data System (ADS)

Suchopár, M.; Wagner, V.; Svoboda, O.; Vrzalová, J.; Chudoba, P.; Tichý, P.; Kugler, A.; Adam, J.; Závorka, L.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunnikov, S.; Bielewicz, M.; Kilim, S.; Strugalska-Gola, E.; Szuta, M.

2017-03-01

The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW) performed intensive studies of several simple accelerator-driven system (ADS) setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

Monitoring Natural Biodegradation of TCE in Fractured Sedimentary Rocks Using delta 13C of TCE and its Degradation Products: Estimating Isotopic Fractionation Factor under Field Conditions

NASA Astrophysics Data System (ADS)

Revesz, K.; Shapiro, A. M.; Tiedeman, C.; Goode, D. J.; Lacombe, P. J.; Imbrigiotta, T. E.

2008-12-01

The isotopic ratio of 13C/12C, expressed in delta13CVPDB per mill for trichloroethene (TCE), can differentiate between microbial degradation and other processes (dilution, dispersion, and sorption) that can also affect the concentration of TCE and its degradation products. The delta13C of TCE isotopically fractionates during microbial degradation; however, it remains practically unchanged during other processes. The isotope fractionation factor (alpha) estimated under laboratory conditions, however, may not be representative of microbial degradation in natural ground waters. Estimating alpha under field conditions provides evidence of the presence or absence of in situ microbial degradation and provides valuable information on the in situ processes that affect the fate and transport of chlorinated hydrocarbons. Our modified analytical method of analyzing for the isotopic ratio proved to be comparable to previously published methods. Isotope values were stable within analytical uncertainty in sample sizes ranging from 22 to 2200 nanomoles. Prepared standard mixtures of TCE and DCEs (trans- and cis- dichloroethene) were analyzed after every five field samples, and were stable during the time period that field samples were processed (a year). Water samples were collected from multiple boreholes completed in the fractured mudstone underlying the former Naval Air Warfare Center, West Trenton, NJ, and analyzed for delta13C of the chlorinated hydrocarbons. The results showed an ongoing natural microbial degradation following the typical dehalogenation pathway: TCE to DCE (trans- and cis-dichloroethene) to VC (vinyl chloride). The carbon isotope enrichment due to fractionation was smaller between TCE to DCE degradation than the enrichment between DCE to VC degradation, which is consistent with previous investigations. Results also showed a correlation between delta13C of TCE and the transmissivity of the boreholes where water samples were collected. We assumed that boreholes with extremely low transmissivity behaved analogously to microbial batch reactors. The value of alpha obtained from the borehole interval with the lowest transmissivity was 0.99345, which is in the range of published values: 0.9862 to 0.9934. We consider this value to represent the "field alpha" for microbial degradation in the absence of other processes. Values of alpha in other boreholes that differ from the field alpha could point to other processes affecting the delta13C and concentration of TCE. The value of alpha from the various monitored intervals is referred to as the "apparent alpha". The apparent alpha is characteristic of the borehole and the time at which the concentrations and the isotope values were measured. The difference between the apparent alpha and the field alpha provides insight into hydrologic conditions around the well. Results from one well showed fluctuation in the TCE concentrations, which were correlated with the calculated apparent alpha, and pointed to the recent introduction of TCE into the ground water that had not been significantly degraded. Recent drilling in the vicinity of this well may have remobilized free-phase TCE.

A new combined method of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in rat brain microdialysates by ultra high performance liquid chromatography tandem mass spectrometry.

PubMed

Zheng, Longfang; Zhao, Xian-En; Zhu, Shuyun; Tao, Yanduo; Ji, Wenhua; Geng, Yanling; Wang, Xiao; Chen, Guang; You, Jinmao

2017-06-01

In this work, for the first time, a new hyphenated technique of stable isotope-labeling derivatization-ultrasound-assisted dispersive liquid-liquid microextraction has been developed for the simultaneous determination of monoamine neurotransmitters (MANTs) and their biosynthesis precursors and metabolites. The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry detection using multiple-reaction monitoring mode. A pair of mass spectrometry sensitizing reagents, d 0 -10-methyl-acridone-2-sulfonyl chloride and d 3 -10-methyl-acridone-2-sulfonyl chloride, as stable isotope probes was utilized to facilely label neurotransmitters, respectively. The heavy labeled MANTs standards were prepared and used as internal standards for quantification to minimize the matrix effects in mass spectrometry analysis. Low toxic bromobenzene (extractant) and acetonitrile (dispersant) were utilized in microextraction procedure. Under the optimized conditions, good linearity was observed with the limits of detection (S/N>3) and limits of quantification (S/N>10) in the range of 0.002-0.010 and 0.015-0.040nmol/L, respectively. Meanwhile, it also brought acceptable precision (4.2-8.8%, peak area RSDs %) and accuracy (recovery, 96.9-104.1%) results. This method was successfully applied to the simultaneous determination of monoamine neurotransmitters and their biosynthesis precursors and metabolites in rat brain microdialysates of Parkinson's disease and normal rats. This provided a new method for the neurotransmitters related studies in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Use of Sensitive and Specific Biomolecular and Mass Spectrometric Techniques to Monitor the Performance of In-Situ Hydrocarbon Biodegradation

NASA Astrophysics Data System (ADS)

Beller, H. R.; Kane, S. R.; Legler, T. C.

2008-12-01

Monitored natural attenuation (MNA) can be a cost-effective and viable approach for remediation of hydrocarbon-contaminated groundwater. However, regulatory acceptance of the approach is often contingent on monitoring that can convincingly demonstrate the role of microbial degradation. Recent advances in anaerobic hydrocarbon biochemistry, analytical chemistry, and molecular biology have fostered the development of powerful techniques that can be applied to MNA of BTEX (benzene, toluene, ethylbenzene, and xylenes). Here, I discuss two independent methods that have been developed to monitor in situ, anaerobic biodegradation of toluene and xylenes. A method has been developed for rapid, sensitive, and highly selective detection of distinctive indicators of anaerobic alkylbenzene metabolism. The target metabolites, benzylsuccinic acid and methylbenzylsuccinic acid isomers, have no known sources other than anaerobic toluene or xylene degradation; thus, their mere presence in groundwater provides definitive evidence of in situ metabolism. The method, which involves small sample size (<1 mL) and no extraction/concentration steps, relies on isotope dilution liquid chromatography/tandem mass spectrometry (LC/MS/MS) with selected reaction monitoring. Detection limits for benzylsuccinates were determined to be ca. 0.3 μg/L and accuracy and precision were favorable in a groundwater matrix. A monitoring method based on quantitative Polymerase Chain Reaction (qPCR) analysis has been developed to specifically quantify populations of anaerobic methylbenzene-degrading bacteria in aquifer sediment. The method targets a catabolic gene (bssA) associated with the first step of anaerobic toluene and xylene degradation. The method has proven to be sensitive (detection limit ca. 5 gene copies) and has a linear range of > 7 orders of magnitude. Application of these two methods in field studies will be discussed in the context of the methods' strengths and limitations. Field data will include a side-by-side comparison of the two methods during a controlled release of BTX and ethanol, simulating release of gasohol from a leaking underground storage tank.

Monitoring steel bridge renovation using lead isotopic tracing.

PubMed

Salome, Fred; Gulson, Brian; Chiaradia, Massimo; Davis, Jeffrey; Morris, Howard

2017-05-01

Monitoring removal of lead (Pb) paint from steel structures usually involves analysis of environmental samples for total lead and determination of blood Pb levels of employees involved in the Pb paint removal. We used high precision Pb isotopic tracing for a bridge undergoing Pb paint removal to determine if Pb in the environmental and blood samples originated from the bridge paint. The paint system on the bridge consisted of an anti-corrosive red Pb primer top-coated with a Micaceous Iron Oxide (MIO) alkyd. Analysis of the red Pb primer gave uniform isotopic ratios indicative of Pb from the geologically-ancient Broken Hill mines in western New South Wales, Australia. Likewise waste abrasive material, as anticipated, had the same isotopic composition as the paint. The isotopic ratios for other samples lay on 2 separate linear arrays on a 207 Pb/ 204 Pb versus 206 Pb/ 204 Pb diagram, one largely defined by gasoline and the majority of the ambient air data, and the other by data for one sample each of gasoline and ambient air and underwater sediments. Isotopic ratios in background ambient air samples for the project were characteristic of leaded gasoline. Air sampling during paint removal showed a contribution of paint Pb ranging from about 20 to 40%. Isotopic ratios in the blood of 8 employees prior to the commencement of work showed that 6 of these had been previously exposed to the Broken Hill Pb possibly from earlier bridge paint removal projects. One subject appeared to have increased exposure to Pb probably from the paint renovations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Using 2H and 18O in assessing evaporation and water residence time of lakes in EPA’s National Lakes Assessment.

EPA Science Inventory

Stable isotopes of water and organic material can be very useful in monitoring programs because stable isotopes integrate information about ecological processes and record this information. Most ecological processes of interest for water quality (i.e. denitrification) require si...

Stable Isotope Mixing Models as a Tool for Tracking Sources of Water and Water Pollutants

EPA Science Inventory

One goal of monitoring pollutants is to be able to trace the pollutant to its source. Here we review how mixing models using stable isotope information on water and water pollutants can help accomplish this goal. A number of elements exist in multiple stable (non-radioactive) i...

Stable isotope analysis of stream organisms - a useful tool for monitoring changes in catchment conditions and effects on stream ecosystems?

EPA Science Inventory

Stable isotope analyses of stream organisms usually are performed as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

Stable Isotope Analysis of stream organisms -- a potential tool for monitoring changes in catchment conditions and effects on stream ecosystems

EPA Science Inventory

Stable isotope analyses of stream organisms are performed usually as discrete site experiments (e.g., to study the effect of a direct manipulation), synoptically (e.g. to illustrate effects of longitudinal variation of influencing factors), or, less frequently, over the course of...

UTILIZATION OF THE CARBON AND HYDROGEN ISOTOPIC COMPOSITION OF INDIVIDUAL COMPOUNDS IN REFINED HYDROCARBON PRODUCTS TO MONITOR THEIR FATE IN THE ENVIRONMENT

EPA Science Inventory

Isotope effects resulting from biodegradation of MTBE
To conduct the microcosm biodegradation study, sediment samples were collected from sites offering high potential of MTBE biodegradation. Sites where sediment samples were collected for the MTBE microcosm c...

A novel method for the quantitation of gingerol glucuronides in human plasma or urine based on stable isotope dilution assays.

PubMed

Schoenknecht, Carola; Andersen, Gaby; Schieberle, Peter

2016-11-15

The bio-active compounds of ginger (Zingiber officinale Roscoe), the gingerols, are gaining considerable attention due to their numerous beneficial health effects. In order to elucidate the physiological relevance of the ascribed effects their bioavailability has to be determined taking their metabolization into account. To quantitate in vivo generated [6]-, [8]- and [10]-gingerol glucuronides in human plasma and urine after ginger tea consumption, a simultaneous and direct liquid chromatography-tandem mass spectrometry method based on stable isotope dilution assays was established and validated. The respective references as well as the isotopically labeled substances were synthesized and characterized by mass spectrometry and NMR. Selective isolation of gingerol glucuronides from human plasma and urine by a mixed-phase anion-exchange SPE method led to recovery rates between 80.8 and 98.2%. LC-MS/MS analyses in selected reaction monitoring modus enabled a highly sensitive quantitation of gingerol glucuronides with LoQs between 3.9-9.8nmol/L in plasma and 39.3-161.1nmol/L in urine. The method precision in plasma and urine varied in the range±15%, whereas the intra-day accuracy in plasma and urine showed values between 78 and 122%. The developed method was then applied to a pilot study in which two volunteers consumed one liter ginger tea. Pharmacokinetic parameters like the maximum concentration (c max ), the time to reach c max (t max ), area under the curve (AUC), elimination rate constant (k el ) and elimination half-life (t 1/2 ) were calculated from the concentration-time curve of each gingerol glucuronide. The obtained results will enable more detailed investigation of gingerol glucuronides as bioactives in their physiologically relevant concentrations. Copyright © 2016 Elsevier B.V. All rights reserved.

Isotope separation by photochromatography

DOEpatents

Suslick, Kenneth S.

1977-01-01

An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations

NASA Astrophysics Data System (ADS)

Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.

2016-05-01

Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic (δ13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

Statistical characterization of multiple-reaction monitoring mass spectrometry (MRM-MS) assays for quantitative proteomics

PubMed Central

2012-01-01

Multiple reaction monitoring mass spectrometry (MRM-MS) with stable isotope dilution (SID) is increasingly becoming a widely accepted assay for the quantification of proteins and peptides. These assays have shown great promise in relatively high throughput verification of candidate biomarkers. While the use of MRM-MS assays is well established in the small molecule realm, their introduction and use in proteomics is relatively recent. As such, statistical and computational methods for the analysis of MRM-MS data from proteins and peptides are still being developed. Based on our extensive experience with analyzing a wide range of SID-MRM-MS data, we set forth a methodology for analysis that encompasses significant aspects ranging from data quality assessment, assay characterization including calibration curves, limits of detection (LOD) and quantification (LOQ), and measurement of intra- and interlaboratory precision. We draw upon publicly available seminal datasets to illustrate our methods and algorithms. PMID:23176545

Statistical characterization of multiple-reaction monitoring mass spectrometry (MRM-MS) assays for quantitative proteomics.

PubMed

Mani, D R; Abbatiello, Susan E; Carr, Steven A

2012-01-01

Multiple reaction monitoring mass spectrometry (MRM-MS) with stable isotope dilution (SID) is increasingly becoming a widely accepted assay for the quantification of proteins and peptides. These assays have shown great promise in relatively high throughput verification of candidate biomarkers. While the use of MRM-MS assays is well established in the small molecule realm, their introduction and use in proteomics is relatively recent. As such, statistical and computational methods for the analysis of MRM-MS data from proteins and peptides are still being developed. Based on our extensive experience with analyzing a wide range of SID-MRM-MS data, we set forth a methodology for analysis that encompasses significant aspects ranging from data quality assessment, assay characterization including calibration curves, limits of detection (LOD) and quantification (LOQ), and measurement of intra- and interlaboratory precision. We draw upon publicly available seminal datasets to illustrate our methods and algorithms.

Integrated modelling of enhanced in situ biodenitrification in a fractured aquifer: biogeochemistry and isotope geochemistry

NASA Astrophysics Data System (ADS)

Rodríguez-Escales, Paula; Folch, Albert; van Breukelen, Boris M.; Vidal-Gavilan, Georgina; Soler, Albert

2014-05-01

Enhanced in-situ biodenitrification is a feasible technology to recovery groundwater polluted by nitrates and achieves drinking water standards. Under optimum conditions, nitrate is reduced by autochthonous bacteria trough different reactions until arrive to harmless dinitrogen gas. Isotopic fractionation monitoring in field applications allows knowing the exact degree and the real scope of this technology. Using the Rayleigh equation the change in the isotope ratio of the nitrate molecule (δ15N-NO3-, δ18O-NO3-) is related to the fraction of molecules remaining as a result of biodenitrification. However, Rayleigh application at field scale is sometimes limited due to other processes involved during groundwater flow such as dispersion or adsorption and geological media heterogeneities that interferes in concentration values. Then, include isotope fractionation processes in reactive transport models is a useful tool to interpret and predict data from in-situ biodenitrification. We developed a reactive transport model of enhanced in situ application at field scale in a fractured aquifer that considers biogeochemical processes as well as isotope fractionation to enable better monitoring and management of this technology. Processes considered were: microbiological- exogenous and endogenous nitrate and sulfate respiration coupled with microbial growth and decay, geochemical reactions (precipitation of calcite) and isotopic fractionation (δ15N-NO3-; δ18O- NO3- and carbon isotope network). The 2-D simulations at field scale were developed using PHAST code. Modeling of nitrate isotope geochemistry has allowed determining the extent of biodenitrification in model domain. We have quantified which is the importance in decreasing of nitrate concentrations due to biodegradation (percentage of biodegradation, 'B%') and due to dilution process (percentage of dilution, 'D%'). On the other hand, the stable carbon isotope geochemistry has been modeled. We have considered the isotopic carbon fractionation of different carbon species involved in enhanced biodenitrification: external organic carbon, biomass, inorganic carbon (in different forms) and calcite. The inclusion of carbon isotopes in the model, which are involved in both direct (oxidation of organic carbon) and indirect (carbonate mineral interaction) processes of enhanced biodenitrification, improves the evaluation of the overall model consistency due to the central role of carbon in the reaction network.

Adélie Penguin Population Diet Monitoring by Analysis of Food DNA in Scats

PubMed Central

Jarman, Simon N.; McInnes, Julie C.; Faux, Cassandra; Polanowski, Andrea M.; Marthick, James; Deagle, Bruce E.; Southwell, Colin; Emmerson, Louise

2013-01-01

The Adélie penguin is the most important animal currently used for ecosystem monitoring in the Southern Ocean. The diet of this species is generally studied by visual analysis of stomach contents; or ratios of isotopes of carbon and nitrogen incorporated into the penguin from its food. There are significant limitations to the information that can be gained from these methods. We evaluated population diet assessment by analysis of food DNA in scats as an alternative method for ecosystem monitoring with Adélie penguins as an indicator species. Scats were collected at four locations, three phases of the breeding cycle, and in four different years. A novel molecular diet assay and bioinformatics pipeline based on nuclear small subunit ribosomal RNA gene (SSU rDNA) sequencing was used to identify prey DNA in 389 scats. Analysis of the twelve population sample sets identified spatial and temporal dietary change in Adélie penguin population diet. Prey diversity was found to be greater than previously thought. Krill, fish, copepods and amphipods were the most important food groups, in general agreement with other Adélie penguin dietary studies based on hard part or stable isotope analysis. However, our DNA analysis estimated that a substantial portion of the diet was gelatinous groups such as jellyfish and comb jellies. A range of other prey not previously identified in the diet of this species were also discovered. The diverse prey identified by this DNA-based scat analysis confirms that the generalist feeding of Adélie penguins makes them a useful indicator species for prey community composition in the coastal zone of the Southern Ocean. Scat collection is a simple and non-invasive field sampling method that allows DNA-based estimation of prey community differences at many temporal and spatial scales and provides significant advantages over alternative diet analysis approaches. PMID:24358158

Adélie penguin population diet monitoring by analysis of food DNA in scats.

PubMed

Jarman, Simon N; McInnes, Julie C; Faux, Cassandra; Polanowski, Andrea M; Marthick, James; Deagle, Bruce E; Southwell, Colin; Emmerson, Louise

2013-01-01

The Adélie penguin is the most important animal currently used for ecosystem monitoring in the Southern Ocean. The diet of this species is generally studied by visual analysis of stomach contents; or ratios of isotopes of carbon and nitrogen incorporated into the penguin from its food. There are significant limitations to the information that can be gained from these methods. We evaluated population diet assessment by analysis of food DNA in scats as an alternative method for ecosystem monitoring with Adélie penguins as an indicator species. Scats were collected at four locations, three phases of the breeding cycle, and in four different years. A novel molecular diet assay and bioinformatics pipeline based on nuclear small subunit ribosomal RNA gene (SSU rDNA) sequencing was used to identify prey DNA in 389 scats. Analysis of the twelve population sample sets identified spatial and temporal dietary change in Adélie penguin population diet. Prey diversity was found to be greater than previously thought. Krill, fish, copepods and amphipods were the most important food groups, in general agreement with other Adélie penguin dietary studies based on hard part or stable isotope analysis. However, our DNA analysis estimated that a substantial portion of the diet was gelatinous groups such as jellyfish and comb jellies. A range of other prey not previously identified in the diet of this species were also discovered. The diverse prey identified by this DNA-based scat analysis confirms that the generalist feeding of Adélie penguins makes them a useful indicator species for prey community composition in the coastal zone of the Southern Ocean. Scat collection is a simple and non-invasive field sampling method that allows DNA-based estimation of prey community differences at many temporal and spatial scales and provides significant advantages over alternative diet analysis approaches.

Prototyping of beam position monitor for medium energy beam transport section of RAON heavy ion accelerator

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

Jang, Hyojae, E-mail: lkcom@ibs.re.kr; Jin, Hyunchang; Jang, Ji-Ho

2016-02-15

A heavy ion accelerator, RAON is going to be built by Rare Isotope Science Project in Korea. Its target is to accelerate various stable ions such as uranium, proton, and xenon from electron cyclotron resonance ion source and some rare isotopes from isotope separation on-line. The beam shaping, charge selection, and modulation should be applied to the ions from these ion sources because RAON adopts a superconducting linear accelerator structure for beam acceleration. For such treatment, low energy beam transport, radio frequency quadrupole, and medium energy beam transport (MEBT) will be installed in injector part of RAON accelerator. Recently, developmentmore » of a prototype of stripline beam position monitor (BPM) to measure the position of ion beams in MEBT section is under way. In this presentation, design of stripline, electromagnetic (EM) simulation results, and RF measurement test results obtained from the prototyped BPM will be described.« less

Evaluation of positron emission tomography as a method to visualize subsurface microbial processes

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

Kinsella K.; Schlyer D.; Kinsella, K.

2012-01-18

Positron emission tomography (PET) provides spatiotemporal monitoring in a nondestructive manner and has higher sensitivity and resolution relative to other tomographic methods. Therefore, this technology was evaluated for its application to monitor in situ subsurface bacterial activity. To date, however, it has not been used to monitor or image soil microbial processes. In this study, PET imaging was applied as a 'proof-of-principle' method to assess the feasibility of visualizing a radiotracer labeled subsurface bacterial strain (Rahnella sp. Y9602), previously isolated from uranium contaminated soils and shown to promote uranium phosphate precipitation. Soil columns packed with acid-purified simulated mineral soils weremore » seeded with 2-deoxy-2-[{sup 18}F]fluoro-d-glucose ({sup 18}FDG) labeled Rahnella sp. Y9602. The applicability of [{sup 18}F]fluoride ion as a tracer for measuring hydraulic conductivity and {sup 18}FDG as a tracer to identify subsurface metabolically active bacteria was successful in our soil column studies. Our findings indicate that positron-emitting isotopes can be utilized for studies aimed at elucidating subsurface microbiology and geochemical processes important in contaminant remediation.« less

A New Method to Quantify the Isotopic Signature of Leaf Transpiration: Implications for Landscape-Scale Evapotranspiration Partitioning Studies

NASA Astrophysics Data System (ADS)

Wang, L.; Good, S. P.; Caylor, K. K.

2010-12-01

Characterizing the constituent components of evapotranspiration is crucial to better understand ecosystem-level water budgets and water use dynamics. Isotope based evapotranspiration partitioning methods are promising but their utility lies in the accurate estimation of the isotopic composition of underlying transpiration and evaporation. Here we report a new method to quantify the isotopic signature of leaf transpiration under field conditions. This method utilizes a commercially available laser-based isotope analyzer and a transparent leaf chamber, modified from Licor conifer leaf chamber. The method is based on the water mass balance in ambient air and leaf transpired air. We verified the method using “artificial leaves” and glassline extracted samples. The method provides a new and direct way to estimate leaf transpiration isotopic signatures and it has wide applications in ecology, hydrology and plant physiology.

Lead concentration and isotope chronology in two coastal environments in Western and South East Asia

NASA Astrophysics Data System (ADS)

Carrasco, G. G.; Chen, M.; Boyle, E. A.; Zhao, N.; Nurhati, I. S.; Gevao, B.; al Ghadban, A.; Switzer, A.; Lee, J. M.

2014-12-01

Lead is a trace metal that is closely related to anthropogenic activity, mainly via leaded gasoline and coal combustion. The study of lead concentrations and isotopes in seawater, sediments, corals and aerosols allows for a systematic look at its sources and their time evolution in a natural environment. We will discuss results from two projects in Western and South East Asia, regions that have seen dramatic socio-economical changes over the past half-century that may have left environmental signals. These results highlight the usefulness of the method, indicate the degree of complexity of these systems, and point to the need for a continuous monitoring of anthropogenic trace metals in the small-medium coastal scale to be able to asses the larger scale effects of human activity. On the one hand, coastal Kuwait is heavily influenced by the Shat al-Arab river and shows a clear anthropogenic signature from Kuwait city. A mix of two sources can be tracked through the coral and sediment chronological records, with Pb206/Pb207 ratios (1.202 and 1.151) that approach the suspected source values (1.21 and 1.12) and eliminate the possibility of other sources. Through a wide sediment geographic distribution, the strength of the anthropogenic signature is modulated. On the other hand, Singapore offers a more complex system, where an apparent mix of two sources (extreme isotope ratios 1.215 and ~1.14) occurs also, but where either an unresolved potentially important third source (isotope ratio ~1.18), or an isotope exchange process should be invoked. The sediment and coral records allows us to track the changes through time; however, there seems to be incongruence with the aerosol isotope record. Further potential sources are being explored currently and will be discussed.

Isotope separation by photochromatography

DOEpatents

Suslick, K.S.

1975-10-03

A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

Estimates of Radioxenon Released from Southern Hemisphere Medical isotope Production Facilities Using Measured Air Concentrations and Atmospheric Transport Modeling

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

Eslinger, Paul W.; Friese, Judah I.; Lowrey, Justin D.

2014-09-01

Abstract The International Monitoring System (IMS) of the Comprehensive-Nuclear-Test-Ban-Treaty monitors the atmosphere for radioactive xenon leaking from underground nuclear explosions. Emissions from medical isotope production represent a challenging background signal when determining whether measured radioxenon in the atmosphere is associated with a nuclear explosion prohibited by the treaty. The Australian Nuclear Science and Technology Organisation (ANSTO) operates a reactor and medical isotope production facility in Lucas Heights, Australia. This study uses two years of release data from the ANSTO medical isotope production facility and Xe-133 data from three IMS sampling locations to estimate the annual releases of Xe-133 from medicalmore » isotope production facilities in Argentina, South Africa, and Indonesia. Atmospheric dilution factors derived from a global atmospheric transport model were used in an optimization scheme to estimate annual release values by facility. The annual releases of about 6.8×1014 Bq from the ANSTO medical isotope production facility are in good agreement with the sampled concentrations at these three IMS sampling locations. Annual release estimates for the facility in South Africa vary from 1.2×1016 to 2.5×1016 Bq and estimates for the facility in Indonesia vary from 6.1×1013 to 3.6×1014 Bq. Although some releases from the facility in Argentina may reach these IMS sampling locations, the solution to the objective function is insensitive to the magnitude of those releases.« less

Real time, ambient air laser monitor for rare CO2 isotopic tracers: Δ13 C18 O16 O and Δ17 O

NASA Astrophysics Data System (ADS)

Nelson, David; Shorter, Joanne; McManus, Barry; Jervis, Dylan; Zahniser, Mark; Ono, Shuhei

2017-04-01

Greenhouse gas (GHG) emissions are the primary drivers of global climate change and hence there is a crucial need to quantify their sources and sinks. A powerful technique to help constrain source and sink strengths in GHG exchange processes is the analysis of the relative proportions of isotopic variants of GHGs. We present a new laser isotope monitor based on Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS) to measure the primary clumped isotopologue of CO2 (Δ13 C18 O16 O) and to simultaneously measure the mass independent 17 O-CO2 content (Δ17 O). The instrument directly measures dried atmospheric samples without cryogenic preconcentration of CO2 . The instrument has several novel features. The instrument's sensitivity is enhanced by employing a 400 meter optical absorption cell. Measurement drift is suppressed by using a rapid sample switching method with frequent comparison to a working reference. A new dual-pressure measurement scheme is demonstrated. This scheme solves the dynamic range challenge that arises in simultaneously measuring the main isotopologues of CO2 together with much less abundant clumped isotopologue species. Our initial results address measurement precision, measurement drift and calibration. We show the potential to reach 0.03 per mil repeatability with time resolution of 3 minutes and with minimal drift over an 18 hour measurement period. The instrument is sufficiently compact to be field deployed thus providing the possibility of continuous measurements of Δ13 C18 O16 O and Δ17 O rather than occasional flask samples.

Multi-tracer investigation of river and groundwater interactions: a case study in Nalenggele River basin, northwest China

NASA Astrophysics Data System (ADS)

Xu, Wei; Su, Xiaosi; Dai, Zhenxue; Yang, Fengtian; Zhu, Pucheng; Huang, Yong

2017-11-01

Environmental tracers (such as major ions, stable and radiogenic isotopes, and heat) monitored in natural waters provide valuable information for understanding the processes of river-groundwater interactions in arid areas. An integrated framework is presented for interpreting multi-tracer data (major ions, stable isotopes (2H, 18O), the radioactive isotope 222Rn, and heat) for delineating the river-groundwater interactions in Nalenggele River basin, northwest China. Qualitative and quantitative analyses were undertaken to estimate the bidirectional water exchange associated with small-scale interactions between groundwater and surface water. Along the river stretch, groundwater and river water exchange readily. From the high mountain zone to the alluvial fan, groundwater discharge to the river is detected by tracer methods and end-member mixing models, but the river has also been identified as a losing river using discharge measurements, i.e. discharge is bidirectional. On the delta-front of the alluvial fan and in the alluvial plain, in the downstream area, the characteristics of total dissolved solids values, 222Rn concentrations and δ18O values in the surface water, and patterns derived from a heat-tracing method, indicate that groundwater discharges into the river. With the environmental tracers, the processes of river-groundwater interaction have been identified in detail for better understanding of overall hydrogeological processes and of the impacts on water allocation policies.

[Determination of endogenous agmatine in rat plasma by isotope dilution-gas chromatography-mass spectrometry].

PubMed

Qiu, Zhongli; Lin, Ying; Xiong, Zhili; Xie, Jianwei

2014-07-01

A method for the determination of endogenous agmatine in rat plasma was developed by isotope dilution-gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The plasma samples were analyzed after protein precipitation, evaporation, derivatization by hexafluoroacetone (HFAA), and clean-up on a Florisil SPE column. The GC-MS analysis utilized stable isotope d8-agmatine as internal standard. The samples after treatme were tested by negative chemical ionization with selected ion monitoring (SIM) which was set at m/z 492 (molecular ion of agmatine) and m/z 500 (molecular ion of internal standard). The limit of detection (LOD) of agmatine standard solution was 0.005 7 ng/mL. The calibration curve of the agmatine spiked in rat plasma showed a good linear relationship at the range of 1.14-57.0 ng/mL (r = 0.997). The recoveries of agmatine spiked in rat plasma ranged from 92.3% to 109.8%. Inter-day and intra-day precisions were less than 15%. The average concentration level of agmatine in rat plasma was (22 +/- 9) ng/mL, and there was no significant difference between male and female SD rats (p > 0.05). The method is high sensitive and specific, and can be used for the determination of endogenous agmatine in plasma. It provides a strong support for the subsequent research of agmatine.

Assessment of In-Situ Reductive Dechlorination Using Compound-Specific Stable Isotopes, Functional-Gene Pcr, and Geochemical Data

PubMed Central

Carreón-Diazconti, Concepción; Santamaría, Johanna; Berkompas, Justin; Field, James A.; Brusseau, Mark L.

2010-01-01

Isotopic analysis and molecular-based bioassay methods were used in conjunction with geochemical data to assess intrinsic reductive dechlorination processes for a chlorinated-solvent contaminated site in Tucson, Arizona. Groundwater samples were obtained from monitoring wells within a contaminant plume comprising tetrachloroethene and its metabolites trichloroethene, cis-1,2-dichloroethene, vinyl chloride, and ethene, as well as compounds associated with free-phase diesel present at the site. Compound specific isotope (CSI) analysis was performed to characterize biotransformation processes influencing the transport and fate of the chlorinated contaminants. PCR analysis was used to assess the presence of indigenous reductive dechlorinators. The target regions employed were the 16s rRNA gene sequences of Dehalococcoides sp. and Desulfuromonas sp., and DNA sequences of genes pceA, tceA, bvcA, and vcrA, which encode reductive dehalogenases. The results of the analyses indicate that relevant microbial populations are present and that reductive dechlorination is presently occurring at the site. The results further show that potential degrader populations as well as biotransformation activity is non-uniformly distributed within the site. The results of laboratory microcosm studies conducted using groundwater collected from the field site confirmed the reductive dechlorination of tetrachloroethene to dichloroethene. This study illustrates the use of an integrated, multiple-method approach for assessing natural attenuation at a complex chlorinated-solvent contaminated site. PMID:19603638

Method for laser induced isotope enrichment

DOEpatents

Pronko, Peter P.; Vanrompay, Paul A.; Zhang, Zhiyu

2004-09-07

Methods for separating isotopes or chemical species of an element and causing enrichment of a desired isotope or chemical species of an element utilizing laser ablation plasmas to modify or fabricate a material containing such isotopes or chemical species are provided. This invention may be used for a wide variety of materials which contain elements having different isotopes or chemical species.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

2H and 18O Freshwater Isoscapes of Scotland

NASA Astrophysics Data System (ADS)

Meier-Augenstein, Wolfram; Hoogewerff, Jurian; Kemp, Helen; Frew, Danny

2013-04-01

Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwaters by the Scottish Environment Protection Agency (SEPA) fulfils legislative requirements with regards to water quality but new scientific methods involving stable isotope analysis present an opportunity combining these mandatory monitoring schemes with fundamental research to inform and deliver on current and nascent government policies [1] through gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and food security. For example, 2H and 18O isoscapes of Scottish freshwater could be used to underpin research and its applications in: • Climate change - Using longitudinal changes in the characteristic isotope composition of freshwater lochs and reservoirs as proxy, isoscapes will provide a means to assess if and how changes in temperature and weather patterns might impact on precipitation patterns and amount. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish soft fruit and Scottish Whisky. During 2011 and 2012, with the support of SEPA more than 110 samples from freshwater lochs and reservoirs were collected from 127 different locations across Scotland including the Highlands and Islands. Here we present the results of this sampling and analysis exercise isotope analyses in form of 2H and 18O isoscapes with an unprecedented grid resolution of 26.5 × 26.5 km (or 16.4 × 16.4 miles). [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland's National Food and Drink Policy (2009); Scottish Planning Policy Environmental Report (2009); Scottish Planning Policy (SPP) 15 Planning for Rural Development (2005); National Planning Policy Guideline (NPPG) 14: Natural Heritage (1999).

High-resolution stable isotope monitoring reveals differential vegetation-soil water feedbacks among plant functional types

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Haberer, K.; Troch, P. A. A.; Gessler, A.; Weiler, M.

2016-12-01

Understanding the linked dynamics of rain water recharge to soils and its utilization by plants is critical for predicting the impact of climate and land use changes on the productivity of ecosystems and the hydrologic cycle. While plants require vast quantities of water from the soil to sustain growth and function, they exert important direct and indirect controls on the movement of water through the rooted soil horizons, thereby potentially affecting their own resource availability. However, the specific ecohydrological belowground processes associated with different plant types and their rooting systems have been difficult to quantify with traditional methods. Here, we report on the use of techniques for monitoring stable isotopes in soil and plant water pools that allow us to track water infiltration and root uptake dynamics non-destructively and in high resolution. The techniques were applied in controlled rain pulse experiments with distinct plant types (grass, deciduous trees, grapevine) that we let develop on an initially uniform soil for two years. Our results show that plant species and types differed widely in their plasticity and pattern of root uptake under variable water availability. Thereby, and through notably co-acting indirect effects related to differential root system traits and co-evolution of soil properties, the different plants induced contrasting hydrological dynamics in the soil they had inhabited for only a short period of time. Taken together, our data suggest that the studied soil-vegetation systems evolved a positive infiltration-uptake feedback in which hydrological flow pathways underlying different species diverged in a way that complemented their specific water utilization strategy. Such a feedback could present an indirect competitive mechanism by which plants improve their own water supply and modulate hydrological cycling at the land surface. The ability to directly measure this feedback using in situ isotope methodology highlights the great potential for stable isotope research to improve our understanding of the soil-vegetation-atmosphere system.

Determining Timing and Magnitude of Dietary Shifts in Black Guillemots (Cepphus grylle) Using Stable Isotope Analysis of Flight Feathers

NASA Astrophysics Data System (ADS)

Kleese, M. C.; Boswell, K. M.; Divoky, G.; Barton, M. B.

2016-02-01

Recent decreases in Artic summer sea and increases in SST have caused changes in the marine ecosystems associated with ice-covered waters. A four-decade study of Black Guillemots (Cepphus grylle) on Cooper Island near Point Barrow, AK has shown that nestling quality and survival is linked to proximity to sea ice and SST. In recent years when sea ice retreats from the foraging area and SST increases to >4°C during the nestling period, parent guillemots have switched from their preferred prey, Arctic cod (Boreogadus saida), to less desirable fourhorn sculpin (Myoxocephalus quadricornis). The guillemots' shift from a cryopelagic fish to a nearshore demersal is hard to monitor through direct observation and we suggest a new method to assess the timing and magnitude of this dietary shift using stable isotope analysis of nestling flight feathers. Flight feathers (primaries, secondaries and tail feathers) provide a linear record of material incorporated into the body of the chick from the start of feather growth to fledging, a period of approximately 30 days. Arctic cod and fourhorn sculpin have distinctive diets and are reliant on different basal resources and should produce distinct isotopic signatures in guillemot tissues. We extracted vane tissues from sections of 30 black guillemot feathers grown in a breeding season that experienced an observed prey shift, and conducted stable carbon and nitrogen isotope analyses to determine whether such analyses could be used to assess the dietary shift linked with loss of sea ice and increasing SST. Most seabird populations are not as easily accessible as the guillemots of Cooper Island and thus observations of dietary composition are difficult to obtain. Development of a technique using nestling feathers to examine timing and magnitude of seasonal shifts in prey would preclude the need for daily observations and have great utility for monitoring the ecological effects of the continuing annual decrease in Arctic summer ice.

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

USGS Publications Warehouse

Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

2007-01-01

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Collaborative Study for Analysis of High Resolution Infrared Atmospheric Spectra Between NASA Langley Research Center and the University of Denver

NASA Technical Reports Server (NTRS)

Goldman, A.

2002-01-01

The Langley-D.U. collaboration on the analysis of high resolultion infrared atmospheric spectra covered a number of important studies of trace gases identification and quantification from field spectra, and spectral line parameters analysis. The collaborative work included: 1) Quantification and monitoring of trace gases from ground-based spectra available from various locations and seasons and from balloon flights; 2) Identification and preliminary quantification of several isotopic species, including oxygen and Sulfur isotopes; 3) Search for new species on the available spectra, including the use of selective coadding of ground-based spectra for high signal to noise; 4) Update of spectroscopic line parameters, by combining laboratory and atmospheric spectra with theoretical spectroscopy methods; 5) Study of trends and correlations of atmosphere trace constituents; and 6) Algorithms developments, retrievals intercomparisons and automatization of the analysis of NDSC spectra, for both column amounts and vertical profiles.

The beam diagnostic instruments in Beijing radioactive ion-beam facilities isotope separator on-line

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

Ma, Y., E-mail: yjma@ciae.ac.cn; Cui, B.; Ma, R.

The beam diagnostic instruments for Beijing Radioactive Ion-beam Facilities Isotope Separator On-Line are introduced [B. Q. Cui, Z. H. Peng, Y. J. Ma, R. G. Ma, B. Tang, T. Zhang, and W. S. Jiang, Nucl. Instrum. Methods 266, 4113 (2008); T. J. Zhang, X. L. Guan, and B. Q. Cui, in Proceedings of APAC 2004, Gyeongju, Korea, 2004, http://www.jacow.org , p. 267]. For low intensity ion beam [30–300 keV/1 pA–10 μA], the beam profile monitor, the emittance measurement unit, and the analyzing slit will be installed. For the primary proton beam [100 MeV/200 μA], the beam profile scanner will bemore » installed. For identification of the nuclide, a beam identification unit will be installed. The details of prototype of the beam diagnostic units and some experiment results will be described in this article.« less

Selenium and stable isotopes of carbon and nitrogen in the benthic clam Corbula amurensis from Northern San Francisco Bay, California: May 1995-February 2010

USGS Publications Warehouse

Kleckner, Amy E.; Stewart, A. Robin; Luoma, Samuel N.

2010-01-01

The clam-based food webs of San Francisco Bay, California efficiently bioaccumlate selenium and thus provide pathways for exposure to predators important to the estuary. This study documents changes in monthly selenium concentrations for the clam Corbula amurensis, a keystone species of the estuary, at five locations in northern San Francisco Bay from 1995 through 2010. Samples were collected from designated U.S. Geological Survey stations and prepared and analyzed by U.S. Geological Survey methods. Stable isotopes of carbon and nitrogen in soft tissues of clams also were measured as an indicator of sources of selenium for the clams. These monitoring data indicate that clam selenium concentrations ranged from a low of 2 to a high of 22 micrograms per gram dry weight with strong spatial and seasonal variation over the period of study.

Theory and methods for measuring the effective multiplication constant in ADS

NASA Astrophysics Data System (ADS)

Rugama Saez, Yolanda

2001-10-01

In the thesis an absolute measurements technique for the subcriticality determination is presented. The ADS is a hybrid system where a subcritical system is fed by a proton accelerator. There are different proposals to define an ADS, one is to use plutonium and minor actinides from power plants waste as fuel to be transmuted into non radioactive isotopes (transmuter/burner, ATW). Another proposal is to use a Th232-U233 cycle (Energy Amplifier), being that thorium is an interesting and abundant fertile isotope. The development of accelerator driven systems (ADS) requires the development of methods to monitor and control the subcriticality of this kind of system without interfering with its normal operation mode. With this finality, we have applied noise analysis techniques that allow us to characterise the system when it is operating. The method presented in this thesis is based on the stochastic neutron and photon transport theory that can be implemented by presently available neutron/photon transport codes. In this work, first we analyse the stochastic transport theory which has been applied to define a parameter to determine the subcritical reactivity monitoring measurements. Finally we give the main limitations and recommendations for these subcritical monitoring methodology. As a result of the theoretical methodology, done in the first part of this thesis, a monitoring measurement technique has been developed and verified using two coupled Monte Carlo programs. The first one, LAHET, simulates the spallation collisions and the high energy transport and the other, MCNP-DSP, is used to estimate the counting statistics from a neutron/photon ray counter in a fissile system, as well as the transport for neutron with energies less than 20 MeV. From the coupling of both codes we developed the LAHET/MCNP-DSP code which, has the capability to simulate the total process in the ADS from the proton interaction to the signal detector processing. In these simulations, we compute the cross power spectral densities between pairs of detectors located inside the system which, is defined as the measured parameter. From the comparison of the theoretical predictions with the Monte Carlo simulations, we obtain some practical and simple methods to determine the system multiplication constant. (Abstract shortened by UMI.)

Biomonitoring of Environmental Status and Trends (BEST) Program: selected methods for monitoring chemical contaminants and their effects in aquatic ecosystems

USGS Publications Warehouse

Schmitt, Christopher J.; Dethloff, Gail M.

2000-01-01

This document describes the suite of biological methods of the U.S. Geological Survey- Biomonitoring of Environmental Status and Trends program for monitoring chemical contaminants and their effects on fish. The methods, which were selected by panels of experts, are being field-tested in rivers of the Mississippi River, Columbia River, and Rio Grande basins. General health biomarkers include a health assessment index based on gross observation; histopathological examination of selected organs and tissues; condition factor; and the heptosomatic and splenosomatic indices. Immune system indicators are plasma lysozyme activity and measures of splenic macrophage aggregates. Reproductive biomarkers include plasma concentrations of sex steroid hormones (17b-estradiol and 11-ketotestosterone) and vitellogenin, gonadal histopathology (including reproductive stage and, in females, gonadal atresia), and the gonadosomatic index. Indicators of exposure to polycyclic aromatic and polyhalogenated hydrocarbons are the H4IIE rat hepatoma cell bioassay (performed on solvent extracts of composite fish samples) and hepatic ethoxyresorufin-O-deethylase activity. Stable nitrogen isotope ratios are used to assess the trophic position of the fish and their exposure to sewage and other animal wastes. For each indicator we describe endpoint(s) and methods, and discuss the indicator?s value and limitations for contaminant monitoring and assessment.

Characterizing fallout material using Cs and Pu atom ratios in environmental samples from the FDNPP fallout zone

NASA Astrophysics Data System (ADS)

Richards, David; Dunne, James; Martin, Peter; Scott, Tom; Yamashiki, Yosuke; Coath, Chris; Chen, Hart

2017-04-01

Here we report the use of combined of Cs and Pu isotope measurements to investigate the extensive plumes of radioactive fallout from the disaster at Fukishima Daiichi nuclear power plant (FNDPP) in March 2011. Among the aims of our study are improved assessment of the physico-chemical nature and changing distribution of land-based fallout. 135Cs/137Cs and 134Cs/137Cs atom ratios are indicative of conditions that relate to the nuclear fission reactions responsible for producing the respective radiocaesium isotopes, and offer much more in terms of forensic and chronological analysis than monitoring 137Cs alone. We briefly present methods to quantify the atom ratios of Cs and Pu isotopes in soil, lichen and moss samples from FDNPP catchment using mass spectrometry (ThermoTRITON for Cs and ThermoNEPTUNE for Pu). High precision data from Fukushima are presented (e.g decay corrected 135Cs/137Cs atom ratio = 0.384 ± 0.001 (n = 5) for roadside dust from Iitate region), and these are in agreement with prelimary estimates by others. We also confirm results for IAEA-330, a spinach sample collected from Polesskoe, Ukraine and subject to contamination from the Chernobyl accident. In addition to Cs isotopes, we adopt Pu isotopes to add a further dimension to the forensic analysis. We discuss the corrections required for background levels prior to the disaster, possibility for multiple components of fallout and complicating factors associated with remobilisation during the clean-up operation. In parallel with this work on digests and leaches from bulk environmental samples, we are refining methods for particle identification, isolation and characterisation using a complementary sequence of cutting-edge materials and manipulation techniques, including combined electron microscopy, focused ion beam techniques (Dualbeam), nano/micro manipulators and nano-scale imaging x-ray photoelectron spectroscopy (NanoESCA) and microCT.

87Sr/ 86Sr Concentrations in the Appalachian Basin: A Review

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

Mordensky, Stanley P.; Lieuallen, A. Erin; Verba, Circe

This document reviews 87Sr/ 86Sr isotope data across the Appalachian Basin from existing literature to show spatial and temporal variation. Isotope geochemistry presents a means of understanding the geochemical effects hydraulic fracturing may have on shallow ground substrates. Isotope fractionation is a naturally occurring phenomenon brought about by physical, chemical, and biological processes that partition isotopes between substances; therefore, stable isotope geochemistry allows geoscientists to understand several processes that shape the natural world. Strontium isotopes can be used as a tool to answer an array of geological and environmental inquiries. In some cases, strontium isotopes are sensitive to the introductionmore » of a non-native fluid into a system. This ability allows strontium isotopes to serve as tracers in certain systems. Recently, it has been demonstrated that strontium isotopes can serve as a monitoring tool for groundwater and surface water systems that may be affected by hydraulic fracturing fluids (Chapman et al., 2013; Kolesar Kohl et al., 2014). These studies demonstrated that 87Sr/ 86Sr values have the potential to monitor subsurface fluid migration in regions where extraction of Marcellus Shale gas is occurring. This document reviews publicly available strontium isotope data from 39 sample locations in the Appalachian Basin (Hamel et al., 2010; Chapman et al., 2012; Osborn et al., 2012; Chapman et al., 2013; Capo et al., 2014; Kolesar Kohl et al., 2014). The data is divided into two sets: stratigraphic (Upper Devonian/Lower Mississippi, Middle Devonian, and Silurian) and groundwater. ArcMap™ (ESRI, Inc.) was used to complete inverse distance weighting (IDW) analyses for each dataset to create interpolated surfaces in an attempt to find regional trends or variations in strontium isotopic values across the Appalachian Basin. 87Sr/ 86Sr varies up to ~ 0.011 across the Appalachian Basin, but the current publicly available data is limited in frequency and regional extent, causing artifacts and high uncertainty when interpolating data for locations far from sampling sites. These factors highlight the need for additional strontium isotope sampling across the region. Identifying potential contamination from hydraulic fracturing fluid in Appalachian Basin groundwater using strontium isotopes would require additional sampling. For a more comprehensive strontium isotope database, samples would need to be collected during prefracturing, syn-fracturing, and post-fracturing stages. This would add a temporal component to the spatial data and make tracing of fluid migration with strontium isotopes more accurate. Future research and modeling that incorporates subsurface geology and watershed data would also serve to increase the accuracy and certainty of the interpolations of these analyses. Prospective geospatial Appalachian Basin isotope studies would also benefit from the integration of geologic mapping because surface and subsurface geology influences observed strontium isotope values.« less

Temporal and spatial distribution of isotopes in river water in Central Europe: 50 years experience with the Austrian network of isotopes in rivers.

PubMed

Rank, Dieter; Wyhlidal, Stefan; Schott, Katharina; Weigand, Silvia; Oblin, Armin

2018-05-01

The Austrian network of isotopes in rivers comprises about 15 sampling locations and has been operated since 1976. The Danube isotope time series goes back to 1963. The isotopic composition of river water in Central Europe is mainly governed by the isotopic composition of precipitation in the catchment area; evaporation effects play only a minor role. Short-term and long-term isotope signals in precipitation are thus transmitted through the whole catchment. The influence of climatic changes has become observable in the long-term stable isotope time series of precipitation and surface waters. Environmental 3 H values were around 8 TU in 2015, short-term 3 H pulses up to about 80 TU in the rivers Danube and March were a consequence of releases from nuclear power plants. The complete isotope data series of this network will be included in the Global Network of Isotopes in Rivers database of the International Atomic Energy Agency (IAEA) in 2017. This article comprises a review of 50 years isotope monitoring on rivers and is also intended to provide base information on the (isotope-)hydrological conditions in Central Europe specifically for the end-users of these data, e.g. for modelling hydrological processes. Furthermore, this paper includes the 2006-2015 supplement adding to the Danube isotope set published earlier.

[Camera-cinematography of the heart (author's transl)].

PubMed

Adam, W E; Meyer, G; Bitter, F; Kampmann, H; Bargon, G; Stauch, M

1975-07-01

By "camera-cinematography" of the heart, we mean an isotope method which permits detailed observation of cardiac mechanics without the use of a catheter. All that is necessary is an intravenous injection of 10 to 15 mCi 99mTc human serum albumen followed after ten minutes by a five to ten minute period of observation with a scintilation camera. At this time the isotope has become distributed in the blood. Variations in the precordial impulses correspond with intra-cardiac changes of blood volume during a cardiac cycle. Analysis of the R-wave provides adequate information of cyclical volume changes in limited portions of the heart. This is achieved by a monitor with a pseudo-3-dimensional display; contraction and relaxation of the myocardium can be shown for any chosen longitudinal or horizontal diameter of the heart. Our programme allows simultaneous presentation of the movement of any point on the myocardium as a time-activity curve. The method is recommended as an addition to chest radiography, heart screening or cardiac kymography before carrying out cardiac catheterisation.

High-sensitivity stable-isotope probing by a quantitative terminal restriction fragment length polymorphism protocol.

PubMed

Andeer, Peter; Strand, Stuart E; Stahl, David A

2012-01-01

Stable-isotope probing (SIP) has proved a valuable cultivation-independent tool for linking specific microbial populations to selected functions in various natural and engineered systems. However, application of SIP to microbial populations with relatively minor buoyant density increases, such as populations that utilize compounds as a nitrogen source, results in reduced resolution of labeled populations. We therefore developed a tandem quantitative PCR (qPCR)-TRFLP (terminal restriction fragment length polymorphism) protocol that improves resolution of detection by quantifying specific taxonomic groups in gradient fractions. This method combines well-controlled amplification with TRFLP analysis to quantify relative taxon abundance in amplicon pools of FAM-labeled PCR products, using the intercalating dye EvaGreen to monitor amplification. Method accuracy was evaluated using mixtures of cloned 16S rRNA genes, DNA extracted from low- and high-G+C bacterial isolates (Escherichia coli, Rhodococcus, Variovorax, and Microbacterium), and DNA from soil microcosms amended with known amounts of genomic DNA from bacterial isolates. Improved resolution of minor shifts in buoyant density relative to TRFLP analysis alone was confirmed using well-controlled SIP analyses.

Precise quantitation of 136 urinary proteins by LC/MRM-MS using stable isotope labeled peptides as internal standards for biomarker discovery and/or verification studies.

PubMed

Percy, Andrew J; Yang, Juncong; Hardie, Darryl B; Chambers, Andrew G; Tamura-Wells, Jessica; Borchers, Christoph H

2015-06-15

Spurred on by the growing demand for panels of validated disease biomarkers, increasing efforts have focused on advancing qualitative and quantitative tools for more highly multiplexed and sensitive analyses of a multitude of analytes in various human biofluids. In quantitative proteomics, evolving strategies involve the use of the targeted multiple reaction monitoring (MRM) mode of mass spectrometry (MS) with stable isotope-labeled standards (SIS) used for internal normalization. Using that preferred approach with non-invasive urine samples, we have systematically advanced and rigorously assessed the methodology toward the precise quantitation of the largest, multiplexed panel of candidate protein biomarkers in human urine to date. The concentrations of the 136 proteins span >5 orders of magnitude (from 8.6 μg/mL to 25 pg/mL), with average CVs of 8.6% over process triplicate. Detailed here is our quantitative method, the analysis strategy, a feasibility application to prostate cancer samples, and a discussion of the utility of this method in translational studies. Copyright © 2015 Elsevier Inc. All rights reserved.

Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

PubMed

Matthies, R; Krahé, L; Blowes, D W

2014-07-15

Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

Data from a thick unsaturated zone underlying Oro Grande and Sheep Creek washes in the western part of the Mojave Desert, near Victorville, San Bernardino County, California

USGS Publications Warehouse

Izbicki, John A.; Clark, Dennis A.; Pimental, Maria I.; Land, Michael; Radyk, John C.; Michel, Robert L.

2000-01-01

This report presents data on the physical properties of unsaturated alluvial deposits and on the chemical and isotopic composition of soil water and soil gas collected at 12 monitoring sites in the western part of the Mojave Desert, near Victorville, California. Sites were installed using the ODEX air-hammer method. Seven sites were located in the active channels of Oro Grande and Sheep Creek Washes. The remaining five sites were located away from the active washes. Most sites were drilled to a depth of about 100 feet below land surface; two sites were drilled to the water table almost 650 feet below land surface. Drilling procedures, lithologic and geophysical data, and site construction and instrumentation are described. Core material was analyzed for water content, bulk density, water potential, particle size, and water retention. The chemical composition of leachate from almost 1,000 subsamples of cores and cuttings was determined. Water extracted from selected subsamples of cores was analyzed for tritium and the stable isotopes of oxygen and hydrogen. Water from suction-cup lysimeters and soil-gas samples also were analyzed for chemical and isotopic composition. In addition, data on the chemical and isotopic composition of bulk precipitation from five sites and on ground water from two water-table wells are reported.

An Isotopic view of water and nitrogen transport through the ...

EPA Pesticide Factsheets

Background/Question/MethodsGroundwater nitrate contamination affects thousands of households in Oregon's southern Willamette Valley and many more across the Pacific Northwest. The southern Willamette Valley Groundwater Management Area (SWV GWMA) was established in 2004 due to nitrate levels in the groundwater exceeding the human health standard of 10 mg nitrate-N L-1. Much of the nitrogen inputs to the GWMA comes from agricultural nitrogen use, and thus efforts to reduce N inputs to groundwater are focused upon improving N management. However, the effectiveness of these improvements on groundwater quality is unclear because of the complexity of nutrient transport through the vadose zone and long groundwater residence times. Our objective was to focus on vadose zone transport and understand the dynamics and timing of N and water movement below the rooting zone in relation to N management and water inputs. Stable isotopes are a powerful tool for tracking water movement, and understanding nitrogen transformations within the vadose zone. In partnership with local farmers, and state agencies, we established lysimeters and groundwater wells in multiple agricultural fields in the GWMA, and have monitored nitrate, nitrate isotopes, and water isotopes weekly for multiple years Results/ConclusionsOur results indicate that vadose zone transport is highly complex, and the residence time of water collected in lysimeters was much longer than expected. While input precipitatio

Multi-isotope tracers to investigate processes in the Elbe, Weser and Ems river catchment using B, Mo, Sr, and Pb isotope ratios assessed by MC ICP-MS

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Reese, Anna; Zimmermann, Tristan; Prohaska, Thomas; Retzmann, Anika; Wieser, Michael E.; Zitek, Andreas; Proefrock, Daniel

2017-04-01

Environmental monitoring of complex ecosystems requires reliable sensitive techniques based on sound analytical strategies to identify the source, fate and sink of elements and matter. Isotopic signatures can serve to trace pathways by making use of specific isotopic fingermarks or to distinguish between natural and anthropogenic sources. The presented work shows the potential of using the isotopic variation of Sr, Pb (as well-established isotopic systems), Mo and B (as novel isotopic system) assessed by MC ICP-MS in water and sediment samples to study aquatic ecosystem transport processes. The isotopic variation of Sr, Pb, Mo and B was determined in different marine and estuarine compartments covering the catchment of the German Wadden Sea and its main tributaries, the Elbe, Weser and Ems River. The varying elemental concentrations, the complex matrix and the expected small variations in the isotopic composition required the development and application of reliable analytical measurement approaches as well as suited metrological data evaluation strategies. Aquatic isoscapes were created using ArcGIS® by relating spatial isotopic data with geographical and geological maps. The elemental and isotopic distribution maps show large variation for different parameters and also reflect the numerous impact factors (e.g. geology, anthropogenic sources) influencing the catchment area.

Use of a multi-isotope and multi-tracer approach including organic matter isotopes for quantifying nutrient contributions from agricultural vs wastewater sources

NASA Astrophysics Data System (ADS)

Kendall, C.; Silva, S. R.; Young, M. B.

2013-12-01

While nutrient isotopes are a well-established tool for quantifying nutrients inputs from agricultural vs wastewater treatment plant (WWTP) sources, we have found that combining nutrient isotopes with the C, N, and S isotopic compositions of dissolved and particulate organic matter, as part of a comprehensive multi-isotope and multi-tracer approach, is a much more diagnostic approach. The main reasons why organic matter C-N-S isotopes are a useful adjunct to studies of nutrient sources and biogeochemical processes are that the dissolved and particulate organic matter associated with (1) different kinds of animals (e.g., humans vs cows) often have distinctive isotopic compositions reflecting the different diets of the animals, and (2) the different processes associated with the different land uses (e.g., in the WWTP or associated with different crop types) often result in significant differences in the isotopic compositions of the organics. The analysis of the δ34S of particulate organic matter (POM) and dissolved organic matter (DOM) has been found to be especially useful for distinguishing and quantifying water, nutrient, and organic contributions from different land uses in aquatic systems where much of the organic matter is aquatic in origin. In such environments, the bacteria and algae incorporate S from sulfate and sulfide that is isotopically labeled by the different processes associated with different land uses. We have found that there is ~35 permil range in δ34S of POM along the river-estuary continuum in the San Joaquin/Sacramento River basin, with low values associated with sulfate reduction in the upstream wetlands and high values associated with tidal inputs of marine water into the estuary. Furthermore, rice agriculture results in relatively low δ34S values whereas WWTP effluent in the Sacramento River produces distinctly higher values than upstream of the WWTP, presumably because SO2 is used to treat chlorinated effluent. The fish living downstream of these different land uses become isotopically labeled by the environments, making δ34S a useful tracer of fish derived from these different environments. This presentation will use examples from several large-scale river and wetlands studies to demonstrate useful applications of POM and DOM isotopes for environmental monitoring studies, and will discuss the relative merits of different methods for the collection and analysis of POM and DOM samples for C, N, and S isotopes.

Prototype Demonstration of Gamma- Blind Tensioned Metastable Fluid Neutron/Multiplicity/Alpha Detector – Real Time Methods for Advanced Fuel Cycle Applications

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

McDeavitt, Sean M.

The content of this report summarizes a multi-year effort to develop prototype detection equipment using the Tensioned Metastable Fluid Detector (TMFD) technology developed by Taleyarkhan [1]. The context of this development effort was to create new methods for evaluating and developing advanced methods for safeguarding nuclear materials along with instrumentation in various stages of the fuel cycle, especially in material balance areas (MBAs) and during reprocessing of used nuclear fuel. One of the challenges related to the implementation of any type of MBA and/or reprocessing technology (e.g., PUREX or UREX) is the real-time quantification and control of the transuranic (TRU)more » isotopes as they move through the process. Monitoring of higher actinides from their neutron emission (including multiplicity) and alpha signatures during transit in MBAs and in aqueous separations is a critical research area. By providing on-line real-time materials accountability, diversion of the materials becomes much more difficult. The Tensioned Metastable Fluid Detector (TMFD) is a transformational technology that is uniquely capable of both alpha and neutron spectroscopy while being “blind” to the intense gamma field that typically accompanies used fuel – simultaneously with the ability to provide multiplicity information as well [1-3]. The TMFD technology was proven (lab-scale) as part of a 2008 NERI-C program [1-7]. The bulk of this report describes the advancements and demonstrations made in TMFD technology. One final point to present before turning to the TMFD demonstrations is the context for discussing real-time monitoring of SNM. It is useful to review the spectrum of isotopes generated within nuclear fuel during reactor operations. Used nuclear fuel (UNF) from a light water reactor (LWR) contains fission products as well as TRU elements formed through neutron absorption/decay chains. The majority of the fission products are gamma and beta emitters and they represent the more significant hazards from a radiation protection standpoint. However, alpha and neutron emitting uranium and TRU elements represent the more significant safeguards and security concerns. Table 1.1 presents a representative PWR inventory of the uranium and actinide isotopes present in a used fuel assembly. The uranium and actinide isotopes (chiefly the Pu, Am and Cm elements) are all emitters of alpha particles and some of them release significant quantities of neutrons through spontaneous fissions« less

Determination of thiol metabolites in human urine by stable isotope labeling in combination with pseudo-targeted mass spectrometry analysis

NASA Astrophysics Data System (ADS)

Liu, Ping; Qi, Chu-Bo; Zhu, Quan-Fei; Yuan, Bi-Feng; Feng, Yu-Qi

2016-02-01

Precursor ion scan and multiple reaction monitoring scan (MRM) are two typical scan modes in mass spectrometry analysis. Here, we developed a strategy by combining stable isotope labeling (IL) with liquid chromatography-mass spectrometry (LC-MS) under double precursor ion scan (DPI) and MRM for analysis of thiols in 5 types of human cancer urine. Firstly, the IL-LC-DPI-MS method was applied for non-targeted profiling of thiols from cancer samples. Compared to traditional full scan mode, the DPI method significantly improved identification selectivity and accuracy. 103 thiol candidates were discovered in all cancers and 6 thiols were identified by their standards. It is worth noting that pantetheine, for the first time, was identified in human urine. Secondly, the IL-LC-MRM-MS method was developed for relative quantification of thiols in cancers compared to healthy controls. All the MRM transitions of light and heavy labeled thiols were acquired from urines by using DPI method. Compared to DPI method, the sensitivity of MRM improved by 2.1-11.3 folds. In addition, the concentration of homocysteine, γ-glutamylcysteine and pantetheine enhanced more than two folds in cancer patients compared to healthy controls. Taken together, the method demonstrated to be a promising strategy for identification and comprehensive quantification of thiols in human urines.

Determination of thiol metabolites in human urine by stable isotope labeling in combination with pseudo-targeted mass spectrometry analysis

PubMed Central

Liu, Ping; Qi, Chu-Bo; Zhu, Quan-Fei; Yuan, Bi-Feng; Feng, Yu-Qi

2016-01-01

Precursor ion scan and multiple reaction monitoring scan (MRM) are two typical scan modes in mass spectrometry analysis. Here, we developed a strategy by combining stable isotope labeling (IL) with liquid chromatography-mass spectrometry (LC-MS) under double precursor ion scan (DPI) and MRM for analysis of thiols in 5 types of human cancer urine. Firstly, the IL-LC-DPI-MS method was applied for non-targeted profiling of thiols from cancer samples. Compared to traditional full scan mode, the DPI method significantly improved identification selectivity and accuracy. 103 thiol candidates were discovered in all cancers and 6 thiols were identified by their standards. It is worth noting that pantetheine, for the first time, was identified in human urine. Secondly, the IL-LC-MRM-MS method was developed for relative quantification of thiols in cancers compared to healthy controls. All the MRM transitions of light and heavy labeled thiols were acquired from urines by using DPI method. Compared to DPI method, the sensitivity of MRM improved by 2.1–11.3 folds. In addition, the concentration of homocysteine, γ-glutamylcysteine and pantetheine enhanced more than two folds in cancer patients compared to healthy controls. Taken together, the method demonstrated to be a promising strategy for identification and comprehensive quantification of thiols in human urines. PMID:26888486

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.

Why Methane Increasing in the Atmosphere is Pushing us Towards New Analytical Approaches for Stable Isotope Ratios

NASA Astrophysics Data System (ADS)

White, J. W. C.; Michel, S. E.; Vaughn, B. H.; Miller, J. B.; Masarie, K. A.; Dlugokencky, E. J.; Sherwood, O.; Tans, P. P.

2015-12-01

Methane is increasing again in the atmosphere after nearly a decade of stable concentrations. As methane has risen by 2.5 times since the beginning of the industrial era, such a rise in concentrations is not surprising. Carbon isotopes, however, make it clear that the recent rise is not simply a resumption of the dramatic rise in the 1900s, but that other causes are at play, and that multiple fluxes may be interacting to yield the observed rise. At the same time, cautious attention is focused on the Arctic, where vast stores of carbon are poised for release as frozen soils melt, and some of that carbon will be released as methane. These realities make it imperative that we improve our monitoring of methane and methane isotopes in the atmosphere. This talk will address the issues that we face in meeting this challenge in the NOAA Global Greenhouse Gas Reference Network, including targets for precision and accuracy needed to calculate regional and global fluxes, technological advances in analytical equipment, maintaining standards, ensuring adequate monitoring sites and meeting all of these needs in an era of funding cuts and uncertainty for environmental monitoring.

LC/MS Method for the Determination of Stable Isotope Labeled Promethazine in Human Plasma

NASA Technical Reports Server (NTRS)

Zuwei, Wang; Boyd, Jason; Berens, Kurt L.; Putcha, Lakshmi

2004-01-01

Promethazine (PMZ) is taken by astronauts orally (PO), intramuscularly (IM) or rectally (PR) for space motion sickness. LC/MS method was developed with off-line solid phase extraction to measure plasma concentrations of PMZ given as stable isotope-labeled (SIL) formulations by the three different routes of administration simultaneously. Samples (0.5ml) were loaded on to Waters Oasis HLB co-polymer cartridges and eluted with 1.0 mL methanol. HPLC separation of the eluted sample was performed using an Agilent Zorbax SB-CN column (50 x 2.1 mm) at a flow rate of 0.2 mL/min for 6 min. Acetonitrile/ ammonium acetate (30 mM) in water (3:2, v/v), pH 5.6 plus or minus 0.1, was used as the mobile phase for separation. Concentrations of PMZ, PMZ-d4 and PMZ-d7 and chlorpromazine (internal standard) were determined using a Micromass ZMD single quadrupole mass spectrometer with Electrospray Ionization (ESI). ESI mass spectra were acquired in positive ion mode with selected ion monitoring of [M+ H]dot plus. The method is rapid, reproducible and the assay specific parameters are listed in a table. A novel, sensitive and specific method for the measurement of PMZ and SIL PMZ in human plasma is reported.

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 resolution over a long period. We observed an increasing δ in the evaporating water vapor due to more enriched surface water. This leads to a higher transport resistances and an increasing αK. References Braud, I., Bariac, T., Biron, P., and Vauclin, M.: Isotopic composition of bare soil evaporated water vapor. Part II: Modeling of RUBIC IV experimental results, J. Hydrol., 369, 17-29. Craig, H. et al., 1965. Deuterium and oxygen 18 variations in the ocean and marine atmosphere. In: E. Tongiogi (Editor), Stable Isotopes in Oceanographic Studies and Paleotemperatures. V. Lishi, Spoleto, Italy, pp. 9-130. Keeling, C. D.: The Concentration and Isotopic Abundances of Atmospheric Carbon Dioxide in Rural Areas, Geochim. Cosmochim. Acta, 13, 322-334. Merlivat, L., 1978. Molecular Diffusivities of H216O, HD16O, and H218O in Gases. J Chem Phys, 69, 2864-2871. Rothfuss, Y. et al., 2013. Monitoring water stable isotopic composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy. Water Resour. Res., 49, 1-9.

Carbon isotope systematics of Turrialba volcano, Costa Rica, using a portable cavity ring-down spectrometer

NASA Astrophysics Data System (ADS)

Malowany, K. S.; Stix, J.; de Moor, J. M.; Chu, K.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2017-07-01

Over the past two decades, activity at Turrialba volcano, Costa Rica, has shifted from hydrothermal to increasingly magmatic in character, with enhanced degassing and eruption potential. We have conducted a survey of the δ13C signatures of gases at Turrialba using a portable field-based CRDS with comparison to standard IRMS techniques. Our δ13C results of the volcanic plume, high-temperature vents, and soil gases reveal isotopic heterogeneity in the CO2 gas composition at Turrialba prior to its recent phase of eruptive activity. The isotopic value of the regional fault system, Falla Ariete (-3.4 ± 0.1‰), is in distinct contrast with the Central crater gases (-3.9 ± 0.1‰) and the 2012 high-temperature vent (-4.4 ± 0.2‰), an indication that spatial variability in δ13C may be linked to hydrothermal transport of volcanic gases, heterogeneities in the source composition, or magmatic degassing. Isotopic values of CO2 samples collected in the plume vary from δ13C of -5.2 to -10.0‰, indicative of mixing between atmospheric CO2 (-9.2 ± 0.1‰), and a volcanic source. We compare the Keeling method to a traditional mixing model (hyperbolic mixing curve) to estimate the volcanic source composition at Turrialba from the plume measurements. The predicted source compositions from the Keeling and hyperbolic methods (-3.0 ± 0.5‰ and -3.9 ± 0.4‰, respectively) illustrate two potential interpretations of the volcanic source at Turrialba. As of the 29 October 2014, Turrialba has entered a new eruptive period, and continued monitoring of the summit gases for δ13C should be conducted to better understand the dominant processes controlling δ13C fractionation at Turrialba.

The effects of isotope-labeled analogs on the LC-IDMS measurement by comparison of ESI responses and matrix effect of melamine, 13C3-melamine, 13C3+15N3-melamine, and 15N3-melamine.

PubMed

Li, Xiu Qin; Zhang, Qing He; Yang, Zong; Li, Hong Mei; Huang, Dong Feng

2017-05-01

In this paper, the effect of isotope-labeled analogs on the liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) measurement was evaluated based on the comparison research of electrospray ionization responses (ESI) and matrix effect of melamine, 13 C 3 -melamine, 13 C 3 + 15 N 3 -melamine, and 15 N 3 -melamine. The isotope-labeled melamines had similar ionization efficiency with melamine in the electrospray ionization source, but the intensity of corresponding quantitative fragment ions had distinctive differences. Based on the density functional theory at the B3LYP/6-311+G** level, this phenomenon was explained very well. The rare cleavage pathways of melamine, which just could be exactly identified by 15 N-labeled melamines, resulted in the difference of quantitative fragment ions between 15 N-labeled melamines and melamine. The interaction of ESI response between melamine and isotope-labeled melamines was investigated using MRM monitor mode. 15 N-labeled melamine had significant ion inter-suppression effect on melamine, while 13 C-labeled melamine had little influence on melamine. Finally, the influence of different isotope-labeled melamines on the LC-IDMS result was evaluated using the IDMS correction factor (θ). Taking the determination of melamine in milk powder as an example, the matrix effects of different isotope-labeled melamines and melamine had notable difference and the impact of this difference on the measurement results depended on the concentrations of analyte and matrix solution. It was worth noting that 15 N 3 -melamine exhibited significant ion suppression to melamine in matrix solution. The deviation of the results from IDMS method might reach 59% using 15 N 3 -melamine as internal standard in special matrix solution. Graphical Abstract The comparison of ESI responses of melamine, 13 C 3 -melamine, 13 C 3 + 15 N 3 -melamine and 15 N 3 -melamine.

Oxygen-18 isotope of breath CO2 linking to erythrocytes carbonic anhydrase activity: a biomarker for pre-diabetes and type 2 diabetes

PubMed Central

Ghosh, Chiranjit; Banik, Gourab D.; Maity, Abhijit; Som, Suman; Chakraborty, Arpita; Selvan, Chitra; Ghosh, Shibendu; Chowdhury, Subhankar; Pradhan, Manik

2015-01-01

Carbonic anhydrase (CA), a well-characterized metalloenzyme, is associated with oxygen-18 ( 18O)-isotopic fractionations of CO2. To investigate how CA activity links the 18O of breath CO2 to pre-diabetes (PD) and type 2 diabetes (T2D) during metabolism, we studied pre- and post-dose CA activities in erythrocytes with simultaneous monitoring of 18O/ 16O-isotope ratios of breath CO2 and thereafter elucidated potential metabolic pathways underlying CA alteration in the pathogenesis of T2D. Here we show that the post-dose CA activity in both T2D and PD was markedly enhanced, whereas the non-diabetic controls (NDC) exhibited a considerable reduction in post-dose CA activity when compared with their basal CA activities. However, T2D and PD exhibited isotopic enrichments of 18O in breath CO2, while a marked depletion of 18O in CO2 was manifested in NDC. Thus, the isotopic enrichments and depletions of 18O in breath CO2 were well correlated with the changes in CA activities for controls, PD and T2D. Our findings suggest the changes in CA activities in erythrocytes may contribute to the pathogenesis of T2D and the breath C 18O 16O regulated by the CA activity as a potential biomarker for non-invasive assessment of T2D, and thus may open a new method for treating T2D. PMID:25633556

Biochemical Fractionation and Stable Isotope Dilution Liquid Chromatography-mass Spectrometry for Targeted and Microdomain-specific Protein Quantification in Human Postmortem Brain Tissue*

PubMed Central

MacDonald, Matthew L.; Ciccimaro, Eugene; Prakash, Amol; Banerjee, Anamika; Seeholzer, Steven H.; Blair, Ian A.; Hahn, Chang-Gyu

2012-01-01

Synaptic architecture and its adaptive changes require numerous molecular events that are both highly ordered and complex. A majority of neuropsychiatric illnesses are complex trait disorders, in which multiple etiologic factors converge at the synapse via many signaling pathways. Investigating the protein composition of synaptic microdomains from human patient brain tissues will yield valuable insights into the interactions of risk genes in many disorders. These types of studies in postmortem tissues have been limited by the lack of proper study paradigms. Thus, it is necessary not only to develop strategies to quantify protein and post-translational modifications at the synapse, but also to rigorously validate them for use in postmortem human brain tissues. In this study we describe the development of a liquid chromatography-selected reaction monitoring method, using a stable isotope-labeled neuronal proteome standard prepared from the brain tissue of a stable isotope-labeled mouse, for the multiplexed quantification of target synaptic proteins in mammalian samples. Additionally, we report the use of this method to validate a biochemical approach for the preparation of synaptic microdomain enrichments from human postmortem prefrontal cortex. Our data demonstrate that a targeted mass spectrometry approach with a true neuronal proteome standard facilitates accurate and precise quantification of over 100 synaptic proteins in mammalian samples, with the potential to quantify over 1000 proteins. Using this method, we found that protein enrichments in subcellular fractions prepared from human postmortem brain tissue were strikingly similar to those prepared from fresh mouse brain tissue. These findings demonstrate that biochemical fractionation methods paired with targeted proteomic strategies can be used in human brain tissues, with important implications for the study of neuropsychiatric disease. PMID:22942359

Noncontacting measurement technologies for space propulsion condition monitoring

NASA Technical Reports Server (NTRS)

Randall, M. R.; Barkhoudarian, S.; Collins, J. J.; Schwartzbart, A.

1987-01-01

This paper describes four noncontacting measurement technologies that can be used in a turbopump condition monitoring system. The isotope wear analyzer, fiberoptic deflectometer, brushless torque-meter, and fiberoptic pyrometer can be used to monitor component wear, bearing degradation, instantaneous shaft torque, and turbine blade cracking, respectively. A complete turbopump condition monitoring system including these four technologies could predict remaining component life, thus reducing engine operating costs and increasing reliability.

Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

NASA Astrophysics Data System (ADS)

Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

2012-04-01

Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of diffuse agrochemical pollutants in a relatively simple hydrological system. The simulated shifts in isotopic signals are within a range that could be detected with current isotope analytics. Concentrations in the stream vary significantly only for a short period during and after intense rainfall events. In contrast, CSIA values reveal longer response times such that isotopic shifts are likely to be detected in samples with a coarser temporal resolution. Rainfall events which result in fast lateral subsurface transport from the pollution source to the stream can be separated from those that lead to pollution migration through deeper subsurface zones with much longer travel times. Two-dimensional CSIA highlights an increasing importance of the oxic reaction in the topsoil during the wetter period of the year. In order to examine to which extent CSIA is applicable for more complex hydrological systems, it is projected to simulate isotope fractionation in a 3-dimensional catchment featuring additional processes such as migration from several pollution sources or in-stream degradation.

Cosmogenic isotope beryllium-7 in the atmosphere: Production versus transport

NASA Astrophysics Data System (ADS)

Pacini, Alessandra; Usoskin, Ilya; Evangelista, Heitor; Echer, Ezequiel; Mursula, Kalevi; Leppanen, Ari-Pekka

Cosmogenic isotope 7 Be measured near the ground can provide information about its produc-tion (that occurs in the atmosphere due to the interaction of cosmic rays and atmospheric constituents) and its deposition processes (that involves air mass dynamics, stratosphere-troposphere coupling and local climatic conditions). We present the results of an investigation of the atmospheric 7 Be temporal variations at different geographic locations (Finland and Brazil). This study was based on an analysis of three time series of 7 Be concentration measured in near-surface air samples from Rovaniemi and Loviisa (Finland) and Rio de Janeiro (Brazil) for the last decades. We made use of the wavelet spectral method to identify the frequency-temporal features of the 7 Be temporal variations that allowed us to determine the relative importance of production and deposition process for the observed data. By comparing these time series with climatic indices and the values of 7 Be concentration expected from the model for the same period, we found that the climate system is the main driver of the surface isotopic modulation, while the imprints of the production variations are geographically dependent. Thus,7 Be can be considered a good tool to monitor the large-scale air mass dynamics.

Gravitational effects on plant growth hormone concentration

NASA Astrophysics Data System (ADS)

Bandurski, Robert S.; Schulze, Aga

Numerous studies, particularly those of H. Dolk in the 1930's, established by means of bio-assay, that more growth hormone diffused from the lower, than from the upper side of a gravity-stimulated plant shoot. Now, using an isotope dilution assay, with 4,5,6,7 tetradeutero indole-3-acetic acid as internal standard, and selected ion monitoring-gas chromatography-mass spectrometry as the method of determination, we have confirmed Dolk's finding and established that the asymmetrically distributed hormone is, in fact, indole-3-acetic acid (IAA). This is the first physico-chemical demonstration that there is more free IAA on the lower sides of a geo-stimulated plant shoot. We have also shown that free IAA occurs primarily in the conductive vascular tissues of the shoot, whereas IAA esters predominate in the growing cortical cells. Now, using an especially sensitive gas chromatographic isotope dilution assay we have found that the hormone asymmetry also occurs in the non-vascular tissue. Currently, efforts are directed to developing isotope dilution assays, with picogram sensitivity, to determine how this asymmetry of IAA distribution is attained so as to better understand how the plant perceives the geo-stimulus.

Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

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

Makarov, G N; Petin, A N

2016-03-31

We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with amore » surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation. (laser separation of isotopes)« less

Data from a thick unsaturated zone in Joshua Tree, San Bernardino County, California, 2007--09

USGS Publications Warehouse

Burgess, Matthew; Izbicki, John; Teague, Nicholas; O'Leary, David R.; Clark, Dennis; Land, Michael

2012-01-01

Data were collected on the physical properties of unsaturated alluvial deposits, the chemical composition of leachate extracted from unsaturated alluvial deposits, the chemical and isotopic composition of groundwater and unsaturated-zone water, and the chemical composition of unsaturated-zone gas at four monitoring sites in the southwestern part of the Mojave Desert in the town of Joshua Tree, San Bernardino County, California. The presence of denitrifying and nitrate-reducing bacteria from unsaturated alluvial deposits was evaluated for two of these monitoring sites that underlie unsewered residential development. Four unsaturated-zone monitoring sites were installed in the Joshua Tree area—two in an unsewered residential development and two adjacent to a proposed artificial-recharge site in an undeveloped area. The two boreholes in residential development areas were installed by using the ODEX air-hammer method. One borehole was drilled through the unsaturated zone to a depth of 541 ft (feet) below land surface; a well screened across the water table was installed. Groundwater was sampled from this well. The second borehole was drilled to a depth of 81 ft below land surface. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described. Core material was analyzed for water content, bulk density, matric potential, particle size, and water retention. The leachate from over 500 subsamples of cores and cuttings was analyzed for soluble anions, including fluoride, sulfate, bromide, chloride, nitrate, nitrite, and orthophosphate. Groundwater was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone water from suction-cup lysimeters was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone gas samples were analyzed for argon, oxygen, nitrogen, methane, carbon dioxide, ethane, nitrous oxide, and carbon monoxide. Drill cuttings were analyzed for denitrifying and nitrate-reducing bacteria. One of the boreholes installed adjacent to the Joshua Basin Water District proposed groundwater-recharge facility was installed by using the ODEX air-hammer method and the other was installed by using a 7.875-inch hollow-stem auger. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described; however, geochemical data were not available at the time of publication.

Method of isotope separation by chemi-ionization

DOEpatents

Wexler, Sol; Young, Charles E.

1977-05-17

A method for separating specific isotopes present in an isotopic mixture by aerodynamically accelerating a gaseous compound to form a jet of molecules, and passing the jet through a stream of electron donor atoms whereby an electron transfer takes place, thus forming negative ions of the molecules. The molecular ions are then passed through a radiofrequency quadrupole mass filter to separate the specific isotopes. This method may be used for any compounds having a sufficiently high electron affinity to permit negative ion formation, and is especially useful for the separation of plutonium and uranium isotopes.

Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

PubMed

van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

2014-12-16

A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

USGS Publications Warehouse

Sigman, D.M.; Casciotti, K.L.; Andreani, M.; Barford, C.; Galanter, M.; Böhlke, J.K.

2001-01-01

We report a new method for measurement of the isotopic composition of nitrate (NO3-) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N2O) generated from nitrate by denitrifying bacteria that lack N2O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10-day carbon stable isotope data set with 30 minutes resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

PubMed

Quartararo, Christine E; Hadi, Timin; Cahill, Sean M; Blanchard, John S

2013-12-23

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacterium's life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage ((D₂O)V = 2.0 ± 0.1, and (D₂O)[V/K(isocitrate)] = 2.2 ± 0.3) arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of the succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate, and succinate prepared in D₂O would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by ¹H NMR spectroscopy shows a clear equilibrium perturbation in D₂O. The final equilibrium isotopic composition of reactants in D₂O revealed dideuterated succinate, protiated glyoxylate, and monodeuterated isocitrate, with the transient appearance and disappearance of monodeuterated succinate. A model for the equilibrium perturbation of substrate species and their time-dependent isotopic composition is presented.

The zinc stable isotope signature of waste rock drainage in Arctic Canada

NASA Astrophysics Data System (ADS)

Matthies, Romy; Blowes, David

2014-05-01

Leachate emerging from a pilot-scale waste rock pile of the Diavik diamond mine, Northwest Territories, was monitored. The well-characterized waste rock consists of granite, pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0.053 and 0.027 wt. %, respectively. During the field seasons of 2011 and 2012, the Zn stable isotope footprint was characterized alongside standard monitoring parameters. pH ranged between 4.3 and 6.8 and carbonate alkalinity was low or undetectable. Al and Fe concentrations averaged 6.78 mg L-1 and 175 µg L-1, respectively. The pH and metal mobility were governed by sulfide oxidation and sorption and co-precipitation onto iron and aluminium hydroxides. The main processes controlling zinc mobility in the range of 0.4 and 4.7 mg L-1 was the oxidative dissolution of sphalerite (ZnS) in the biotite schist and the attenuation of zinc onto secondary iron and aluminium hydroxides and desorption upon the pH declining below the pHpzc. The isotope ratios between -0.16 and +0.19 ‰ (δ66Zn, avg = +0.05 ‰, n = 43) are consistent with values reported from other sphalerite containing deposits. Zn isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting Zn mobility had little or no impact on the Zn isotope signature. Data indicate, that the Zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic, mine-derived Zn sources under varying environmental conditions.

Measurement of delta13C and delta18O Isotopic Ratios of CaCO3 by a Thermoquest Finnigan GasBench II Delta Plus XL Continous Flow Isotope Ratio Mass Spectrometer with Application to Devils Hole Core DH-11 Calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate Maciunas; Keybl, Jaroslav Edward

2001-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400?20 ?g) of calcium carbonate. This new method streamlines the classical phosphoric acid - calcium carbonate (H3PO4 - CaCO3) reaction method by making use of a Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. To obtain reproducible and accurate results, optimal conditions for the H3PO4 - CaCO3 reaction had to be determined. At the acid-carbonate reaction temperature suggested by the equipment manufacturer, the oxygen isotope ratio results were unsatisfactory (standard deviation () greater than 1.5 per mill), probably because of a secondary reaction. When the acid-carbonate reaction temperature was lowered to 26?C and the reaction time was increased to 24 hours, the precision of the carbon and oxygen isotope ratios for duplicate analyses improved to 0.1 and 0.2 per mill, respectively. The method was tested by analyzing calcite from Devils Hole, Nevada, which was formed by precipitation from ground water onto the walls of a sub-aqueous cavern during the last 500,000 years. Isotope-ratio values previously had been obtained by the classical method for Devils Hole core DH-11. The DH-11 core had been recently re-sampled, and isotope-ratio values were obtained using this new method. The results were comparable to those obtained by the classical method. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, a cutting error that was then independently confirmed. The reproducibility of the isotopic values is demonstrated by a correlation of approximately 0.96 for both isotopes, after correcting for an alignment offset. This result indicates that the new method is a viable alternative to the classical method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable timesavings.

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

Devi, Pooja; Jain, Ashok Kumar; Rao, M Someshwer; Kumar, Bhishm

2015-01-01

A continuous and reliable time series data of the stable isotopic composition of atmospheric moisture is an important requirement for the wider applicability of isotope mass balance methods in atmospheric and water balance studies. This requires routine sampling of atmospheric moisture by an appropriate technique and analysis of moisture for its isotopic composition. We have, therefore, used a much simpler method based on an isotope mass balance approach to derive the isotopic composition of atmospheric moisture using a class-A drying evaporation pan. We have carried out the study by collecting water samples from a class-A drying evaporation pan and also by collecting atmospheric moisture using the cryogenic trap method at the National Institute of Hydrology, Roorkee, India, during a pre-monsoon period. We compared the isotopic composition of atmospheric moisture obtained by using the class-A drying evaporation pan method with the cryogenic trap method. The results obtained from the evaporation pan water compare well with the cryogenic based method. Thus, the study establishes a cost-effective means of maintaining time series data of the isotopic composition of atmospheric moisture at meteorological observatories. The conclusions drawn in the present study are based on experiments conducted at Roorkee, India, and may be examined at other regions for its general applicability.

Carbon isotope ratios and isotopic correlations between components in fruit juices

NASA Astrophysics Data System (ADS)

Wierzchnicki, Ryszard

2013-04-01

Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

Chemical Isotope Labeling LC-MS for Monitoring Disease Progression and Treatment in Animal Models: Plasma Metabolomics Study of Osteoarthritis Rat Model

NASA Astrophysics Data System (ADS)

Chen, Deying; Su, Xiaoling; Wang, Nan; Li, Yunong; Yin, Hua; Li, Liang; Li, Lanjuan

2017-01-01

We report a chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS) method generally applicable for tracking metabolomic changes from samples collected in an animal model for studying disease development and treatment. A rat model of surgically induced osteoarthritis (OA) was used as an example to illustrate the workflow and technical performance. Experimental duplicate analyses of 234 plasma samples were carried out using dansylation labeling LC-MS targeting the amine/phenol submetabolome. These samples composed of 39 groups (6 rats per group) were collected at multiple time points with sham operation, OA control group, and OA rats with treatment, separately, using glucosamine/Celecoxib and three traditional Chinese medicines (Epimedii folium, Chuanxiong Rhizoma and Bushen-Huoxue). In total, 3893 metabolites could be detected and 2923 of them were consistently detected in more than 50% of the runs. This high-coverage submetabolome dataset could be used to track OA progression and treatment. Many differentiating metabolites were found and 11 metabolites including 2-aminoadipic acid, saccharopine and GABA were selected as potential biomarkers of OA progression and OA treatment. This study illustrates that CIL LC-MS is a very useful technique for monitoring incremental metabolomic changes with high coverage and accuracy for studying disease progression and treatment in animal models.

Chemical Isotope Labeling LC-MS for Monitoring Disease Progression and Treatment in Animal Models: Plasma Metabolomics Study of Osteoarthritis Rat Model

PubMed Central

Chen, Deying; Su, Xiaoling; Wang, Nan; Li, Yunong; Yin, Hua; Li, Liang; Li, Lanjuan

2017-01-01

We report a chemical isotope labeling (CIL) liquid chromatography mass spectrometry (LC-MS) method generally applicable for tracking metabolomic changes from samples collected in an animal model for studying disease development and treatment. A rat model of surgically induced osteoarthritis (OA) was used as an example to illustrate the workflow and technical performance. Experimental duplicate analyses of 234 plasma samples were carried out using dansylation labeling LC-MS targeting the amine/phenol submetabolome. These samples composed of 39 groups (6 rats per group) were collected at multiple time points with sham operation, OA control group, and OA rats with treatment, separately, using glucosamine/Celecoxib and three traditional Chinese medicines (Epimedii folium, Chuanxiong Rhizoma and Bushen-Huoxue). In total, 3893 metabolites could be detected and 2923 of them were consistently detected in more than 50% of the runs. This high-coverage submetabolome dataset could be used to track OA progression and treatment. Many differentiating metabolites were found and 11 metabolites including 2-aminoadipic acid, saccharopine and GABA were selected as potential biomarkers of OA progression and OA treatment. This study illustrates that CIL LC-MS is a very useful technique for monitoring incremental metabolomic changes with high coverage and accuracy for studying disease progression and treatment in animal models. PMID:28091618

Sensitive Quantification of Cannabinoids in Milk by Alkaline Saponification-Solid Phase Extraction Combined with Isotope Dilution UPLC-MS/MS.

PubMed

Wei, Binnian; McGuffey, James E; Blount, Benjamin C; Wang, Lanqing

2016-01-01

Maternal exposure to marijuana during the lactation period-either active or passive-has prompted concerns about transmission of cannabinoids to breastfed infants and possible subsequent adverse health consequences. Assessing these health risks requires a sensitive analytical approach that is able to quantitatively measure trace-level cannabinoids in breast milk. Here, we describe a saponification-solid phase extraction approach combined with ultra-high-pressure liquid chromatography-tandem mass spectrometry for simultaneously quantifying Δ9-tetrahydrocannabinol (THC), cannabidiol (CBD), and cannabinol (CBN) in breast milk. We demonstrate for the first time that constraints on sensitivity can be overcome by utilizing alkaline saponification of the milk samples. After extensively optimizing the saponification procedure, the validated method exhibited limits of detections of 13, 4, and 66 pg/mL for THC, CBN, and CBD, respectively. Notably, the sensitivity achieved was significantly improved, for instance, the limits of detection for THC is at least 100-fold more sensitive compared to that previously reported in the literature. This is essential for monitoring cannabinoids in breast milk resulting from passive or nonrecent active maternal exposure. Furthermore, we simultaneously acquired multiple reaction monitoring transitions for 12 C- and 13 C-analyte isotopes. This combined analysis largely facilitated data acquisition by reducing the repetitive analysis rate for samples exceeding the linear limits of 12 C-analytes. In addition to high sensitivity and broad quantitation range, this method delivers excellent accuracy (relative error within ±10%), precision (relative standard deviation <10%), and efficient analysis. In future studies, we expect this method to play a critical role in assessing infant exposure to cannabinoids through breastfeeding.

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

Fish fins as non-lethal surrogates for muscle tissues in freshwater food web studies using stable isotopes.

PubMed

Hette Tronquart, Nicolas; Mazeas, Laurent; Reuilly-Manenti, Liana; Zahm, Amandine; Belliard, Jérôme

2012-07-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. However, sampling white muscle often implies the sacrifice of fish. Thus, we examined whether the non-lethal sampling of fin tissue can substitute muscle sampling in food web studies. Analysing muscle and fin δ(15)N and δ(13)C values of 466 European freshwater fish (14 species) with an elemental analyser coupled with an isotope ratio mass spectrometer, we compared the isotope values of the two tissues. Correlations between fin and muscle isotope ratios were examined for all fish together and specifically for 12 species. We further proposed four methods of assessing muscle from fin isotope ratios and estimated the errors made using these muscle surrogates. Despite significant differences between isotope values of the two tissues, fin and muscle isotopic signals are strongly correlated. Muscle values, estimated with raw fin isotope ratios (1st method), induce an error of ca. 1‰ for both isotopes. In comparison, specific (2nd method) or general (3rd method) correlations provide meaningful corrections of fin isotope ratios (errors <0.6‰). On the other hand, relationships, established for Australian tropical fish, only give poor muscle estimates (errors >0.8‰). There is little chance that a global model can be created. However, the 2nd and 3rd methods of estimating muscle values from fin isotope ratios should provide an acceptable level of error for the studies of European freshwater food web. We thus recommend that future studies use fin tissue as a non-lethal surrogate for muscle. Copyright © 2012 John Wiley & Sons, Ltd.

A METHOD TO IMPROVE DOSE ASSESSMENT BY RECONSTRUCTION OF THE COMPLETE ISOTOPES INVENTORY.

PubMed

Bonin, Alice; Tsilanizara, Aimé

2017-06-01

Radiation shielding assessments may underestimate the expected dose if some isotopes at trace level are not considered in the isotopes inventory of the shielded radioactive materials. Indeed, information about traces is not often available. Nevertheless, the activation of some minor isotopic traces may significantly contribute to the dose build-up. This paper presents a new method (Isotopes Inventory Reconstruction-IIR) estimating the concentration of the minor isotopes in the irradiated material at the beginning of the cooling period. The method requires the solution of the inverse problem describing the irradiated material's decay. In a mixture of an irradiated uranium-plutonium oxide shielded by a set-up made of stainless-steel, porous polyethylene plaster and lead methyl methacrylate, the comparison between different methods proves that the IIR-method allows better assessment of the dose than other approximate methods. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

PubMed

Gourgiotis, Alkiviadis; Manhès, Gérard; Louvat, Pascale; Moureau, Julien; Gaillardet, Jérôme

2015-09-30

During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated. Copyright © 2015 John Wiley & Sons, Ltd.

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 ...

Detecting isotopic ratio outliers

NASA Astrophysics Data System (ADS)

Bayne, C. K.; Smith, D. H.

An alternative method is proposed for improving isotopic ratio estimates. This method mathematically models pulse-count data and uses iterative reweighted Poisson regression to estimate model parameters to calculate the isotopic ratios. This computer-oriented approach provides theoretically better methods than conventional techniques to establish error limits and to identify outliers.

Multiple isotopes (O, C, Li, Sr) as tracers of CO2 and brine leakage from CO2-enhanced oil recovery activities in Permian Basin, Texas, USA

NASA Astrophysics Data System (ADS)

Phan, T. T.; Sharma, S.; Gardiner, J. B.; Thomas, R. B.; Stuckman, M.; Spaulding, R.; Lopano, C. L.; Hakala, A.

2017-12-01

Potential CO2 and brine migration or leakage into shallow groundwater is a critical issue associated with CO2 injection at both enhanced oil recovery (EOR) and carbon sequestration sites. The effectiveness of multiple isotope systems (δ18OH2O, δ13C, δ7Li, 87Sr/86Sr) in monitoring CO2 and brine leakage at a CO2-EOR site located within the Permian basin (Seminole, Texas, USA) was studied. Water samples collected from an oil producing formation (San Andres), a deep groundwater formation (Santa Rosa), and a shallow groundwater aquifer (Ogallala) over a four-year period were analyzed for elemental and isotopic compositions. The absence of any change in δ18OH2O or δ13CDIC values of water in the overlying Ogallala aquifer after CO2 injection indicates that injected CO2 did not leak into this aquifer. The range of Ogallala water δ7Li (13-17‰) overlaps the San Andres water δ7Li (13-15‰) whereas 87Sr/86Sr of Ogallala (0.70792±0.00005) significantly differs from San Andres water (0.70865±0.00003). This observation demonstrates that Sr isotopes are much more sensitive than Li isotopes in tracking brine leakage into shallow groundwater at the studied site. In contrast, deep groundwater δ7Li (21-25‰) is isotopically distinct from San Andres produced water; thus, monitoring this intermitted formation water can provide an early indication of CO2 injection-induced brine migration from the underlying oil producing formation. During water alternating with gas (WAG) operations, a significant shift towards more positive δ13CDIC values was observed in the produced water from several of the San Andres formation wells. The carbon isotope trend suggests that the 13C enriched injected CO2 and formation carbonates became the primary sources of dissolved inorganic carbon in the area surrounding the injection wells. Moreover, one-way ANOVA statistical analysis shows that the differences in δ7Li (F(1,16) = 2.09, p = 0.17) and 87Sr/86Sr (F(1,18) = 4.47, p = 0.05) values of shallow groundwater collected before and during the WAG period are not statistically significant. The results to date suggest that the water chemistry of shallow groundwater has not been influenced by the CO2 injection activities. The efficacy of each isotope system as a monitoring tool will be evaluated and discussed using a Bayesian mixing model.

Development and validation of an universal interface for compound-specific stable isotope analysis of chlorine (37Cl/35Cl) by GC-high-temperature conversion (HTC)-MS/IRMS.

PubMed

Renpenning, Julian; Hitzfeld, Kristina L; Gilevska, Tetyana; Nijenhuis, Ivonne; Gehre, Matthias; Richnow, Hans-Hermann

2015-03-03

A universal application of compound-specific isotope analysis of chlorine was thus far limited by the availability of suitable analysis techniques. In this study, gas chromatography in combination with a high-temperature conversion interface (GC-HTC), converting organic chlorine in the presence of H2 to gaseous HCl, was coupled to a dual-detection system, combining an ion trap mass spectrometer (MS) and isotope-ratio mass spectrometer (IRMS). The combination of the MS/IRMS detection enabled a detailed characterization, optimization, and online monitoring of the high-temperature conversion process via ion trap MS as well as a simultaneous chlorine isotope analysis by the IRMS. Using GC-HTC-MS/IRMS, chlorine isotope analysis at optimized conversion conditions resulted in very accurate isotope values (δ(37)Cl(SMOC)) for measured reference material with known isotope composition, including chlorinated ethylene, chloromethane, hexachlorocyclohexane, and trichloroacetic acids methyl ester. Respective detection limits were determined to be <15 nmol Cl on column with achieved precision of <0.3‰.

Monitoring CO[subscript 2] Fixation Using GC-MS Detection of a [superscript 13]C-Label

ERIC Educational Resources Information Center

Hammond, Daniel G.; Bridgham, April; Reichert, Kara; Magers, Martin

2010-01-01

Much of our understanding of metabolic pathways has resulted from the use of chemical and isotopic labels. In this experiment, a heavy isotope of carbon, [superscript 13]C, is used to label the product of the well-known RuBisCO enzymatic reaction. This is a key reaction in photosynthesis that converts inorganic carbon to organic carbon; a process…

What's New in the Site Characterization Tool Box: Molecular Biological Tools to Identify Microorganisms that Degrade Contaminants and Contaminant-Specific Isotope Analysis to Identify Sources and Document Degradation

EPA Science Inventory

In the past, it was necessary to conduct intensive sampling and monitoring of concentrations of contaminants in ground water to trace plumes back to their true source. Now it is possible to determine the ratio of stable isotopes of carbon, hydrogen or chlorine in the contaminan...

Glucose Measurement: Time for a Gold Standard

PubMed Central

Hagvik, Joakim

2007-01-01

There is no internationally recognized reference method for the measurement of blood glucose. The Centers for Disease Control and Prevention (CDC) highlighted the need for standardization some years ago when a project was started. The project objectives were to (1) investigate whether there are significant differences in calibration levels among currently used glucose monitors for home use and (2) develop a reference method for glucose determination. A first study confirmed the assumption that currently used home-use monitors differ significantly and that standardization is necessary in order to minimize variability and to improve patient care. As a reference method, CDC recommended a method based on isotope dilution gas chromatography–mass spectrometry, an assay that has received support from clinical chemists worldwide. CDC initiated a preliminary study to establish the suitability of this method, but then the project came to a halt. It is hoped that CDC, with support from the industry, as well as academic and professional organizations such as the American Association for Clinical Chemistry and International Federation of Clinical Chemistry and Laboratory Medicine, will be able to finalize the project and develop the long-awaited and much needed “gold standard” for glucose measurement. PMID:19888402

Southern Greenland water vapour isotopic composition at the crossroads of Atlantic and Arctic moisture

NASA Astrophysics Data System (ADS)

Bonne, J. L.; Steen-Larsen, H. C.; Risi, C. M.; Werner, M.; Sodemann, H.; Lacour, J. L.; Fettweis, X.; Cesana, G.; Delmotte, M.; Cattani, O.; Clerbaux, C.; Sveinbjörnsdottir, A. E.; Masson-Delmotte, V.

2014-12-01

Since September 2011, a continuous water vapour isotopic composition monitoring instrument has been remotely operated in Ivittuut (61.21°N, 48.17°W), southern Greenland. Meteorological parameters are monitored and precipitation has been sampled and analysed for isotopic composition, suggesting equilibrium between surface vapour and precipitation. The data depict small summer diurnal variations. δ18O and deuterium excess (d-excess) are generally anti-correlated and show important seasonal variations (with respective amplitudes of 10 and 20 ‰), and large synoptic variations associated to low-pressure systems (typically +5‰ on δ18O and -15‰ on d-excess). The moisture sources, estimated based on Lagrangian back-trajectories, are primarily influenced by the western North Atlantic, and north-eastern American continent. Notable are important seasonal and synoptic shifts of the moisture sources, and sporadic influences of the Arctic or the eastern North Atlantic. Moisture sources variations can be related to changes in water vapour isotopic composition, and the isotopic fingerprints can be attributed to the areas of moisture origins. Isotopic enabled AGCMs nudged to meteorology (LMDZiso, ECHAM5-wiso), despite biases, correctly capture the δ18O changes, but underestimate the d-excess changes. They allow to identify a high correlation between the southern Greenland d-excess and the simulated relative humidity and d-excess in the moisture source region south of Greenland. An extreme high temperature event in July 2012 affecting all Greenland, similar to ice sheet melt events during the medieval periods and one event in 1889 documented by Greenland ice core records, has been analysed regarding water vapour isotopic composition, using remote sensing (IASI) and in situ observations from Bermuda to northern Greenland (NEEM station). Our southern Greenland observations allow to track the water vapour evolution during this event along the moisture transport path, depicting the northward propagation of an isotopic signal inherited from the meteorological conditions during evaporation. Overall, our observations provide valuable information for interpreting Greenland ice core records as well as for evaluating water vapour isotopic simulations in atmospheric models.

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste.

PubMed

Wimmer, Bernhard; Hrad, Marlies; Huber-Humer, Marion; Watzinger, Andrea; Wyhlidal, Stefan; Reichenauer, Thomas G

2013-10-01

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ(13)C, δ(2)H and δ(18)O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ(13)C-value of the dissolved inorganic carbon (δ(13)C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ(13)C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ(13)C-DIC of -20‰ to -25‰. The production of methane under anaerobic conditions caused an increase in δ(13)C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ(13)C-DIC of about -20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation-reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Characterization of phenols biodegradation by compound specific stable isotope analysis

NASA Astrophysics Data System (ADS)

Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

2015-04-01

Biodegradation of phenol and alkylphenols has been described under both oxic and anoxic conditions. In the absence of molecular oxygen, the degradation of phenolic compounds is initiated by microorganisms through carboxylation, fumarate addition to the methyl moiety or anoxic hydroxylation of the methyl moiety. Comparatively, under aerobic condition, the initiation mechanisms are revealed to be monoxygenation or dihydroxylation for phenol and ring hydroxylation or methyl group oxidation for cresols. While several studies biochemically characterized the enzymes and reaction mechanisms in the relevant degradation pathways, isotope fractionation patterns were rarely reported possibly due to constraints in current analytical methods. In this study, the carbon isotope fractionation patterns upon the degradation of phenol and cresols by several strains were analyzed by using isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). The corresponding enrichment factors for carbon (ƐC) have been obtained. Cresols degradation by various strains showed generally moderate carbon isotope fractionation patterns with notable differences. For p-cresol degradation, five strains were examined. The aerobic strain Acinetobacter calcoaceticus NCIMB8250 exploits ring hydroxylation by molecular oxygen as initial reaction, and a ƐC value of -1.4±0.2‰ was obtained. Pseudomonas pseudoalcaligenes NCIMB 9867, an aerobic strain initiating cresols degradation via oxygen-dependent side chain hydroxylation, yielded a ƐC value of -2.3±0.2‰. Under nitrate-reducing conditions, Geobacter metallireducens DSM 7210 and Azoarcus buckelii DSM 14744 attacks p-cresol at the side chain by monohydroxylation using water as oxygen source; the two strains produced ƐC values of -3.6±0.4‰ and -2±0.1‰, accordingly. The sulfate-reducing Desulfosarcina cetonica DSM 7267 activating cresols by fumarate addition to the methyl moiety yielded ƐC values of -1.9±0.2‰ for p-cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

Accurate determination of selected pesticides in soya beans by liquid chromatography coupled to isotope dilution mass spectrometry.

PubMed

Huertas Pérez, J F; Sejerøe-Olsen, B; Fernández Alba, A R; Schimmel, H; Dabrio, M

2015-05-01

A sensitive, accurate and simple liquid chromatography coupled with mass spectrometry method for the determination of 10 selected pesticides in soya beans has been developed and validated. The method is intended for use during the characterization of selected pesticides in a reference material. In this process, high accuracy and appropriate uncertainty levels associated to the analytical measurements are of utmost importance. The analytical procedure is based on sample extraction by the use of a modified QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and subsequent clean-up of the extract with C18, PSA and Florisil. Analytes were separated on a C18 column using gradient elution with water-methanol/2.5 mM ammonium acetate mobile phase, and finally identified and quantified by triple quadrupole mass spectrometry in the multiple reaction monitoring mode (MRM). Reliable and accurate quantification of the analytes was achieved by means of stable isotope-labelled analogues employed as internal standards (IS) and calibration with pure substance solutions containing both, the isotopically labelled and native compounds. Exceptions were made for thiodicarb and malaoxon where the isotopically labelled congeners were not commercially available at the time of analysis. For the quantification of those compounds methomyl-(13)C2(15)N and malathion-D10 were used respectively. The method was validated according to the general principles covered by DG SANCO guidelines. However, validation criteria were set more stringently. Mean recoveries were in the range of 86-103% with RSDs lower than 8.1%. Repeatability and intermediate precision were in the range of 3.9-7.6% and 1.9-8.7% respectively. LODs were theoretically estimated and experimentally confirmed to be in the range 0.001-0.005 mg kg(-1) in the matrix, while LOQs established as the lowest spiking mass fractionation level were in the range 0.01-0.05 mg kg(-1). The method reliably identifies and quantifies the selected pesticides in soya beans at appropriate uncertainty levels, making it suitable for the characterization of candidate reference materials. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Method for separating boron isotopes

DOEpatents

Rockwood, Stephen D.

1978-01-01

A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

Quantifying wetland–aquifer interactions in a humid subtropical climate region: An integrated approach

USGS Publications Warehouse

Mendoza-Sanchez, Itza; Phanikumar, Mantha S.; Niu, Jie; Masoner, Jason R.; Cozzarelli, Isabelle M.; McGuire, Jennifer T.

2013-01-01

Wetlands are widely recognized as sentinels of global climate change. Long-term monitoring data combined with process-based modeling has the potential to shed light on key processes and how they change over time. This paper reports the development and application of a simple water balance model based on long-term climate, soil, vegetation and hydrological dynamics to quantify groundwater–surface water (GW–SW) interactions at the Norman landfill research site in Oklahoma, USA. Our integrated approach involved model evaluation by means of the following independent measurements: (a) groundwater inflow calculation using stable isotopes of oxygen and hydrogen (16O, 18O, 1H, 2H); (b) seepage flux measurements in the wetland hyporheic sediment; and (c) pan evaporation measurements on land and in the wetland. The integrated approach was useful for identifying the dominant hydrological processes at the site, including recharge and subsurface flows. Simulated recharge compared well with estimates obtained using isotope methods from previous studies and allowed us to identify specific annual signatures of this important process during the period of study (1997–2007). Similarly, observations of groundwater inflow and outflow rates to and from the wetland using seepage meters and isotope methods were found to be in good agreement with simulation results. Results indicate that subsurface flow components in the system are seasonal and readily respond to rainfall events. The wetland water balance is dominated by local groundwater inputs and regional groundwater flow contributes little to the overall water balance.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

Hydrologic, chemical, and isotopic characterization of two small watersheds on Catoctin Mountain, north-central Maryland, U.S.A.

USGS Publications Warehouse

Rice, Karen C.; Bricker, O.P.

1993-01-01

Two small (100 ha) watersheds located on Catoctin Mountain in north-central Maryland were intensively instrumented in 1990 and have been hydrologically, chemically, and isotopically monitored for 3 years. Dissolved concentrations of major ions (Ca2+, Mg2+, Na+, K+, total AI, CI-, NO3-, SO42- , HCO3-, and SiO2) and stable isotopic (D and 18O) values have been analyzed for most types of water (precipitation, throughfall, two depths of soil water, shallow groundwater, and streamwater) that enter, travel through, and exit each watershed. The major objectives of the study were to characterize the chemical and isotopic signatures of all aqueous components of the watersheds and to interpret the causes of the changes in chemical and isotopic compositions of streamwater during storm runoff. This paper describes selected results of the study.

Oxygen isotope corrections for online δ34S analysis

USGS Publications Warehouse

Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

2002-01-01

Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

Improvements in the gaseous hydrogen-water equilibration technique for hydrogen isotope ratio analysis

USGS Publications Warehouse

Coplen, T.B.; Wildman, J.D.; Chen, J.

1991-01-01

Improved precision in the H2-H2O equilibration method for ??D analysis has been achieved in an automated system. Reduction in 1-?? standard deviation of a single mass-spectrometer analysis to 1.3??? is achieved by (1) bonding catalyst to glass rods and assigning use to specific equilibration chambers to monitor performance of catalyst, (2) improving the apparatus design, and (3) reducing the H3+ contribution of the mass-spectrometer ion source. For replicate analysis of a water sample, the standard deviation improved to 0.8???. H2S-bearing samples and samples as small as 0.1 mL can be analyzed routinely with this method.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

PubMed

Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

2006-01-01

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented. Copyright 2006 John Wiley & Sons, Ltd.

Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change?

NASA Astrophysics Data System (ADS)

Frei, R.; Gaucher, C.

2010-12-01

Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr(VI) reduction in groundwater: a detailed time-series study of a point-source plume. Environ. Sci. Technol., v. 44, p. 1043-1048. J.A. Izbicki et al. (2008) Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA. Applied Geochemistry, v.23, p. 1325-1352. R. Frei et al. (2009) Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes. Nature, v. 461, p. 250-253. C. Gaucher et al. (2004) Chemostratigraphy of the Lower Arroyo del Soldado Group (Vendian, Uruguay) and palaeoclimatic implications. Gondwana Research, v.7, p. 715-730

[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.

Monitoring Microbial Mineralization Using Reverse Stable Isotope Labeling Analysis by Mid-Infrared Laser Spectroscopy

PubMed Central

2017-01-01

Assessing the biodegradation of organic compounds is a frequent question in environmental science. Here, we present a sensitive, inexpensive, and simple approach to monitor microbial mineralization using reverse stable isotope labeling analysis (RIL) of dissolved inorganic carbon (DIC). The medium for the biodegradation assay contains regular organic compounds and 13C-labeled DIC with 13C atom fractions (x(13C)DIC) higher than natural abundance (typically 2–50%). The produced CO2 (x(13C) ≈ 1.11%) gradually dilutes the initial x(13C)DIC allowing to quantify microbial mineralization using mass-balance calculations. For 13C-enriched CO2 samples, a newly developed isotope ratio mid-infrared spectrometer was introduced with a precision of x(13C) < 0.006%. As an example for extremely difficult and slowly degradable compounds, CO2 production was close to the theoretical stoichiometry for anaerobic naphthalene degradation by a sulfate-reducing enrichment culture. Furthermore, we could measure the aerobic degradation of dissolved organic carbon (DOC) adsorbed to granular activated carbon in a drinking water production plant, which cannot be labeled with 13C. Thus, the RIL approach can be applied to sensitively monitor biodegradation of various organic compounds under anoxic or oxic conditions. PMID:28903553

Set Up of an Automatic Water Quality Sampling System in Irrigation Agriculture

PubMed Central

Heinz, Emanuel; Kraft, Philipp; Buchen, Caroline; Frede, Hans-Georg; Aquino, Eugenio; Breuer, Lutz

2014-01-01

We have developed a high-resolution automatic sampling system for continuous in situ measurements of stable water isotopic composition and nitrogen solutes along with hydrological information. The system facilitates concurrent monitoring of a large number of water and nutrient fluxes (ground, surface, irrigation and rain water) in irrigated agriculture. For this purpose we couple an automatic sampling system with a Wavelength-Scanned Cavity Ring Down Spectrometry System (WS-CRDS) for stable water isotope analysis (δ2H and δ18O), a reagentless hyperspectral UV photometer (ProPS) for monitoring nitrate content and various water level sensors for hydrometric information. The automatic sampling system consists of different sampling stations equipped with pumps, a switch cabinet for valve and pump control and a computer operating the system. The complete system is operated via internet-based control software, allowing supervision from nearly anywhere. The system is currently set up at the International Rice Research Institute (Los Baños, The Philippines) in a diversified rice growing system to continuously monitor water and nutrient fluxes. Here we present the system's technical set-up and provide initial proof-of-concept with results for the isotopic composition of different water sources and nitrate values from the 2012 dry season. PMID:24366178

Monitoring uranium, hydrogen, and lithium and their isotopes using a compact laser-induced breakdown spectroscopy (LIBS) probe and high-resolution spectrometer.

PubMed

Cremers, David A; Beddingfield, Alan; Smithwick, Robert; Chinni, Rosemarie C; Jones, C Randy; Beardsley, Burt; Karch, Larry

2012-03-01

The development of field-deployable instruments to monitor radiological, nuclear, and explosive (RNE) threats is of current interest for a number of assessment needs such as the on-site screening of suspect facilities and nuclear forensics. The presence of uranium and plutonium and radiological materials can be determined through monitoring the elemental emission spectrum using relatively low-resolution spectrometers. In addition, uranium compounds, explosives, and chemicals used in nuclear fuel processing (e.g., tributyl-phosphate) can be identified by applying chemometric analysis to the laser-induced breakdown (LIBS) spectrum recorded by these spectrometers. For nuclear forensic applications, however, isotopes of U and Pu and other elements (e.g., H and Li) must also be determined, requiring higher resolution spectrometers given the small magnitude of the isotope shifts for some of these elements (e.g., 25 pm for U and 13 pm for Pu). High-resolution spectrometers will be preferred for several reasons but these must fit into realistic field-based analysis scenarios. To address the need for field instrumentation, we evaluated a previously developed field-deployable hand-held LIBS interrogation probe combined with two relatively new high-resolution spectrometers (λ/Δλ ~75,000 and ~44,000) that have the potential to meet field-based analysis needs. These spectrometers are significantly smaller and lighter in weight than those previously used for isotopic analysis and one unit can provide simultaneous wide spectral coverage and high resolution in a relatively small package. The LIBS interrogation probe was developed initially for use with low resolution compact spectrometers in a person-portable backpack LIBS instrument. Here we present the results of an evaluation of the LIBS probe combined with a high-resolution spectrometer and demonstrate rapid detection of isotopes of uranium and hydrogen and highly enriched samples of (6)Li and (7)Li. © 2012 Society for Applied Spectroscopy

Development and validation of a liquid chromatography-tandem mass spectrometry analytical method for the therapeutic drug monitoring of eight novel anticancer drugs.

PubMed

Herbrink, M; de Vries, N; Rosing, H; Huitema, A D R; Nuijen, B; Schellens, J H M; Beijnen, J H

2018-04-01

To support therapeutic drug monitoring of patients with cancer, a fast and accurate method for simultaneous quantification of the registered anticancer drugs afatinib, axitinib, ceritinib, crizotinib, dabrafenib, enzalutamide, regorafenib and trametinib in human plasma using liquid chromatography tandem mass spectrometry was developed and validated. Human plasma samples were collected from treated patients and stored at -20°C. Analytes and internal standards (stable isotopically labeled analytes) were extracted with acetonitrile. An equal amount of 10 mm NH 4 CO 3 was added to the supernatant to yield the final extract. A 2 μL aliquot of this extract was injected onto a C 18 -column, gradient elution was applied and triple-quadrupole mass spectrometry in positive-ion mode was used for detection. All results were within the acceptance criteria of the latest US Food and Drug Administration guidance and European Medicines Agency guidelines on method validation, except for the carry-over of ceritinib and crizotinib. These were corrected for by the injection order of samples. Additional stability tests were carried out for axitinib and dabrafenib in relation to their reported photostability. In conclusion, the described method to simultaneously quantify the eight selected anticancer drugs in human plasma was successfully validated and applied for therapeutic drug monitoring in cancer patients treated with these drugs. Copyright © 2017 John Wiley & Sons, Ltd.

Improved performance comparisons of radioxenon systems for low level releases in nuclear explosion monitoring.

PubMed

Haas, Derek A; Eslinger, Paul W; Bowyer, Theodore W; Cameron, Ian M; Hayes, James C; Lowrey, Justin D; Miley, Harry S

2017-11-01

The Comprehensive Nuclear-Test-Ban Treaty bans all nuclear tests and mandates development of verification measures to detect treaty violations. One verification measure is detection of radioactive xenon isotopes produced in the fission of actinides. The International Monitoring System (IMS) currently deploys automated radioxenon systems that can detect four radioxenon isotopes. Radioxenon systems with lower detection limits are currently in development. Historically, the sensitivity of radioxenon systems was measured by the minimum detectable concentration for each isotope. In this paper we analyze the response of radioxenon systems using rigorous metrics in conjunction with hypothetical representative releases indicative of an underground nuclear explosion instead of using only minimum detectable concentrations. Our analyses incorporate the impact of potential spectral interferences on detection limits and the importance of measuring isotopic ratios of the relevant radioxenon isotopes in order to improve discrimination from background sources particularly for low-level releases. To provide a sufficient data set for analysis, hypothetical representative releases are simulated every day from the same location for an entire year. The performance of three types of samplers are evaluated assuming they are located at 15 IMS radionuclide stations in the region of the release point. The performance of two IMS-deployed samplers and a next-generation system is compared with proposed metrics for detection and discrimination using representative releases from the nuclear test site used by the Democratic People's Republic of Korea. Copyright © 2017 Elsevier Ltd. All rights reserved.

Inverse methods for estimating primary input signals from time-averaged isotope profiles

NASA Astrophysics Data System (ADS)

Passey, Benjamin H.; Cerling, Thure E.; Schuster, Gerard T.; Robinson, Todd F.; Roeder, Beverly L.; Krueger, Stephen K.

2005-08-01

Mammalian teeth are invaluable archives of ancient seasonality because they record along their growth axes an isotopic record of temporal change in environment, plant diet, and animal behavior. A major problem with the intra-tooth method is that intra-tooth isotope profiles can be extremely time-averaged compared to the actual pattern of isotopic variation experienced by the animal during tooth formation. This time-averaging is a result of the temporal and spatial characteristics of amelogenesis (tooth enamel formation), and also results from laboratory sampling. This paper develops and evaluates an inverse method for reconstructing original input signals from time-averaged intra-tooth isotope profiles. The method requires that the temporal and spatial patterns of amelogenesis are known for the specific tooth and uses a minimum length solution of the linear system Am = d, where d is the measured isotopic profile, A is a matrix describing temporal and spatial averaging during amelogenesis and sampling, and m is the input vector that is sought. Accuracy is dependent on several factors, including the total measurement error and the isotopic structure of the measured profile. The method is shown to accurately reconstruct known input signals for synthetic tooth enamel profiles and the known input signal for a rabbit that underwent controlled dietary changes. Application to carbon isotope profiles of modern hippopotamus canines reveals detailed dietary histories that are not apparent from the measured data alone. Inverse methods show promise as an effective means of dealing with the time-averaging problem in studies of intra-tooth isotopic variation.

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography.

PubMed

Zheng, Jian; Yamada, Masatoshi

2006-01-15

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios ((235)U/(238)U atom ratio and (234)U/(238)U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise (234)U/(238)U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for (235)U/(238)U atom ratio and lower than 2.0% R.S.D. for (234)U/(238)U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

PubMed

Roussis, Stilianos G; Proulx, Richard

2003-03-15

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

Evaluating cleansing effects on trace elements and stable isotope values in feathers of oiled birds.

PubMed

Valladares, Sonia; Moreno, Roćio; Jover, Lluis; Sanpera, Carola

2010-01-01

Feathers of seabirds are widely used as a nondestructive tissue for pollution monitoring of trace elements, as well as convenient samples for trophic ecology studies by means of stable isotope analysis (SIA). Nevertheless, feathers can be occasionally impregnated with oil from deliberate ship discharges and from massive oil spill accidents. The feather structure makes them effective traps for particles and are subject to external contamination. It is unknown to what extent the oil adhered to feathers can change trace element concentrations or stable isotope signatures. This study has two primary objectives: (1) to assess if there are differences between trace element concentrations and stable isotope signatures of oiled and clean feathers, and (2) to determine if the cleansing of oiled feathers using commonly applied techniques such as sodium hydroxide (NaOH) washes in combination with an organic solvent (hexane) is more effective than using NaOH alone. In order to do this, we analysed trace elements (Se, Hg, Pb, Cu and Zn) and stable isotopes (delta(13)C and delta(15)N) of individual feathers of yellow-legged gulls (Larus michahellis) which were affected by the 2002 Prestige oil spill in Galicia (NW Spain). Two sets of feathers were analysed, one group were oil-free (Control group) and the other had oil adhered to its surface (Oiled group). We expected to find differences between control and oiled feathers when cleaning exclusively with NaOH and no differences when using hexane. Our results did not show significant differences between Control and Oiled groups as a consequence of the cleansing method used. Unexpectedly, the additional cleansing with hexane resulted in decreasing selenium concentrations and increasing zinc and delta(15)N values in all groups of feathers.

Evaluating degradation of hexachlorcyclohexane (HCH) isomers within a contaminated aquifer using compound-specific stable carbon isotope analysis (CSIA).

PubMed

Bashir, Safdar; Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans H; Fischer, Anko

2015-03-15

The applicability of compound-specific stable carbon isotope analysis (CSIA) for assessing biodegradation of hexachlorocyclohexane (HCH) isomers was investigated in a contaminated aquifer at a former pesticide processing facility. A CSIA method was developed and tested for efficacy in determining carbon isotope ratios of HCH isomers in groundwater samples using gas chromatography - isotope ratio mass spectrometry (GC-IRMS). The carbon isotope ratios of HCHs measured for samples taken from the field site confirmed contaminant source zones at former processing facilities, a storage depot and a waste dump site. The (13)C-enrichment in HCHs provided evidence for biodegradation of HCHs especially downstream of the contaminant source zones. CSIA from monitoring campaigns in 2008, 2009 and 2010 revealed temporal trends in HCH biodegradation. Thus, the impact and progress of natural attenuation processes could be evaluated within the investigated aquifer. Calculations based on the Rayleigh-equation approach yielded levels of HCH biodegradation ranging from 30 to 86 %. Moreover, time- and distance-dependent in situ first-order biodegradation rate constants were estimated with maximal values of 3 × 10(-3) d(-1) and 10 × 10(-3) m(-1) for α-HCH, 11 × 10(-3) d(-1) and 37 × 10(-3) m(-1) for β-HCH, and 6 × 10(-3) d(-1) and 19 × 10(-3) m(-1) for δ-HCH, respectively. This study highlights the applicability of CSIA for the assessment of HCH biodegradation within contaminated aquifers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method for discriminative particle selection

DOEpatents

Post, Richard F.

1992-01-01

The invention is a method and means for separating ions or providing an ion beam. The invention generates ions of the isotopes to be separated, and then provides a traveling electric potential hill created by a sequential series of quasi static electric potential hills. By regulating the velocity and potential amplitude of the traveling electric potential hill ionized isotopes are selectively positively or negatively accelerated. Since the ionized isotopes have differing final velocities, the isotopes may be collected separately or used to produce an ion beam of a selected isotope.

The effect of saline groundwater exchange, evaporation and variable river flows and on stable isotopes (18O and 2H) and major ion concentrations along the Darling River, NSW, Australia

NASA Astrophysics Data System (ADS)

Meredith, K. T.; Hughes, C. E.; Hollins, S. E.; Cendón, D. I.; Hankin, S.

2009-04-01

Australia's longest river, the Darling River, faces extreme pressure from drought and over extraction of water from its catchment. The lack of detailed baseline hydrochemical and isotopic data for the Darling River has prompted research aimed at using hydrological tracers to assess water gains and losses within the Darling River Drainage Basin. This study uses temporal hydrochemical and stable isotope data (18O and 2H) that has been monitored from gauging stations along the Barwon-Darling catchment over a five-year period from 2002 to 2007 as part of the Global Network for Isotopes in Rivers (GNIR) monitoring programme. Stream flow data, monthly δ18O and δ2H values and major ion chemistry is presented. Individual flow events were found to be isotopically distinct but the LELs that develop after these events have a very similar slope indicating similar climatic conditions across this region. During low flow conditions, salt concentrations increase systematically, δ18O and δ2H become enriched and d-excess becomes more negative indicating significant evaporation. Flow events input isotopically depleted fresh waters to the system and the d-excess returns towards the local meteoric water line. The major ions increase in concentration at a greater rate at Louth than they do at upstream at Bourke or downstream at Wilcannia, despite similar decreases in flow rates for all three sites. The hydrological response of the river to drought has had detrimental affects on the surface water system because it provides a pathway for saline groundwater to discharge into the river system.

Characteristics of lead isotope ratios and elemental concentrations in PM 10 fraction of airborne particulate matter in Shanghai after the phase-out of leaded gasoline

NASA Astrophysics Data System (ADS)

Zheng, Jian; Tan, Mingguang; Shibata, Yasuyuki; Tanaka, Atsushi; Li, Yan; Zhang, Guilin; Zhang, Yuanmao; Shan, Zuci

The stable lead (Pb) isotope ratios and the concentrations of 23 elements, including heavy metals and toxic elements, were measured in the PM 10 airborne particle samples collected at seven monitoring sites in Shanghai, China, to evaluate the current elemental compositions and local airborne Pb isotope ratio characteristics. Some source-related samples, such as cement, coal and oil combustion dust, metallurgic dust, vehicle exhaust particles derived from leaded gasoline and unleaded gasoline, and polluted soils were analyzed for their Pb content and isotope ratio and compared to those observed in PM 10 samples. Airborne Pb concentration ranged from 167 to 854 ng/m 3 in the seven monitored sites with an average of 515 ng/m 3 in Shanghai, indicating that a high concentration of Pb remains in the air after the phasing out of leaded gasoline. Lead isotopic compositions in airborne particles ( 207Pb/ 206Pb, 0.8608±0.0018; 208Pb/ 206Pb, 2.105±0.005) are clearly distinct from the vehicle exhaust particles ( 207Pb/ 206Pb, 0.8854±0.0075; 208Pb/ 206Pb, 2.145±0.006), suggesting that the automotive lead is not currently the major component of Pb in the air. By using a binary mixing equation, a source apportionment based on 207Pb/ 206Pb ratios, indicates that the contribution from automotive emission to the airborne Pb is around 20%. The Pb isotope ratios obtained in the source-related samples confirmed that the major emission sources are metallurgic dust, coal combustion, and cement.

Monitoring concentration and isotopic composition of methane in groundwater in the Utica Shale hydraulic fracturing region of Ohio.

PubMed

Claire Botner, E; Townsend-Small, Amy; Nash, David B; Xu, Xiaomei; Schimmelmann, Arndt; Miller, Joshua H

2018-05-03

Degradation of groundwater quality is a primary public concern in rural hydraulic fracturing areas. Previous studies have shown that natural gas methane (CH 4 ) is present in groundwater near shale gas wells in the Marcellus Shale of Pennsylvania, but did not have pre-drilling baseline measurements. Here, we present the results of a free public water testing program in the Utica Shale of Ohio, where we measured CH 4 concentration, CH 4 stable isotopic composition, and pH and conductivity along temporal and spatial gradients of hydraulic fracturing activity. Dissolved CH 4 ranged from 0.2 μg/L to 25 mg/L, and stable isotopic measurements indicated a predominantly biogenic carbonate reduction CH 4 source. Radiocarbon dating of CH 4 in combination with stable isotopic analysis of CH 4 in three samples indicated that fossil C substrates are the source of CH 4 in groundwater, with one 14 C date indicative of modern biogenic carbonate reduction. We found no relationship between CH 4 concentration or source in groundwater and proximity to active gas well sites. No significant changes in CH 4 concentration, CH 4 isotopic composition, pH, or conductivity in water wells were observed during the study period. These data indicate that high levels of biogenic CH 4 can be present in groundwater wells independent of hydraulic fracturing activity and affirm the need for isotopic or other fingerprinting techniques for CH 4 source identification. Continued monitoring of private drinking water wells is critical to ensure that groundwater quality is not altered as hydraulic fracturing activity continues in the region. Graphical abstract A shale gas well in rural Appalachian Ohio. Photo credit: Claire Botner.

Identification of energy consumption and nutritional stress by isotopic and elemental analysis of urine in bonobos (Pan paniscus).

PubMed

Deschner, Tobias; Fuller, Benjamin T; Oelze, Vicky M; Boesch, Christophe; Hublin, Jean-Jacques; Mundry, Roger; Richards, Michael P; Ortmann, Sylvia; Hohmann, Gottfried

2012-01-15

A mounting body of evidence suggests that changes in energetic conditions like prolonged starvation can be monitored using stable isotope ratios of tissues such as bone, muscle, hair, and blood. However, it is unclear if urinary stable isotope ratios reflect a variation in energetic condition, especially if these changes in energetic condition are accompanied by shifts in dietary composition. In a feeding experiment conducted on captive bonobos (Pan paniscus), we monitored urinary δ(13)C, δ(15)N, total C (carbon), total N (nitrogen), and C/N ratios and compared these results with glucocorticoid levels under gradually changing energy availability and dietary composition. Measurements of daily collected urine samples over a period of 31 days showed that while shifts in urinary isotope signatures of δ(13)C and δ(15)N as well as total C were best explained by changes in energy consumption, urinary total N excretion as well as the C/N ratios matched the variation in dietary composition. Furthermore, when correcting for fluctuations in dietary composition, the isotope signatures of δ(13)C and δ(15)N as well as total C correlated with urinary glucocorticoid levels; however, the urinary total N and the C/N ratio did not. These results indicate for the first time that it is possible to non-invasively explore specific longitudinal records on animal energetic conditions and dietary compositions with urinary stable isotope ratios and elemental compositions, and this research provides a strong foundation for investigating how ecological factors and social dynamics affect feeding habits in wild animal populations such as primates. Copyright © 2011 John Wiley & Sons, Ltd.

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

PubMed Central

Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

2014-01-01

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

A novel method for rapid in vitro radiobioassay

NASA Astrophysics Data System (ADS)

Crawford, Evan Bogert

Rapid and accurate analysis of internal human exposure to radionuclides is essential to the effective triage and treatment of citizens who have possibly been exposed to radioactive materials in the environment. The two most likely scenarios in which a large number of citizens would be exposed are the detonation of a radiation dispersal device (RDD, "dirty bomb") or the accidental release of an isotope from an industrial source such as a radioisotopic thermal generator (RTG). In the event of the release and dispersion of radioactive materials into the environment in a large city, the entire population of the city -- including all commuting workers and tourists -- would have to be rapidly tested, both to satisfy the psychological needs of the citizens who were exposed to the mental trauma of a possible radiation dose, and to satisfy the immediate medical needs of those who received the highest doses and greatest levels of internal contamination -- those who would best benefit from rapid, intensive medical care. In this research a prototype rapid screening method to screen urine samples for the presence of up to five isotopes, both individually and in a mixture, has been developed. The isotopes used to develop this method are Co-60, Sr-90, Cs-137, Pu-238, and Am-241. This method avoids time-intensive chemical separations via the preparation and counting of a single sample on multiple detectors, and analyzing the spectra for isotope-specific markers. A rapid liquid-liquid separation using an organic extractive scintillator can be used to help quantify the activity of the alpha-emitting isotopes. The method provides quantifiable results in less than five minutes for the activity of beta/gamma-emitting isotopes when present in the sample at the intervention level as defined by the Centers for Disease Control and Prevention (CDC), and quantifiable results for the activity levels of alpha-emitting isotopes present at their respective intervention levels in approximately 30 minutes of sample preparation and counting time. Radiation detector spectra -- e.g. those from high-purity germanium (HPGe) gamma detectors and liquid scintillation detectors -- which contain decay signals from multiple isotopes often have overlapping signals: the counts from one isotope's decay can appear in energy channels associated with another isotope's decay, complicating the calculation of each isotope's activity. The uncertainties associated with analyzing these spectra have been traced in order to determine the effects of one isotope's count rate on the sensitivity and uncertainty associated with each other isotope. The method that was developed takes advantage of activated carbon filtration to eliminate quenching effects and to make the liquid scintillation spectra from different urine samples comparable. The method uses pulse-shape analysis to reduce the interference from beta emitters in the liquid scintillation spectrum and improve the minimum detectable activity (MDA) and minimum quantifiable activity (MQA) for alpha emitters. The method uses an HPGe detector to quantify the activity of gamma emitters, and subtract their isotopes' contributions to the liquid scintillation spectra via a calibration factor, such that the pure beta and pure alpha emitters can be identified and quantified from the resulting liquid scintillation spectra. Finally, the method optionally uses extractive scintillators to rapidly separate the alpha emitters from the beta emitters when the activity from the beta emitters is too great to detect or quantify the activity from the alpha emitters without such a separation. The method is able to detect and quantify all five isotopes, with uncertainties and biases usually in the 10-40% range, depending upon the isotopic mixtures and the activity ratios between each of the isotopes.

Simultaneous stable carbon isotopic analysis of wine glycerol and ethanol by liquid chromatography coupled to isotope ratio mass spectrometry.

PubMed

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2010-01-27

A novel procedure was established for the simultaneous characterization of wine glycerol and ethanol (13)C/(12)C isotope ratio, using liquid chromatography/isotope ratio mass spectrometry (LC-IRMS). Several parameters influencing separation of glycerol and ethanol from wine matrix were optimized. Results obtained for 35 Spanish samples exposed no significant differences and very strong correlations (r = 0.99) between the glycerol (13)C/(12)C ratios obtained by an alternative method (gas chromatography/isotope ratio mass spectrometry) and the proposed new methodology, and between the ethanol (13)C/(12)C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The accuracy of the proposed method varied from 0.01 to 0.19 per thousand, and the analytical precision was better than 0.25 per thousand. The new developed LC-IRMS method it is the first isotopic method that allows (13)C/(12)C determination of both analytes in the same run directly from a liquid sample with no previous glycerol or ethanol isolation, overcoming technical difficulties associated with complex sample treatment and improving in terms of simplicity and speed.

South-France caves monitoring : present day cave air dynamics characterization,paleoclimatic and archaeological interests

NASA Astrophysics Data System (ADS)

Bourges, F.; Genty, D.; Genthon, P.; Mangin, A.; D'Hulst, D.

2012-04-01

Cave climatic environment survey covers different sort of analyses on air and water, and has various interests from the conservation of prehistoric caves to the study of paleoclimates. Depending on the purpose, the cave monitoring can be entirely automatic or combine both automatic and manual data acquisitions. Apparatus are adapted to cave environment to measure specific parameters (i.e. drip rate, air humidity, CO2) and during the long-term monitorings, several generations of techniques have been used. We present here examples of cave monitoring (1996 →) from South-France: Chauvet, Orgnac (Ardèche), Esparros (Hautes-Pyrénées) and Villars (Dordogne). In all these sites, we obtained among the longest series of climatic parameters of inside the caves, coupled sometimes with geochemical and isotopic analyses on air and seepage water, which allow to better understand cave air circulation behaviour and their sensitivity to the external climatic and environmental variations. High precision temperature measurements in Orgnac and Chauvet caves, coupled with pCO2 and radon analyses, allowed the reconstruction of seasonal air circulation patterns in each cave. While the Chauvet and Esparros caves are quite confined environments with temperature changes mainly controlled by air pressure variations, the Orgnac cave, like most caves, shows a well marked summer/winter regime alternation. Quantification of air flows of known CO2 concentration allowed the calculation of carbon fluxes toward the earth atmosphere which is estimated to about 340 gm-2yr-1. Since 15 years, the monitoring made in the Villars cave at two different levels has shown that the air temperature displays small seasonal variations in the upper galleries while it is not detectable in the lower ones. Average annual temperature difference between these two levels is of more than 1°C, showing that local differences in a single cave can be significant. A global warming trend likely correlated with local external temperature changes is observed in both levels since the beginning of the monitoring in 1996 which is not the case in Chauvet and Esparros caves. The stable isotope composition of the seepage water of the Villars cave and drip rates measured under several stalactites give precious information about the mixture of the rainfall infiltration signal in the unsaturated zone; these long isotopic series are discussed and compared with the rainfall (quantity and isotopic composition) sampled at this site.

Direct determination of fatty acid esters of 3-chloro-1, 2-propanediol in edible vegetable oils by isotope dilution - ultra high performance liquid chromatography - triple quadrupole mass spectrometry.

PubMed

Li, Heli; Chen, Dawei; Miao, Hong; Zhao, Yunfeng; Shen, Jianzhong; Wu, Yongning

2015-09-04

A selective and sensitive ultra-high performance liquid chromatography - triple quadrupole mass spectrometry (UHPLC-MS/MS) method coupled with matrix solid phase dispersion (MSPD) extraction was developed for the direct determination of fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible vegetable oils. The method integrated the isotope dilution technique, MSPD extraction and UHPLC - MS/MS analysis with multi-reaction monitoring mode (MRM). Matrix-matched calibration curves showed good linearity within the range of 0.01-10mgL(-1) with the correlation coefficient not less than 0.999. Limits of detection (LODs) and limit of quantification (LOQs) of the 3-MCPD esters fell into the range of 0.0001-0.02mgkg(-1) and 0.0004-0.05mgkg(-1), respectively. The recoveries for the spiked extra virgin olive oils ranged from 94.4% to 108.3%, with the relative standard deviations (RSD) ranging from 0.6% to 10.5%. The method was applied for the oil sample (T2642) of the official Food Analysis Performance Assessment Scheme (FAPAS) in 2014 and other real samples from supermarket, and the results showed that the present method was comparative to the gas chromatography-mass spectrometry (GC-MS) method based on the improved German Society for Fat Science (DGF) standard method C-III 18 (09) except for palm oil. Copyright © 2015. Published by Elsevier B.V.

Radioisotope Concentration in Lake Sediments of Maracaibo, Venezuela

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

Salas, A. Rangel; Viloria, T.; Sajo-Bohus, L.

2007-10-26

Maracaibo Lake is one of the most important water basing and oil producing regions in Venezuela. Changes in the local environment have been monitored for chemical pollution in the past. For this study we selected a set of sediment samples collected in the shore and analyzed for its radioisotope content. Results show the gamma emitting isotopes distribution. Isotopes concentrations have been determined within the natural K, Th and U families.

Using atmospheric chemistry and storm tracks to explain nitrate stable isotope variations in precipitation at a site in central Pennsylvania, USA

USDA-ARS?s Scientific Manuscript database

Stable isotopes of NO3- (delta15N-NO3- and delta18O-NO3-) were monitored in precipitation at a central Pennsylvania site during six storm events in 2005 to determine whether information on atmospheric oxidants (e.g. O3, NO2, and NOx), and storm-tracks were capable of explaining observed seasonal and...

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.

Assay Development for the Determination of Phosphorylation Stoichiometry using MRM methods with and without Phosphatase Treatment: Application to Breast Cancer Signaling Pathways

PubMed Central

Domanski, Dominik; Murphy, Leigh C.; Borchers, Christoph H.

2010-01-01

We have developed a phosphatase-based phosphopeptide quantitation (PPQ) method for determining phosphorylation stoichiometry in complex biological samples. This PPQ method is based on enzymatic dephosphorylation, combined with specific and accurate peptide identification and quantification by multiple reaction monitoring (MRM) detection with stable-isotope-labeled standard peptides. In contrast with the classical MRM methods for the quantitation of phosphorylation stoichiometry, the PPQ-MRM method needs only one non-phosphorylated SIS (stable isotope-coded standard) and two analyses (one for the untreated and one for the phosphatase-treated sample), from which the expression and modification levels can accurately be determined. From these analyses, the % phosphorylation can be determined. In this manuscript, we compare the PPQ-MRM method with an MRM method without phosphatase, and demonstrate the application of these methods to the detection and quantitation of phosphorylation of the classic phosphorylated breast cancer biomarkers (ERα and HER2), and for phosphorylated RAF and ERK1, which also contain phosphorylation sites with important biological implications. Using synthetic peptides spiked into a complex protein digest, we were able to use our PPQ-MRM method to accurately determine the total phosphorylation stoichiometry on specific peptides, as well as the absolute amount of the peptide and phosphopeptide present. Analyses of samples containing ERα protein revealed that the PPQ-MRM is capable of determining phosphorylation stoichiometry in proteins from cell lines, and is in good agreement with determinations obtained using the direct MRM approach in terms of phosphorylation and total protein amount. PMID:20524616

Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α-hexachlorocyclo-hexane in the environment.

PubMed

Badea, Silviu-Laurentiu; Vogt, Carsten; Gehre, Matthias; Fischer, Anko; Danet, Andrei-Florin; Richnow, Hans-Hermann

2011-05-30

α-Hexachlorocyclohexane (α-HCH) is the only chiral isomer of the eight 1,2,3,4,5,6-HCHs and we have developed an enantiomer-specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment. The carbon isotope ratios of the α-HCH enantiomers were determined for a commercially available α-HCH sample using a gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) system equipped with a chiral column. The GC-C-IRMS measurements revealed δ-values of -32.5 ± 0.8‰ and -32.3 ± 0.5‰ for (-) α-HCH and (+) α-HCH, respectively. The isotope ratio of bulk α-HCH was estimated to be -32.4 ± 0.6‰ which was in accordance with the δ-values obtained by GC-C-IRMS (-32.7 ± 0.2‰) and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) of the bulk α-HCH (-32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α-HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the α-HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly < ± 0.5‰. In order to test the chiral GC-C-IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α-HCH with Clostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of the α-HCH enantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotope fractionation can serve as an indicator for biodegradation and source characterization of α-HCH in the environment. Copyright © 2011 John Wiley & Sons, Ltd.

Delta13C and delta18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite.

PubMed

Révész, Kinga M; Landwehr, Jurate M

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was

Sensitive determination of thiols in wine samples by a stable isotope-coded derivatization reagent d0/d4-acridone-10-ethyl-N-maleimide coupled with high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry analysis.

PubMed

Lv, Zhengxian; You, Jinmao; Lu, Shuaimin; Sun, Weidi; Ji, Zhongyin; Sun, Zhiwei; Song, Cuihua; Chen, Guang; Li, Guoliang; Hu, Na; Zhou, Wu; Suo, Yourui

2017-03-31

As the key aroma compounds, varietal thiols are the crucial odorants responsible for the flavor of wines. Quantitative analysis of thiols can provide crucial information for the aroma profiles of different wine styles. In this study, a rapid and sensitive method for the simultaneous determination of six thiols in wine using d 0 /d 4 -acridone-10-ethyl-N-maleimide (d 0 /d 4 -AENM) as stable isotope-coded derivatization reagent (SICD) by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) has been developed. Quantification of thiols was performed by using d 4 -AENM labeled thiols as the internal standards (IS), followed by stable isotope dilution HPLC-ESI-MS/MS analysis. The AENM derivatization combined with multiple reactions monitoring (MRM) not only allowed trace analysis of thiols due to the extremely high sensitivity, but also efficiently corrected the matrix effects during HPLC-MS/MS and the fluctuation in MS/MS signal intensity due to instrument. The obtained internal standard calibration curves for six thiols were linear over the range of 25-10,000pmol/L (R 2 ≥0.9961). Detection limits (LODs) for most of analytes were below 6.3pmol/L. The proposed method was successfully applied for the simultaneous determination of six kinds of thiols in wine samples with precisions ≤3.5% and recoveries ≥78.1%. In conclusion, the developed method is expected to be a promising tool for detection of trace thiols in wine and also in other complex matrix. Copyright © 2017 Elsevier B.V. All rights reserved.

Method of separating boron isotopes

DOEpatents

Jensen, R.J.; Thorne, J.M.; Cluff, C.L.

1981-01-23

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)-dichloroborane as the feed material. The photolysis can readily by achieved with CO/sub 2/ laser radiation and using fluences significantly below those required to dissociate BCl/sub 3/.

Method of separating boron isotopes

DOEpatents

Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.

1984-01-01

A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE PAGES

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.; ...

2016-06-23

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

NASA Astrophysics Data System (ADS)

Knowles, Justin; Skutnik, Steven; Glasgow, David; Kapsimalis, Roger

2016-10-01

Rapid nondestructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the Oak Ridge National Laboratory High Flux Isotope Reactor Neutron Activation Analysis facility has developed a generalized nondestructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and makes use of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a complete characterization of isotopic identification, mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% recovery bias have been conducted on standards of 235U and 239Pu as low as 12 ng in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 198 ng of fissile mass with less than 7% recovery bias. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. It is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation facilities, and account for increasingly complex sample matrices.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

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

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

Method for separating isotopes

DOEpatents

Jepson, B.E.

1975-10-21

Isotopes are separated by contacting a feed solution containing the isotopes with a cyclic polyether wherein a complex of one isotope is formed with the cyclic polyether, the cyclic polyether complex is extracted from the feed solution, and the isotope is thereafter separated from the cyclic polyether.

Method for isotope separation by photodeflection

DOEpatents

Bernhardt, Anthony F.

1977-01-01

In the method of separating isotopes wherein a desired isotope species is selectively deflected out of a beam of mixed isotopes by irradiating the beam with a directed beam of light of narrowly defined frequency which is selectively absorbed by the desired species, the improvement comprising irradiating the deflected beam with light from other light sources whose frequencies are selected to cause the depopulation of any metastable excited states.

Evaporation and abstraction determined from stable isotopes during normal flow on the Gariep River, South Africa

NASA Astrophysics Data System (ADS)

Diamond, Roger E.; Jack, Sam

2018-04-01

Changes in the stable isotope composition of water can, with the aid of climatic parameters, be used to calculate the quantity of evaporation from a water body. Previous workers have mostly focused on small, research catchments, with abundant data, but of limited scope. This study aimed to expand such work to a regional or sub-continental scale. The first full length isotope survey of the Gariep River quantifies evaporation on the river and the man-made reservoirs for the first time, and proposes a technique to calculate abstraction from the river. The theoretically determined final isotope composition for an evaporating water body in the given climate lies on the empirically determined local evaporation line, validating the assumptions and inputs to the Craig-Gordon evaporation model that was used. Evaporation from the Gariep River amounts to around 20% of flow, or 40 m3/s, of which about half is due to evaporation from the surface of the Gariep and Vanderkloof Reservoirs, showing the wastefulness of large surface water impoundments. This compares well with previous estimates based on evapotranspiration calculations, and equates to around 1300 GL/a of water, or about the annual water consumption of Johannesburg and Pretoria, where over 10 million people reside. Using similar evaporation calculations and applying existing transpiration estimates to a gauged length of river, the remaining quantity can be attributed to abstraction, amounting to 175 L/s/km in the lower middle reaches of the river. Given that high water demand and climate change are global problems, and with the challenges of maintaining water monitoring networks, stable isotopes are shown to be applicable over regional to national scales for modelling hydrological flows. Stable isotopes provide a complementary method to conventional flow gauging for understanding hydrology and management of large water resources, particularly in arid areas subject to significant evaporation.

Quantification of short chain amines in aqueous matrices using liquid chromatography electrospray ionization tandem mass spectrometry.

PubMed

Viidanoja, Jyrki

2017-01-13

A new liquid chromatography-electrospray ionization-tandem Mass Spectrometry (LC-ESI-MS/MS) method was developed for the determination of more than 20 C 1 -C 6 alkyl and alkanolamines in aqueous matrices. The method employs Hydrophilic Interaction Liquid Chromatography Multiple Reaction Monitoring (HILIC-MRM) with a ZIC-pHILIC column and four stable isotope labeled amines as internal standards for signal normalization and quantification of the amines. The method was validated using a refinery process water sample that was obtained from a cooling cycle of crude oil distillation. The averaged within run precision, between run precision and accuracy were generally within 2-10%, 1-9% and 80-120%, respectively, depending on the analyte and concentration level. Selected aqueous process samples were analyzed with the method. Copyright © 2016 Elsevier B.V. All rights reserved.

Novel rapid liquid chromatography tandem masspectrometry method for vemurafenib and metabolites in human plasma, including metabolite concentrations at steady state.

PubMed

Vikingsson, Svante; Strömqvist, Malin; Svedberg, Anna; Hansson, Johan; Höiom, Veronica; Gréen, Henrik

2016-08-01

A novel, rapid and sensitive liquid chromatography tandem-mass spectrometry method for quantification of vemurafenib in human plasma, that also for the first time allows for metabolite semi-quantification, was developed and validated to support clinical trials and therapeutic drug monitoring. Vemurafenib was analysed by precipitation with methanol followed by a 1.9 min isocratic liquid chromatography tandem masspectrometry analysis using an Acquity BEH C18 column with methanol and formic acid using isotope labelled internal standards. Analytes were detected in multireaction monitoring mode on a Xevo TQ. Semi-quantification of vemurafenib metabolites was performed using the same analytical system and sample preparation with gradient elution. The vemurafenib method was successfully validated in the range 0.5-100 μg/mL according to international guidelines. The metabolite method was partially validated owing to the lack of commercially available reference materials. For the first time concentration levels at steady state for melanoma patients treated with vemurafenib is presented. The low abundance of vemurafenib metabolites suggests that they lack clinical significance. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Establishing a reliable multiple reaction monitoring-based method for the quantification of obesity-associated comorbidities in serum and adipose tissue requires intensive clinical validation.

PubMed

Oberbach, Andreas; Schlichting, Nadine; Neuhaus, Jochen; Kullnick, Yvonne; Lehmann, Stefanie; Heinrich, Marco; Dietrich, Arne; Mohr, Friedrich Wilhelm; von Bergen, Martin; Baumann, Sven

2014-12-05

Multiple reaction monitoring (MRM)-based mass spectrometric quantification of peptides and their corresponding proteins has been successfully applied for biomarker validation in serum. The option of multiplexing offers the chance to analyze various proteins in parallel, which is especially important in obesity research. Here, biomarkers that reflect multiple comorbidities and allow monitoring of therapy outcomes are required. Besides the suitability of established MRM assays for serum protein quantification, it is also feasible for analysis of tissues secreting the markers of interest. Surprisingly, studies comparing MRM data sets with established methods are rare, and therefore the biological and clinical value of most analytes remains questionable. A MRM method using nano-UPLC-MS/MS for the quantification of obesity related surrogate markers for several comorbidities in serum, plasma, visceral and subcutaneous adipose tissue was established. Proteotypic peptides for complement C3, adiponectin, angiotensinogen, and plasma retinol binding protein (RBP4) were quantified using isotopic dilution analysis and compared to the standard ELISA method. MRM method variabilities were mainly below 10%. The comparison with other MS-based approaches showed a good correlation. However, large differences in absolute quantification for complement C3 and adiponectin were obtained compared to ELISA, while less marked differences were observed for angiotensinogen and RBP4. The verification of MRM in obesity was performed to discriminate first lean and obese phenotype and second to monitor excessive weight loss after gastric bypass surgery in a seven-month follow-up. The presented MRM assay was able to discriminate obese phenotype from lean and monitor weight loss related changes of surrogate markers. However, inclusion of additional biomarkers was necessary to interpret the MRM data on obesity phenotype properly. In summary, the development of disease-related MRMs should include a step of matching the MRM data with clinically approved standard methods and defining reference values in well-sized representative age, gender, and disease-matched cohorts.

Calibration of CR-39-based thoron progeny device.

PubMed

Fábián, F; Csordás, A; Shahrokhi, A; Somlai, J; Kovács, T

2014-07-01

Radon isotopes and their progenies have proven significant role in respiratory tumour formation. In most cases, the radiological effect of one of the radon isotopes (thoron) and its progenies has been neglected together with its measurement technique; however, latest surveys proved that thoron's existence is expectable in flats and in workplace in Europe. Detectors based on different track detector measurement technologies have recently spread for measuring thoron progenies; however, the calibration is not yet completely elaborated. This study deals with the calibration of the track detector measurement method suitable for measuring thoron progenies using different devices with measurement techniques capable of measuring several progenies (Pylon AB5 and WLx, Sarad EQF 3220). The calibration factor values related to the thoron progeny monitors, the measurement uncertainty, reproducibility and other parameters were found using the calibration chamber. In the future, the effects of the different parameters (aerosol distribution, etc.) will be determined. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Analysis of high-resolution spectra from a hybrid interferometric/dispersive spectrometer

DOE PAGES

Ko, Phyllis; Scott, Jill R.; Jovanovic, Igor

2015-09-05

To fully take advantage of a low-cost, small footprint hybrid interferometric/dispersive spectrometer, a math- ematical reconstruction technique was developed to accurately capture the high-resolution and relative peak intensities from complex patterns. A Fabry-Perot etalon was coupled to a Czerny-Turner spectrometer, in- creasing spectral resolution by an order of magnitude without the commensurate increase in spectrometer size. Measurement of the industry standard Hg 313.1555/313.1844 nm doublet yielded a ratio of 0.682 with 1.8%error, which agreed well with an independent measurement and literature values. The doublet separation (29 pm), is similar to the U isotope shift (25 pm) at 424.437 nm thatmore » is of interest to monitoring nuclear nonpro-liferation activities. Additionally, the technique was applied to a LIBS measurement of the mineral cinnabar (HgS) and resulted in a ratio of 0.681. In addition, this reconstruction method could enable significantly smaller, portable high-resolution instruments with isotopic specificity, benefiting a variety of spectroscopic applications.« less

Identification of sinensetin metabolites in rat urine by an isotope-labeling method and ultrahigh-performance liquid chromatography-electrospray ionization mass spectrometry.

PubMed

Wei, Guor-Jien; Sheen, Jenn-Feng; Lu, Wen-Chien; Hwang, Lucy Sun; Ho, Chi-Tang; Lin, Ching-I

2013-05-29

Sinensetin (SIN), one of the major polymethoxyflavones (PMFs) contained mainly in the citrus peels, has been reported to possess various bioactivities, including antifungal, antimutagenic, anticancer, and anti-inflammatory activities. Although the biotransformation of SIN in fungi and insects has been reported, the information about the metabolism of SIN in mammals is still unclear. In this study, formation of SIN metabolites in rats was investigated. Four isotope-labeled SINs ([4'-D3]SIN, [3'-D3]SIN, [5-D3]SIN, and [6-D3]SIN) were synthesized and administered to rat. The urine samples were collected and main metabolites were monitored by ultrahigh-performance liquid chromatography-electrospray ionization mass spectrometry. The administered compound and four SIN metabolites were detected in rat urine. These metabolites were identified as 4'-hydroxy-5,6,7,3'-tetramethoxyflavone, 5-hydroxy-6,7,3',4'-tetramethoxyflavone, 6-hydroxy-5,7,3',4'-tetramethoxyflavone, and 7-hydroxy-5,6,3',4'-tetramethoxyflavone sulfate.

Intramolecular carbon and nitrogen isotope analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector/capillary reactor prior to GC separation.

PubMed

Penning, Holger; Elsner, Martin

2007-11-01

Potentially, compound-specific isotope analysis may provide unique information on source and fate of pesticides in natural systems. Yet for isotope analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen isotope analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isotopically different batches of isoproturon. For all three products, the same isotope fractionation factors were observed during conversion and the difference in isotope composition between the batches was preserved. This study demonstrates that fragmentation of phenylurea herbicides does not only make them accessible to isotope analysis but even enables determination of intramolecular isotope fractionation.

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.

Determination of δ13C, δ15N, or δ34S by isotope-ratio-monitoring mass spectrometry using an elemental analyzer

USGS Publications Warehouse

Johnson, Craig A.; Stricker, Craig A.; Gulbransen, Cayce A.; Emmons, Matthew P.

2018-02-14

This report describes procedures used in the Geology, Geophysics, and Geochemistry Science Center of the U.S. Geological Survey in Denver, Colorado, to determine the stable-isotope ratios 13C/12C, 15N/14N, and 34S/32S in solid materials. The procedures use elemental analyzers connected directly to gas-source isotope-ratio mass spectrometers. A different elemental–analyzer–mass-spectrometer system is used for 13C/12C and 15N/14N than is used for 34S/32S to accommodate differences in reagents, catalysts, and instrument settings.

WOSMIP II- Workshop on Signatures of Medical and Industrial Isotope Production

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

Matthews, Murray; Achim, Pascal; Auer, M.

2011-11-01

Medical and industrial fadioisotopes are fundamental tools used in science, medicine and industry with an ever expanding usage in medical practice where their availability is vital. Very sensitive environmental radionuclide monitoring networks have been developed for nuclear-security-related monitoring [particularly Comprehensive Test-Ban-Treaty (CTBT) compliance verification] and are now operational.

Quantitative Proteomics by Metabolic Labeling of Model Organisms*

PubMed Central

Gouw, Joost W.; Krijgsveld, Jeroen; Heck, Albert J. R.

2010-01-01

In the biological sciences, model organisms have been used for many decades and have enabled the gathering of a large proportion of our present day knowledge of basic biological processes and their derailments in disease. Although in many of these studies using model organisms, the focus has primarily been on genetics and genomics approaches, it is important that methods become available to extend this to the relevant protein level. Mass spectrometry-based proteomics is increasingly becoming the standard to comprehensively analyze proteomes. An important transition has been made recently by moving from charting static proteomes to monitoring their dynamics by simultaneously quantifying multiple proteins obtained from differently treated samples. Especially the labeling with stable isotopes has proved an effective means to accurately determine differential expression levels of proteins. Among these, metabolic incorporation of stable isotopes in vivo in whole organisms is one of the favored strategies. In this perspective, we will focus on methodologies to stable isotope label a variety of model organisms in vivo, ranging from relatively simple organisms such as bacteria and yeast to Caenorhabditis elegans, Drosophila, and Arabidopsis up to mammals such as rats and mice. We also summarize how this has opened up ways to investigate biological processes at the protein level in health and disease, revealing conservation and variation across the evolutionary tree of life. PMID:19955089

Integrated carbon and chlorine isotope modeling: applications to chlorinated aliphatic hydrocarbons dechlorination.

PubMed

Jin, Biao; Haderlein, Stefan B; Rolle, Massimo

2013-02-05

We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.

Diagnostics of wear in aeronautical systems

NASA Technical Reports Server (NTRS)

Wedeven, L. D.

1979-01-01

The use of appropriate diagnostic tools for aircraft oil wetted components is reviewed, noting that it can reduce direct operating costs through reduced unscheduled maintenance, particularly in helicopter engine and transmission systems where bearing failures are a significant cost factor. Engine and transmission wear modes are described, and diagnostic methods for oil and wet particle analysis, the spectrometric oil analysis program, chip detectors, ferrography, in-line oil monitor and radioactive isotope tagging are discussed, noting that they are effective over a limited range of particle sizes but compliment each other if used in parallel. Fine filtration can potentially increase time between overhauls, but reduces the effectiveness of conventional oil monitoring techniques so that alternative diagnostic techniques must be used. It is concluded that the development of a diagnostic system should be parallel and integral with the development of a mechanical system.

Metabolic networks in motion: 13C-based flux analysis

PubMed Central

Sauer, Uwe

2006-01-01

Many properties of complex networks cannot be understood from monitoring the components—not even when comprehensively monitoring all protein or metabolite concentrations—unless such information is connected and integrated through mathematical models. The reason is that static component concentrations, albeit extremely informative, do not contain functional information per se. The functional behavior of a network emerges only through the nonlinear gene, protein, and metabolite interactions across multiple metabolic and regulatory layers. I argue here that intracellular reaction rates are the functional end points of these interactions in metabolic networks, hence are highly relevant for systems biology. Methods for experimental determination of metabolic fluxes differ fundamentally from component concentration measurements; that is, intracellular reaction rates cannot be detected directly, but must be estimated through computer model-based interpretation of stable isotope patterns in products of metabolism. PMID:17102807

Accelerator-based method of producing isotopes

DOEpatents

Nolen, Jr., Jerry A.; Gomes, Itacil C.

2015-11-03

The invention provides a method using accelerators to produce radio-isotopes in high quantities. The method comprises: supplying a "core" of low-enrichment fissile material arranged in a spherical array of LEU combined with water moderator. The array is surrounded by substrates which serve as multipliers and moderators as well as neutron shielding substrates. A flux of neutrons enters the low-enrichment fissile material and causes fissions therein for a time sufficient to generate desired quantities of isotopes from the fissile material. The radio-isotopes are extracted from said fissile material by chemical processing or other means.

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, scientists and researchers with temporally and spatially resolved data (including measurements of important greenhouse gases, isotopes and pollutants) necessary for compliance monitoring, hot-spot detection, as well as cap and trade, at any location. Details of extended measurement campaigns (including lessons learned) at the various field sites (urban and rural environments) will be presented.

A Continuous Holocene Record of Hydroclimate from Kartchner Cavern, AZ, Supported by Multiyear Dripwater Monitoring

NASA Astrophysics Data System (ADS)

Cole, J. E.; Hlohowskyj, S.; Vetter, L.; King, J.; Casavant, R. R.; Woodhead, J. D.; Drysdale, R.; Truebe, S.; Henderson, G. M.

2017-12-01

In the arid southwest, hydroclimatic variability is critical to natural and human systems. Cave records provide the chance to reconstruct past variations in moisture, including the seasonal hydroclimatic response to known forcings such as the seasonal distribution of insolation. At Kartchner Caverns State Park, AZ, a sample dating to 12,000 years before present reveals a continuous Holocene history of the Southwest monsoon in its stable isotope content. We interpret the large ( 4‰) changes in speleothem d18O in terms of seasonal precipitation balance, based on modern isotope studies. The Kartchner record confirms a shorter ( 6500 yr) reconstruction from the neighboring Cave of the Bells in describing a strong trend of declining monsoon moisture during the Holocene. The Kartchner sample reveals an early Holocene monsoon peak defined by a broad δ18O peak between 7000 and 9000 years ago, following a gradual strengthening from the start of the record. Between 7000-2000 years ago, the monsoon weakened, and the oxygen isotope values show no trend over the past 2000 years. Substantial multidecadal-multicentury variability is present throughout the record. This pattern is consistent with a sensitive response of the Southwest monsoon to orbital forcing of seasonal radiation. A new laser-ICPMS multi-element dataset spans the past 2400 years and adds information to our isotope-based reconstruction. In particular, Ba and Sr highlight intervals of overall wet and dry conditions, complementing the isotopic record of seasonal precipitation distribution. Dripwater monitoring since 2011 at 4 sites in the cave allows us to identify seasonal and interannual controls on the isotopic and elemental variations of dripwater. Drips differ in their isotopic behavior, with some dominated by relatively steady, low (winter) values and others exhibiting highly variable δ18O. This study provides one of the first cave-based reconstructions of the North American monsoon spanning the entire Holocene. The modern dripwater data shed light on how isotopic and elemental signals vary over space and time and create the multivariate climate record preserved in cave calcite.

Estimates of water source contributions in a dynamic urban water supply system inferred via a Bayesian stable isotope mixing model

NASA Astrophysics Data System (ADS)

Jameel, M. Y.; Brewer, S.; Fiorella, R.; Tipple, B. J.; Bowen, G. J.; Terry, S.

2017-12-01

Public water supply systems (PWSS) are complex distribution systems and critical infrastructure, making them vulnerable to physical disruption and contamination. Exploring the susceptibility of PWSS to such perturbations requires detailed knowledge of the supply system structure and operation. Although the physical structure of supply systems (i.e., pipeline connection) is usually well documented for developed cities, the actual flow patterns of water in these systems are typically unknown or estimated based on hydrodynamic models with limited observational validation. Here, we present a novel method for mapping the flow structure of water in a large, complex PWSS, building upon recent work highlighting the potential of stable isotopes of water (SIW) to document water management practices within complex PWSS. We sampled a major water distribution system of the Salt Lake Valley, Utah, measuring SIW of water sources, treatment facilities, and numerous sites within in the supply system. We then developed a hierarchical Bayesian (HB) isotope mixing model to quantify the proportion of water supplied by different sources at sites within the supply system. Known production volumes and spatial distance effects were used to define the prior probabilities for each source; however, we did not include other physical information about the supply system. Our results were in general agreement with those obtained by hydrodynamic models and provide quantitative estimates of contributions of different water sources to a given site along with robust estimates of uncertainty. Secondary properties of the supply system, such as regions of "static" and "dynamic" source (e.g., regions supplied dominantly by one source vs. those experiencing active mixing between multiple sources), can be inferred from the results. The isotope-based HB isotope mixing model offers a new investigative technique for analyzing PWSS and documenting aspects of supply system structure and operation that are otherwise challenging to observe. The method could allow water managers to document spatiotemporal variation in PWSS flow patterns, critical for interrogating the distribution system to inform operation decision making or disaster response, optimize water supply and, monitor and enforce water rights.

Water isotopic ratios from a continuously melted ice core sample

NASA Astrophysics Data System (ADS)

Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Johnsen, S. J.

2011-06-01

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We build an interface between an Infra Red Cavity Ring Down Spectrometer (IR-CRDS) and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100 % efficiency in a home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on humidity levels. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1 ‰ and 0.5 ‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the framework of the NEEM deep ice core drilling project in Greenland, during the 2010 field season.

Water isotopic ratios from a continuously melted ice core sample

NASA Astrophysics Data System (ADS)

Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Kettner, E.; Johnsen, S. J.

2011-11-01

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW-SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

NASA Astrophysics Data System (ADS)

Lauwens, Sara; Costas-Rodríguez, Marta; van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

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

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is important for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament- uranium interaction points. The resulting uranium oxide emission exhibitsmore » a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. Lastly, the results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.« less

Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

1989-01-01

On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

PubMed Central

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-01-01

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity. PMID:28272450

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

DOE PAGES

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-03-08

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is important for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament- uranium interaction points. The resulting uranium oxide emission exhibitsmore » a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. Lastly, the results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.« less

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

PubMed Central

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-01-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about −0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure. PMID:27468898

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study.

PubMed

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-29

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient's condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ(65)Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

NASA Astrophysics Data System (ADS)

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-03-01

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.

Simultaneous determination of the quantity and isotopic ratios of uranium in individual micro-particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS).

PubMed

Park, Jong-Ho; Choi, Eun-Ju

2016-11-01

A method to determine the quantity and isotopic ratios of uranium in individual micro-particles simultaneously by isotope dilution thermal ionization mass spectrometry (ID-TIMS) has been developed. This method consists of sequential sample and spike loading, ID-TIMS for isotopic measurement, and application of a series of mathematical procedures to remove the contribution of uranium in the spike. The homogeneity of evaporation and ionization of uranium content was confirmed by the consistent ratio of n((233)U)/n((238)U) determined by TIMS measurements. Verification of the method was performed using U030 solution droplets and U030 particles. Good agreements of resulting uranium quantity, n((235)U)/n((238)U), and n((236)U)/n((238)U) with the estimated or certified values showed the validity of this newly developed method for particle analysis when simultaneous determination of the quantity and isotopic ratios of uranium is required. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Comparative study of ¹³C composition in ethanol and bulk dry wine using isotope ratio monitoring by mass spectrometry and by nuclear magnetic resonance as an indicator of vine water status.

PubMed

Guyon, Francois; van Leeuwen, Cornelis; Gaillard, Laetitia; Grand, Mathilde; Akoka, Serge; Remaud, Gérald S; Sabathié, Nathalie; Salagoïty, Marie-Hélène

2015-12-01

The potential of wine (13)C isotope composition (δ(13)C) is presented to assess vine water status during grape ripening. Measurements of δ(13)C have been performed on a set of 32 authentic wines and their ethanol recovered after distillation. The data, obtained by isotope ratio monitoring by mass spectrometry coupled to an elemental analyser (irm-EA/MS), show a high correlation between δ(13)C of the bulk wine and its ethanol, indicating that the distillation step is not necessary when the wine has not been submitted to any oenological treatment. Therefore, the ethanol/wine δ(13)C correlation can be used as an indicator of possible enrichment of the grape must or the wine with exogenous organic compounds. Wine ethanol δ(13)C is correlated to predawn leaf water potential (R(2) = 0.69), indicating that this parameter can be used as an indicator of vine water status. Position-specific (13)C analysis (PSIA) of ethanol extracted from wine, performed by isotope ratio monitoring by nuclear magnetic resonance (irm-(13)C NMR), confirmed the non-homogenous repartition of (13)C on ethanol skeleton. It is the δ(13)C of the methylene group of ethanol, compared to the methyl moiety, which is the most correlated to predawn leaf water potential, indicating that a phase of photorespiration of the vine during water stress period is most probably occurring due to stomata closure. However, position-specific (13)C analysis by irm-(13)C NMR does not offer a greater precision in the assessment of vine water status compared to direct measurement of δ(13)C on bulk wine by irm-EA/MS.

Electron linac for medical isotope production with improved energy efficiency and isotope recovery

DOEpatents

Noonan, John; Walters, Dean; Virgo, Matt; Lewellen, John

2015-09-08

A method and isotope linac system are provided for producing radio-isotopes and for recovering isotopes. The isotope linac is an energy recovery linac (ERL) with an electron beam being transmitted through an isotope-producing target. The electron beam energy is recollected and re-injected into an accelerating structure. The ERL provides improved efficiency with reduced power requirements and provides improved thermal management of an isotope target and an electron-to-x-ray converter.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

A Bat's-Eye View of Holocene Climate Change in the Southwest: Resolving Ambiguities in Cave Isotopic Records

NASA Astrophysics Data System (ADS)

Cole, J. E.; Truebe, S. A.; Harrington, M. D.; Woodhead, J. D.; Overpeck, J. T.; Hlohowskyj, S.; Henderson, G. M.

2015-12-01

In dry environments, speleothems provide an outstanding archive of information on past climate change, particularly since lakes are typically absent or intermittent. Speleothem stable isotopes are widely used for climate reconstruction, but the isotope-climate relationship is complex in arid-region precipitation, and within-cave processes further complicate climate interpretations. Our isotope results from 3 southeastern Arizona caves, spanning the past 3.5-12 kyr, collectively indicate a weakening monsoon from 7kyr to present. These records exhibit substantial multidecadal-multicentury variability that is sometimes shared, and sometimes independent among caves. Strategies to overcome ambiguities in isotope records include long-term monitoring of cave dripwaters, multi-site comparisons, and multiproxy measurements. Monthly dripwater measurements from two caves spanning several years highlight substantial seasonal biases that create distinct differences in the climate sensitivity of individual cave records. These biases can lead to lack of correlation between records, but also creates opportunities for seasonally specific moisture reconstructions. New preliminary analyses suggest that elemental data can help to unravel the multivariate signal contained in speleothem oxygen isotope records.

The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

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

Liezers, Martin; Farmer, Orville T.; Dion, Michael P.

2015-01-01

We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recoverymore » of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.« less

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.

Using combinations of metal isotopes as tracers of tailings pond discharges to subsurface aquifers in the Athabasca Oil Sands area, Canada.

NASA Astrophysics Data System (ADS)

Gammon, P. R.; Savard, M. M.; Ahad, J. M.; Girard, I.

2016-12-01

The Athabasca Oil Sands (AOS) industry in Alberta, Canada deposits voluminous waste streams in Earth's largest tailings ponds (TPs). Detecting and tracing contaminant discharge from TPs to subsurface aquifers has proven difficult because tailings have the same composition as the surrounding environment of unmined oil sand. To trace pond discharge to the subsurface therefore relies on the waste stream hosting additions or alterations induced by mining or industrial processes. Inorganic element or contaminant concentration data have proven ineffective at tracing because there is insufficient alteration of the chemical constituents or their ratios. Metal isotopes have not generally been applied to tracing emissions even though isotopic fractionation is likely induced via the high temperature and pH industrial process. We have generated Mg, Li, Pb and Zn isotopic data for a range of groundwater wells and TPs. Mg isotopes are excellent for distinguishing deep saline brines that are pumped into the waste stream during mine dewatering. Li isotopes appear to be heavily fractionated during processing, which produces a heavy isotopic signature that is an excellent tracer of production water. Pb isotopes discriminate Pb derived from oil-sand versus bedrock carbonate. Juxtapositions of TPs, carbonates and near-surface aquifers are common and of significant regulatory concern, making Pb isotopes particularly useful. Zn isotopic data indicates similarities to Pb isotopes, but are difficult to obtain due to low concentrations. Combining the isotopic data with concentration data and hydrologic models will assist in determining the fluxes of discharges from the TPs to near-surface aquifers. The range of environmental contexts of AOS TPs is limited and thus monitoring discharges to nearby aquifers from TPs could feasibly be accomplished using tailored suites of metal isotopes.

Closed-loop 15N measurement of N2O and its isotopomers for real-time greenhouse gas tracing

NASA Astrophysics Data System (ADS)

Slaets, Johanna; Mayr, Leopold; Heiling, Maria; Zaman, Mohammad; Resch, Christian; Weltin, Georg; Gruber, Roman; Dercon, Gerd

2016-04-01

Quantifying sources of nitrous oxide is essential to improve understanding of the global N cycle and to develop climate-smart agriculture, as N2O has a global warming potential 300 times higher than CO2. The isotopic signature and the intramolecular distribution (site preference) of 15N are powerful tools to trace N2O, but the application of these methods is limited as conventional methods cannot provide continuous and in situ data. Here we present a method for closed-loop, real time monitoring of the N2O flux, the isotopic signature and the intramolecular distribution of 15N by using off-axis integrated cavity output spectroscopy (ICOS, Los Gatos Research). The developed method was applied to a fertilizer inhibitor experiment, in which N2O emissions were measured on undisturbed soil cores for three weeks. The treatments consisted of enriched urea-N (100 kg urea-N/ha), the same fertilizer combined with the nitrification inhibitor nitrapyrin (375 g/100 kg urea), and control cores. Monitoring the isotopic signature makes it possible to distinguish emissions from soil and fertilizer. Characterization of site preference could additionally provide a tool to identify different microbial processes leading to N2O emissions. Furthermore, the closed-loop approach enables direct measurement on site and does not require removal of CO2 and H2O. Results showed that 75% of total N2O emissions (total=11 346 μg N2O-N/m2) in the fertilized cores originated from fertilizer, while only 55% of total emissions (total=2 450 μg N2ON/m2) stemmed from fertilizer for the cores treated with nitrapyrin. In the controls, N2O derived from soil was only 40% of the size of the corresponding pool from the fertilized cores, pointing towards a priming effect on the microbial community from the fertilizer and demonstrating the bias that could be introduced by relying on non-treated cores to estimate soil emission rates, rather than using the isotopic signature. The site preference increased linearly over time for the cores with fertilizer and those with nitrapyrin, but the increase was stronger for the fertilized cores: during the first 10 days of the experiment, theses cores showed a more negative site preference than the cores with inhibitor, while during the last 10 days, the site preference for the fertilized cores was more positive than that of the inhibitor. This change indicates that the site preference of 15N can be used to distinguish the processes of nitrification and denitrification, the former having been supressed by nitrapyrin in the cores treated with the inhibitor. Low enrichment levels (5% atomic excess in this study) sufficed in order to separate emissions from soil and fertilizer, making the proposed closed-loop approach a cost-effective and practical tool to obtain a continuous, in situ characterization of N2O sources.

Rapid Verification of Candidate Serological Biomarkers Using Gel-based, Label-free Multiple Reaction Monitoring

PubMed Central

Tang, Hsin-Yao; Beer, Lynn A.; Barnhart, Kurt T.; Speicher, David W.

2011-01-01

Stable isotope dilution-multiple reaction monitoring-mass spectrometry (SID-MRM-MS) has emerged as a promising platform for verification of serological candidate biomarkers. However, cost and time needed to synthesize and evaluate stable isotope peptides, optimize spike-in assays, and generate standard curves, quickly becomes unattractive when testing many candidate biomarkers. In this study, we demonstrate that label-free multiplexed MRM-MS coupled with major protein depletion and 1-D gel separation is a time-efficient, cost-effective initial biomarker verification strategy requiring less than 100 μl serum. Furthermore, SDS gel fractionation can resolve different molecular weight forms of targeted proteins with potential diagnostic value. Because fractionation is at the protein level, consistency of peptide quantitation profiles across fractions permits rapid detection of quantitation problems for specific peptides from a given protein. Despite the lack of internal standards, the entire workflow can be highly reproducible, and long-term reproducibility of relative protein abundance can be obtained using different mass spectrometers and LC methods with external reference standards. Quantitation down to ~200 pg/mL could be achieved using this workflow. Hence, the label-free GeLC-MRM workflow enables rapid, sensitive, and economical initial screening of large numbers of candidate biomarkers prior to setting up SID-MRM assays or immunoassays for the most promising candidate biomarkers. PMID:21726088

Rapid verification of candidate serological biomarkers using gel-based, label-free multiple reaction monitoring.

PubMed

Tang, Hsin-Yao; Beer, Lynn A; Barnhart, Kurt T; Speicher, David W

2011-09-02

Stable isotope dilution-multiple reaction monitoring-mass spectrometry (SID-MRM-MS) has emerged as a promising platform for verification of serological candidate biomarkers. However, cost and time needed to synthesize and evaluate stable isotope peptides, optimize spike-in assays, and generate standard curves quickly becomes unattractive when testing many candidate biomarkers. In this study, we demonstrate that label-free multiplexed MRM-MS coupled with major protein depletion and 1D gel separation is a time-efficient, cost-effective initial biomarker verification strategy requiring less than 100 μL of serum. Furthermore, SDS gel fractionation can resolve different molecular weight forms of targeted proteins with potential diagnostic value. Because fractionation is at the protein level, consistency of peptide quantitation profiles across fractions permits rapid detection of quantitation problems for specific peptides from a given protein. Despite the lack of internal standards, the entire workflow can be highly reproducible, and long-term reproducibility of relative protein abundance can be obtained using different mass spectrometers and LC methods with external reference standards. Quantitation down to ~200 pg/mL could be achieved using this workflow. Hence, the label-free GeLC-MRM workflow enables rapid, sensitive, and economical initial screening of large numbers of candidate biomarkers prior to setting up SID-MRM assays or immunoassays for the most promising candidate biomarkers.

Linking high resolution mass spectrometry data with exposure and toxicity forecasts to advance high-throughput environmental monitoring

EPA Pesticide Factsheets

There is a growing need in the field of exposure science for monitoring methods that rapidly screen environmental media for suspect contaminants. Measurement and analysis platforms, based on high resolution mass spectrometry (HRMS), now exist to meet this need. Here we describe results of a study that links HRMS data with exposure predictions from the U.S. EPA's ExpoCast? program and in vitro bioassay data from the U.S. interagency Tox21 consortium. Vacuum dust samples were collected from 56 households across the U.S. as part of the American Healthy Homes Survey (AHHS). Sample extracts were analyzed using liquid chromatography time-of-flight mass spectrometry (LC??TOF/MS) with electrospray ionization. On average, approximately 2000 molecular features were identified per sample (based on accurate mass) in negative ion mode, and 3000 in positive ion mode. Exact mass, isotope distribution, and isotope spacing were used to match molecular features with a unique listing of chemical formulas extracted from EPA's Distributed Structure-Searchable Toxicity (DSSTox) database. A total of 978 DSSTox formulas were consistent with the dust LC??TOF/molecular feature data (match score ? 90); these formulas mapped to 3228 possible chemicals in the database. Correct assignment of a unique chemical to a given formula required additional validation steps. Each suspect chemical was prioritized for follow-up confirmation using abundance and detection frequency results, along with exp

Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

USGS Publications Warehouse

Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

2002-01-01

We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

PubMed Central

Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

2014-01-01

Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

Application of the Reference Method Isotope Dilution Gas Chromatography Mass Spectrometry (ID/GC/MS) to Establish Metrological Traceability for Calibration and Control of Blood Glucose Test Systems

PubMed Central

Andreis, Elisabeth; Küllmer, Kai

2014-01-01

Self-monitoring of blood glucose (BG) by means of handheld BG systems is a cornerstone in diabetes therapy. The aim of this article is to describe a procedure with proven traceability for calibration and evaluation of BG systems to guarantee reliable BG measurements. Isotope dilution gas chromatography mass spectrometry (ID/GC/MS) is a method that fulfills all requirements to be used in a higher-order reference measurement procedure. However, this method is not applicable for routine measurements because of the time-consuming sample preparation. A hexokinase method with perchloric acid (PCA) sample pretreatment is used in a measurement procedure for such purposes. This method is directly linked to the ID/GC/MS method by calibration with a glucose solution that has an ID/GC/MS-determined target value. BG systems are calibrated with whole blood samples. The glucose levels in such samples are analyzed by this ID/GC/MS-linked hexokinase method to establish traceability to higher-order reference material. For method comparison, the glucose concentrations in 577 whole blood samples were measured using the PCA-hexokinase method and the ID/GC/MS method; this resulted in a mean deviation of 0.1%. The mean deviation between BG levels measured in >500 valid whole blood samples with BG systems and the ID/GC/MS was 1.1%. BG systems allow a reliable glucose measurement if a true reference measurement procedure, with a noninterrupted traceability chain using ID/GC/MS linked hexokinase method for calibration of BG systems, is implemented. Systems should be calibrated by means of a traceable and defined measurement procedure to avoid bias. PMID:24876614

Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

PubMed

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2008-10-01

Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment.

Methods for determination of radioactive substances in water and fluvial sediments

USGS Publications Warehouse

Thatcher, Leland Lincoln; Janzer, Victor J.; Edwards, Kenneth W.

1977-01-01

Analytical methods for the determination of some of the more important components of fission or neutron activation product radioactivity and of natural radioactivity found in water are reported. The report for each analytical method includes conditions for application of the method, a summary of the method, interferences, required apparatus and reagents, analytical procedures, calculations, reporting of results, and estimation of precision. The fission product isotopes considered are cesium-137, strontium-90, and ruthenium-106. The natural radioelements and isotopes considered are uranium, lead-210, radium-226, radium-228, tritium, and carbon-14. A gross radioactivity survey method and a uranium isotope ratio method are given. When two analytical methods are in routine use for an individual isotope, both methods are reported with identification of the specific areas of application of each. Techniques for the collection and preservation of water samples to be analyzed for radioactivity are discussed.

Isolation and Puification of Uranium Isotopes for Measurement by Mass-Spectrometry (233, 234, 235, 236, 238U) and Alpha Spectrometry (232U)

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

Marinelli, R; Hamilton, T; Brown, T

2006-05-30

This report describes a standardized methodology used by researchers from the Center for Accelerator Mass Spectrometry (CAMS) (Energy and Environment Directorate) and the Environmental Radiochemistry Group (Chemistry and Materials Science Directorate) at the Lawrence Livermore National Laboratory (LLNL) for the full isotopic analysis of uranium from solution. The methodology has largely been developed for use in characterizing the uranium composition of selected nuclear materials but may also be applicable to environmental studies and assessments of public, military or occupational exposures to uranium using in-vitro bioassay monitoring techniques. Uranium isotope concentrations and isotopic ratios are measured using a combination of Multimore » Collector Inductively Coupled Plasma Mass Spectrometry (MC ICP-MS), Accelerator Mass Spectrometry (AMS) and Alpha Spectrometry.« less

Quasi solution of radiation transport equation

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

Pogosbekyan, L.R.; Lysov, D.A.

There is uncertainty with experimental data as well as with input data of theoretical calculations. The neutron distribution from the variational principle, which takes into account both theoretical and experimental data, is obtained to increase the accuracy and speed of neutronic calculations. The neutron imbalance in mesh cells and the discrepancy between experimentally measured and calculated functional of the neutron distribution are simultaneously minimized. A fast-working and simple-programming iteration method is developed to minimize the objective functional. The method can be used in the core monitoring and control system for (a) power distribution calculations, (b) in- and ex-core detector calibration,more » (c) macro-cross sections or isotope distribution correction by experimental data, and (d) core and detector diagnostics.« less

Precise and accurate in situ Pb-Pb dating of apatite, monazite, and sphene by laser ablation multiple-collector ICP-MS

NASA Astrophysics Data System (ADS)

Willigers, B. J. A.; Baker, J. A.; Krogstad, E. J.; Peate, D. W.

2002-03-01

To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (≪1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (˜1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.

Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS.

PubMed

Noble, Stephen R; Horstwood, Matthew S A; Davy, Pamela; Pashley, Vanessa; Spiro, Baruch; Smith, Steve

2008-07-01

Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

DOE PAGES

Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

2014-12-31

Carbon stable isotopes can be used in characterization and monitoring of CO 2 sequestration sites to track the migration of the CO 2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO 2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO 2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport modulemore » of TOUGHREACT was modified to include separate isotopic species of CO 2 gas and dissolved inorganic carbon (CO 2, CO 3 2-, HCO 3 -,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO 2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

[Progress in stable isotope labeled quantitative proteomics methods].

PubMed

Zhou, Yuan; Shan, Yichu; Zhang, Lihua; Zhang, Yukui

2013-06-01

Quantitative proteomics is an important research field in post-genomics era. There are two strategies for proteome quantification: label-free methods and stable isotope labeling methods which have become the most important strategy for quantitative proteomics at present. In the past few years, a number of quantitative methods have been developed, which support the fast development in biology research. In this work, we discuss the progress in the stable isotope labeling methods for quantitative proteomics including relative and absolute quantitative proteomics, and then give our opinions on the outlook of proteome quantification methods.

A Database of Reaction Monitoring Mass Spectrometry Assays for Elucidating Therapeutic Response in Cancer

PubMed Central

Remily-Wood, Elizabeth R.; Liu, Richard Z.; Xiang, Yun; Chen, Yi; Thomas, C. Eric; Rajyaguru, Neal; Kaufman, Laura M.; Ochoa, Joana E.; Hazlehurst, Lori; Pinilla-Ibarz, Javier; Lancet, Jeffrey; Zhang, Guolin; Haura, Eric; Shibata, David; Yeatman, Timothy; Smalley, Keiran S.M.; Dalton, William S.; Huang, Emina; Scott, Ed; Bloom, Gregory C.; Eschrich, Steven A.; Koomen, John M.

2012-01-01

Purpose The Quantitative Assay Database (QuAD), http://proteome.moffitt.org/QUAD/, facilitates widespread implementation of quantitative mass spectrometry in cancer biology and clinical research through sharing of methods and reagents for monitoring protein expression and modification. Experimental Design Liquid chromatography coupled to multiple reaction monitoring mass spectrometry (LC-MRM) assays are developed using SDS-PAGE fractionated lysates from cancer cell lines. Pathway maps created using GeneGO Metacore provide the biological relationships between proteins and illustrate concepts for multiplexed analysis; each protein can be selected to examine assay development at the protein and peptide level. Results The coupling of SDS-PAGE and LC-MRM screening has been used to detect 876 peptides from 218 cancer-related proteins in model systems including colon, lung, melanoma, leukemias, and myeloma, which has led to the development of 95 quantitative assays including stable-isotope labeled peptide standards. Methods are published online and peptide standards are made available to the research community. Protein expression measurements for heat shock proteins, including a comparison with ELISA and monitoring response to the HSP90 inhibitor, 17-DMAG, are used to illustrate the components of the QuAD and its potential utility. Conclusions and Clinical Relevance This resource enables quantitative assessment of protein components of signaling pathways and biological processes and holds promise for systematic investigation of treatment responses in cancer. PMID:21656910

δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate M.

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings. 

Characterizing the intrinsic bioremediation potential of 1,4-dioxane and trichloroethene using innovative environmental diagnostic tools.

PubMed

Chiang, Sheau-Yun Dora; Mora, Rebecca; Diguiseppi, William H; Davis, Greg; Sublette, Kerry; Gedalanga, Phillip; Mahendra, Shaily

2012-09-01

An intrinsic biodegradation study involving the design and implementation of innovative environmental diagnostic tools was conducted to evaluate whether monitored natural attenuation (MNA) could be considered as part of the remedial strategy to treat an aerobic aquifer contaminated with 1,4-dioxane and trichloroethene (TCE). In this study, advanced molecular biological and stable isotopic tools were applied to confirm in situ intrinsic biodegradation of 1,4-dioxane and TCE. Analyses of Bio-Trap® samplers and groundwater samples collected from monitoring wells verified the abundance of bacteria and enzymes capable of aerobically degrading TCE and 1,4-dioxane. Furthermore, phospholipid fatty acid analysis with stable isotope probes (PLFA-SIP) of the microbial community validated the ability for microbial degradation of TCE and 1,4-dioxane. Compound specific isotope analysis (CSIA) of groundwater samples for TCE resulted in δ(13)C values that indicated likely biodegradation of TCE in three of the four monitoring wells sampled. Results of the MNA evaluation showed that enzymes capable of aerobically degrading TCE and 1,4-dioxane were present, abundant, and active in the aquifer. Taken together, these results provide direct evidence of the occurrence of TCE and 1,4-dioxane biodegradation at the study site, supporting the selection of MNA as part of the final remedy at some point in the future.

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis.

PubMed

Lojkasek-Lima, Paulo; Aravena, Ramon; Parker, Beth L; Cherry, John A

2012-01-01

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation. © 2012, The Author(s). Ground Water © 2012, National Ground Water Association.

A fully automated meltwater monitoring and collection system for spatially distributed isotope analysis in snowmelt-dominated catchments

NASA Astrophysics Data System (ADS)

Rücker, Andrea; Boss, Stefan; Von Freyberg, Jana; Zappa, Massimiliano; Kirchner, James

2016-04-01

In many mountainous catchments the seasonal snowpack stores a significant volume of water, which is released as streamflow during the melting period. The predicted change in future climate will bring new challenges in water resource management in snow-dominated headwater catchments and their receiving lowlands. To improve predictions of hydrologic extreme events, particularly summer droughts, it is important characterize the relationship between winter snowpack and summer (low) flows in such areas (e.g., Godsey et al., 2014). In this context, stable water isotopes (18O, 2H) are a powerful tool for fingerprinting the sources of streamflow and tracing water flow pathways. For this reason, we have established an isotope sampling network in the Alptal catchment (46.4 km2) in Central-Switzerland as part of the SREP-Drought project (Snow Resources and the Early Prediction of hydrological DROUGHT in mountainous streams). Samples of precipitation (daily), snow cores (weekly) and runoff (daily) are analyzed for their isotopic signature in a regular cycle. Precipitation is also sampled along a horizontal transect at the valley bottom, and along an elevational transect. Additionally, the analysis of snow meltwater is of importance. As the sample collection of snow meltwater in mountainous terrain is often impractical, we have developed a fully automatic snow lysimeter system, which measures meltwater volume and collects samples for isotope analysis at daily intervals. The system consists of three lysimeters built from Decagon-ECRN-100 High Resolution Rain Gauges as standard component that allows monitoring of meltwater flow. Each lysimeter leads the meltwater into a 10-liter container that is automatically sampled and then emptied daily. These water samples are replaced regularly and analyzed afterwards on their isotopic composition in the lab. Snow melt events as well as system status can be monitored in real time. In our presentation we describe the automatic snow lysimeter system and present initial results from field tests in winter 2015/2016 under natural conditions at an experimental field site. Fully functional deployment in a forested and an open field location in the Erlenbach subcatchment (0.7 km2) is envisaged for winter 2016/2017. Godsey, S.E.,* J.W. Kirchner and C.L. Tague, Effects of changes in winter snowpacks on summer low flows: case studies in the Sierra Nevada, California, USA, Hydrological Processes, 28, 5048-5064, doi: 10.1002/hyp.9943, 2014.

Modeling the isotopic evolution of snowpack and snowmelt: Testing a spatially distributed parsimonious approach.

PubMed

Ala-Aho, Pertti; Tetzlaff, Doerthe; McNamara, James P; Laudon, Hjalmar; Kormos, Patrick; Soulsby, Chris

2017-07-01

Use of stable water isotopes has become increasingly popular in quantifying water flow paths and travel times in hydrological systems using tracer-aided modeling. In snow-influenced catchments, snowmelt produces a traceable isotopic signal, which differs from original snowfall isotopic composition because of isotopic fractionation in the snowpack. These fractionation processes in snow are relatively well understood, but representing their spatiotemporal variability in tracer-aided studies remains a challenge. We present a novel, parsimonious modeling method to account for the snowpack isotope fractionation and estimate isotope ratios in snowmelt water in a fully spatially distributed manner. Our model introduces two calibration parameters that alone account for the isotopic fractionation caused by sublimation from interception and ground snow storage, and snowmelt fractionation progressively enriching the snowmelt runoff. The isotope routines are linked to a generic process-based snow interception-accumulation-melt model facilitating simulation of spatially distributed snowmelt runoff. We use a synthetic modeling experiment to demonstrate the functionality of the model algorithms in different landscape locations and under different canopy characteristics. We also provide a proof-of-concept model test and successfully reproduce isotopic ratios in snowmelt runoff sampled with snowmelt lysimeters in two long-term experimental catchment with contrasting winter conditions. To our knowledge, the method is the first such tool to allow estimation of the spatially distributed nature of isotopic fractionation in snowpacks and the resulting isotope ratios in snowmelt runoff. The method can thus provide a useful tool for tracer-aided modeling to better understand the integrated nature of flow, mixing, and transport processes in snow-influenced catchments.

Potential application of radiogenic isotopes and geophysical methods to understand the hydrothermal dystem of the Upper Geyser Basin, Yellowstone National Park

USGS Publications Warehouse

Paces, James B.; Long, Andrew J.; Koth, Karl R.

2015-01-01

Numerous geochemical and geophysical studies have been conducted at Yellowstone National Park to better understand the hydrogeologic processes supporting the thermal features of the Park. This report provides the first 87Sr/86Sr and 234U/238U data for thermal water from the Upper Geyser Basin (UGB) intended to evaluate whether heavy radiogenic isotopes might provide insight to sources of groundwater supply and how they interact over time and space. In addition, this report summarizes previous geophysical studies made at Yellowstone National Park and provides suggestions for applying non-invasive ground and airborne studies to better understand groundwater flow in the subsurface of the UGB. Multiple samples from Old Faithful, Aurum, Grand, Oblong, and Daisy geysers characterized previously for major-ion concentrations and isotopes of water (δ2H, δ18O, and 3H) were analyzed for Sr and U isotopes. Concentrations of dissolved Sr and U are low (4.3–128 ng g-1 Sr and 0.026–0.0008 ng g-1 U); consequently only 87Sr/86Sr data are reported for most samples. Values of 87Sr/86Sr for most geysers remained uniform between April and September 2007, but show large increases in all five geysers between late October 2007 and early April, 2008. By late summer of 2008, 87Sr/86Sr values returned to values similar to those observed a year earlier. Similar patterns are not present in major-ion data measured on the same samples. Furthermore, large geochemical differences documented between geysers are not observed in 87Sr/86Sr data, although smaller differences between sites may be present. Sr-isotope data are consistent with a stratified hydrologic system where water erupted in spring and summer of 2007 and summer of 2008 equilibrated with local intracaldera rhyolite flows at shallower depths. Water erupted between October 2007 and April 2008 includes greater amounts of groundwater that circulated deep enough to acquire a radiogenic 87Sr/86Sr, most likely from Archean basement rocks. Details of how the shallow and deep components interact and mechanisms causing these interactions remain unknown, but the data demonstrate the usefulness of obtaining Sr-isotope data from future sample campaigns. Geophysical methods that would be useful for characterization of the UGB subsurface properties and geothermal system include electromagnetic (EM), gravity, and ambient seismic. A suite of ground-based EM methods could be used in a synergistic combination together with airborne EM surveys to provide data for a range of spatial scales and resolutions. Existing thermal data for the shallow subsurface could be used to relate ground and airborne EM survey data to locations of geothermal fluids near the surface. Gravity surveys would be useful for mapping subsurface density anomalies and possibly monitoring changes in degree of saturation with groundwater. Ambient seismic surveys would be useful for estimating the thickness of unconsolidated deposits that contain the shallow groundwater system. A study that combines radiogenic isotope tracers with geophysical methods has the potential to better characterize the geothermal workings in the UGB. Insights gained could lead to a better understanding of the geothermal system and how Park infrastructure may cause perturbations. Measurements of radiogenic isotopes from multiple geysers and pools in localized areas within the UGB that are coupled with data from geophysical surveys would help refine conceptual models of mixing between deep- and shallow-derived subsurface fluids.

Distribution and geochemical characterization of coalbed gases at excavation fields at natural analogue site area Velenje Basin, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Žigon, Stojan; Grassa, Fausto; Sedlar, Jerneja; Zadnik, Ivo; Zavšek, Simon

2016-04-01

Unconventional gas resources, including coal bed methane and shale gas, are a growing part of the global energy mix, which has changed the economic and strategic picture for gas consuming and producing countries, including the USA, China and Australia that, together are responsible for around half the currently recoverable unconventional gas resources. However, CBM production was often hindered by low permeability and mineralization in cleats and fractures, necessitating the development of cost effective horizontal drilling and completion techniques. Geochemical and isotopic monitoring of coalbed gases at excavation fields in Velenje Basin started in year 2000, with the aim to obtain better insights into the origin of coalbed gases. Results from active excavation fields in the mining areas Pesje and Preloge in the year period 2014-2015 are presented in this study. Composition and isotopic composition of coalbed gases were determined with mass - spectrometric methods. The chemical (methane, carbon dioxide, nitrogen) and isotopic composition of carbon in methane and carbon dioxide in the Velenje Basin vary and depend on the composition of the source of coalbed gas before excavation, advancement of the working face, depth of the longwall face, pre-mining activity and newly mined activity. The basic gas components determined in excavation fields are carbon dioxide and methane. Knowledge of the stable isotope geochemistry of coal bed and shale gas and the related production water is essential to determine not only gas origins but also the dominant methanogenic pathway in the case of microbial gas. Concentrations of methane at active excavation fields are changing from 1.8 to 63.9 %, concentrations of carbon dioxide are changing from 36.1 to 98.2% and CDMI (Carbon Dioxide Methane Index) index from 0.2 to 100 %. Isotopic composition of carbon dioxide is changing from -11.0 to -1.9‰ , isotopic composition of methane from -71.8 to -43.3‰ , isotopic composition of deuterium in methane from -343.9 to -223.1‰ , respectively. Further, these characteristics of methane have been compared with those observed in other coal sedimentary basins worldwide. The isotopic compositions of carbon and hydrogen in methane in the excavation fields show its biogenic origin, while a high Carbon Dioxide Methane Index (CDMI index) indicates the bacterial and endogenic origin of carbon dioxide.

From soil to grape and wine: Variation of light and heavy elements isotope ratios.

PubMed

Durante, Caterina; Bertacchini, Lucia; Bontempo, Luana; Camin, Federica; Manzini, Daniela; Lambertini, Paolo; Marchetti, Andrea; Paolini, Mauro

2016-11-01

In the development of a geographical traceability model, it is necessary to understand if the value of the monitored indicators in a food is correlated to its origin or if it is also influenced by 'external factors' such as those coming from its production. In this study, a deeper investigation of the trend of direct geographical traceability indicators along the winemaking process of two traditional oenological products was carried out. Different processes were monitored, sampling each step of their production (grape juice, intermediate products and wine). The results related to the determinations of δ(18)O, (D/H)I, (D/H)II, δ(13)C, δ(15)N and (87)Sr/(86)Sr have been reported. Furthermore, correspondence with the isotopic values coming from the respective soil and vine-branch samples have been investigated as well, showing the optimal traceability power of the monitored geographical tracers. Copyright © 2016 Elsevier Ltd. All rights reserved.

A prototype experiment for cooperative monitoring of nuclear reactors with cubic meter scale antineutrino detectors

NASA Astrophysics Data System (ADS)

Bernstein, A.; Allen, M.; Bowden, N.; Brennan, J.; Carr, D. J.; Estrada, J.; Hagmann, C.; Lund, J. C.; Madden, N. W.; Winant, C. D.

2005-09-01

Our Lawrence Livermore National Laboratory/Sandia National Laboratories collaboration has deployed a cubic-meter-scale antineutrino detector to demonstrate non-intrusive and automatic monitoring of the power levels and plutonium content of a nuclear reactor. Reactor monitoring of this kind is required for all non-nuclear weapons states under the Nuclear Nonproliferation Treaty (NPT), and is implemented by the International Atomic Energy Agency (IAEA). Since the antineutrino count rate and energy spectrum depend on the relative yields of fissioning isotopes in the reactor core, changes in isotopic composition can be observed without ever directly accessing the core. Data from a cubic meter scale antineutrino detector, coupled with the well-understood principles that govern the core's evolution in time, can be used to determine whether the reactor is being operated in an illegitimate way. Our group has deployed a detector at the San Onofre reactor site in California to demonstrate this concept. This paper describes the concept and shows preliminary results from 8 months of operation.

Rapid and high-resolution stable isotopic measurement of biogenic accretionary carbonate using an online CO2 laser ablation system: Standardization of the analytical protocol.

PubMed

Sreemany, Arpita; Bera, Melinda Kumar; Sarkar, Anindya

2017-12-30

The elaborate sampling and analytical protocol associated with conventional dual-inlet isotope ratio mass spectrometry has long hindered high-resolution climate studies from biogenic accretionary carbonates. Laser-based on-line systems, in comparison, produce rapid data, but suffer from unresolvable matrix effects. It is, therefore, necessary to resolve these matrix effects to take advantage of the automated laser-based method. Two marine bivalve shells (one aragonite and one calcite) and one fish otolith (aragonite) were first analysed using a CO 2 laser ablation system attached to a continuous flow isotope ratio mass spectrometer under different experimental conditions (different laser power, sample untreated vs vacuum roasted). The shells and the otolith were then micro-drilled and the isotopic compositions of the powders were measured in a dual-inlet isotope ratio mass spectrometer following the conventional acid digestion method. The vacuum-roasted samples (both aragonite and calcite) produced mean isotopic ratios (with a reproducibility of ±0.2 ‰ for both δ 18 O and δ 13 C values) almost identical to the values obtained using the conventional acid digestion method. As the isotopic ratio of the acid digested samples fall within the analytical precision (±0.2 ‰) of the laser ablation system, this suggests the usefulness of the method for studying the biogenic accretionary carbonate matrix. When using laser-based continuous flow isotope ratio mass spectrometry for the high-resolution isotopic measurements of biogenic carbonates, the employment of a vacuum-roasting step will reduce the matrix effect. This method will be of immense help to geologists and sclerochronologists in exploring short-term changes in climatic parameters (e.g. seasonality) in geological times. Copyright © 2017 John Wiley & Sons, Ltd.

Effects of euthanasia method on stable-carbon and stable-nitrogen isotope analysis for an ectothermic vertebrate.

PubMed

Atwood, Meredith A

2013-04-30

Stable isotope analysis is a critical tool for understanding ecological food webs; however, results can be sensitive to sample preparation methods. To limit the possibility of sample contamination, freezing is commonly used to euthanize invertebrates and preserve non-lethal samples from vertebrates. For destructive sampling of vertebrates, more humane euthanasia methods are preferred to freezing and it is essential to evaluate how these euthanasia methods affect stable isotope results. Stable isotope ratios and elemental composition of carbon and nitrogen were used to evaluate whether the euthanasia method compromised the integrity of the sample for analysis. Specifically, the stable isotope and C:N ratios were compared for larval wood frogs (Rana sylvatica  =  Lithobates sylvaticus), an ectothermic vertebrate, that had been euthanized by freezing with four different humane euthanasia methods: CO2, benzocaine, MS-222 (tricaine methanesulfonate), and 70% ethanol. The euthanasia method was not related to the δ(13)C or δ(15)N values and the comparisons revealed no differences between freezing and any of the other treatments. However, there were slight (non-significant) differences in the isotope ratios of benzocaine and CO2 when each was compared with freezing. The elemental composition was altered by the euthanasia method employed. The percentage nitrogen was higher in CO2 treatments than in freezing, and similar (non-significant) trends were seen for ethanol treatments relative to freezing. The resulting C:N ratios were higher for benzocaine treatments than for both CO2 and ethanol. Similar (non-significant) trends suggested that the C:N ratios were also higher for animals euthanized by freezing than for both CO2 and ethanol euthanasia methods. The euthanasia method had a larger effect on elemental composition than stable isotope ratios. The percentage nitrogen and the subsequent C:N ratios were most affected by the CO2 and ethanol euthanasia methods, whereas non-significant trends suggested that benzocaine and CO2 altered the stable isotope ratios. It appears that the use of MS-222 and freezing with dry ice are the most appropriate euthanasia methods for ectothermic vertebrates. Copyright © 2013 John Wiley & Sons, Ltd.

First-principles investigation of vanadium isotope fractionation in solution and during adsorption

NASA Astrophysics Data System (ADS)

Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang

2015-09-01

Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ⁡α V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ⁡α V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.

Monitoring of catalyst performance in CO2 lasers using frequency modulation spectroscopy with diode lasers

NASA Technical Reports Server (NTRS)

Wang, Liang-Guo; Sachse, Glen

1990-01-01

Closed-cycle CO2 laser operation with removal of O2 and regeneration of CO2 can be achieved by catalytic CO-O2 recombination. Both parametric studies of the optimum catalyst formulation and long-term performance tests require on line monitoring of CO, O2 and CO2 concentrations. There are several existing methods for molecular oxygen detection. These methods are either intrusive (such as electrochemical method or mass spectrometry) or very expensive (such as CARS, UV laser absorption). Researchers demonstrated a high-sensitivity spectroscopic measurement of O2 using the two-tone frequency modulation spectroscopy (FMS) technique with a near infrared GaAlAs diode laser. Besides its inexpensive cost, fast response time, nonintrusive measurements and high sensitivity, this technique may also be used to differentiate between isotopes due to its high spectroscopic resolution. This frequency modulation spectroscopy technique could also be applied for the on-line monitoring of CO and CO2 using InGaAsP diode lasers operation in the 1.55 microns region and H2O in the 1.3 microns region. The existence of single mode optical fibers at the near infrared region makes it possible to combine FMS with optical fiber technology. Optical fiber FMS is particularly suitable for making point-measurements at one or more locations in the CO2 laser/catalyst system.

Installation and Implementation of a Comprehensive Groundwater Monitoring Program for the Indian Wells Valley, California

DTIC Science & Technology

2010-04-01

isotopes. Laboratory analysis for general chemistry included Na, Ca, Mg, K, Fe, Cl, HCO3, CO3 , SO4, F, B, NO3, arsenic (As), hardness, alkalinity...used for interpretations within the project. Prior to this effort, a single -location repository for isotopic data related to IWV investigations...canyons of importance to this study (Indian Wells Canyon, Freeman Canyon, and the upgradient canyons of Cow Haven, Sage, and Horse). Single samples

Worldwide measurements of radioxenon background near isotope production facilities, a nuclear power plant and at remote sites: the ‘‘EU/JA-II’’ Project

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

Saey, P. R.J.; Ringbom, Anders; Bowyer, Ted W.

The Comprehensive Nuclear-Test-Ban Treaty (CTBT) specifies that radioxenon measurements should be performed at 40 or more stations worldwide within the International Monitoring System (IMS). Measuring radioxenon is one of the principle techniques to detect underground nuclear explosions. Specifically, presence and ratios of different radioxenon isotopes allows determining whether a detection event under consideration originated from a nuclear explosion or a civilian source. However, radioxenon monitoring on a global scale is a novel technology and the global civil background must be characterized sufficiently. This paper lays out a study, based on several unique measurement campaigns, of the worldwide concentrations and sourcesmore » of verification relevant xenon isotopes. It complements the experience already gathered with radioxenon measurements within the CTBT IMS programme and focuses on locations in Belgium, Germany, Kuwait, Thailand and South Africa where very little information was available on ambient xenon levels or interesting sites offered opportunities to learn more about emissions from known sources. The findings corroborate the hypothesis that a few major radioxenon sources contribute in great part to the global radioxenon background. Additionally, the existence of independent sources of 131mXe (the daughter of 131I) has been demonstrated, which has some potential to bias the isotopic signature of signals from nuclear explosions.« less

Integrating Stomach Content and Stable Isotope Analyses to Quantify the Diets of Pygoscelid Penguins

PubMed Central

Polito, Michael J.; Trivelpiece, Wayne Z.; Karnovsky, Nina J.; Ng, Elizabeth; Patterson, William P.; Emslie, Steven D.

2011-01-01

Stomach content analysis (SCA) and more recently stable isotope analysis (SIA) integrated with isotopic mixing models have become common methods for dietary studies and provide insight into the foraging ecology of seabirds. However, both methods have drawbacks and biases that may result in difficulties in quantifying inter-annual and species-specific differences in diets. We used these two methods to simultaneously quantify the chick-rearing diet of Chinstrap (Pygoscelis antarctica) and Gentoo (P. papua) penguins and highlight methods of integrating SCA data to increase accuracy of diet composition estimates using SIA. SCA biomass estimates were highly variable and underestimated the importance of soft-bodied prey such as fish. Two-source, isotopic mixing model predictions were less variable and identified inter-annual and species-specific differences in the relative amounts of fish and krill in penguin diets not readily apparent using SCA. In contrast, multi-source isotopic mixing models had difficulty estimating the dietary contribution of fish species occupying similar trophic levels without refinement using SCA-derived otolith data. Overall, our ability to track inter-annual and species-specific differences in penguin diets using SIA was enhanced by integrating SCA data to isotopic mixing modes in three ways: 1) selecting appropriate prey sources, 2) weighting combinations of isotopically similar prey in two-source mixing models and 3) refining predicted contributions of isotopically similar prey in multi-source models. PMID:22053199

Hydrogen/deuterium exchange in mass spectrometry.

PubMed

Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

2018-03-30

The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Accuracy of delta 18O isotope ratio measurements on the same sample by continuous-flow isotope-ratio mass spectrometry

USDA-ARS?s Scientific Manuscript database

The doubly labeled water method is considered the reference method to measure energy expenditure. Conventional mass spectrometry requires a separate aliquot of the same sample to be prepared and analyzed separately. With continuous-flow isotope-ratio mass spectrometry, the same sample could be analy...

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

PubMed

Chen, Shasha; Jia, Wanglu; Peng, Ping'an

2016-08-15

Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Device and method for separating oxygen isotopes

DOEpatents

Rockwood, Stephen D.; Sander, Robert K.

1984-01-01

A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

Novel methods for estimating 3D distributions of radioactive isotopes in materials

NASA Astrophysics Data System (ADS)

Iwamoto, Y.; Kataoka, J.; Kishimoto, A.; Nishiyama, T.; Taya, T.; Okochi, H.; Ogata, H.; Yamamoto, S.

2016-09-01

In recent years, various gamma-ray visualization techniques, or gamma cameras, have been proposed. These techniques are extremely effective for identifying "hot spots" or regions where radioactive isotopes are accumulated. Examples of such would be nuclear-disaster-affected areas such as Fukushima or the vicinity of nuclear reactors. However, the images acquired with a gamma camera do not include distance information between radioactive isotopes and the camera, and hence are "degenerated" in the direction of the isotopes. Moreover, depth information in the images is lost when the isotopes are embedded in materials, such as water, sand, and concrete. Here, we propose two methods of obtaining depth information of radioactive isotopes embedded in materials by comparing (1) their spectra and (2) images of incident gamma rays scattered by the materials and direct gamma rays. In the first method, the spectra of radioactive isotopes and the ratios of scattered to direct gamma rays are obtained. We verify experimentally that the ratio increases with increasing depth, as predicted by simulations. Although the method using energy spectra has been studied for a long time, an advantage of our method is the use of low-energy (50-150 keV) photons as scattered gamma rays. In the second method, the spatial extent of images obtained for direct and scattered gamma rays is compared. By performing detailed Monte Carlo simulations using Geant4, we verify that the spatial extent of the position where gamma rays are scattered increases with increasing depth. To demonstrate this, we are developing various gamma cameras to compare low-energy (scattered) gamma-ray images with fully photo-absorbed gamma-ray images. We also demonstrate that the 3D reconstruction of isotopes/hotspots is possible with our proposed methods. These methods have potential applications in the medical fields, and in severe environments such as the nuclear-disaster-affected areas in Fukushima.

High accuracy method for the application of isotope dilution to gas chromatography/mass spectrometric analysis of gases.

PubMed

Milton, Martin J T; Wang, Jian

2003-01-01

A new isotope dilution mass spectrometry (IDMS) method for high-accuracy quantitative analysis of gases has been developed and validated by the analysis of standard mixtures of carbon dioxide in nitrogen. The method does not require certified isotopic reference materials and does not require direct measurements of the highly enriched spike. The relative uncertainty of the method is shown to be 0.2%. Reproduced with the permission of Her Majesty's Stationery Office. Copyright Crown copyright 2003.

A standardized kit for automated quantitative assessment of candidate protein biomarkers in human plasma.

PubMed

Percy, Andrew J; Mohammed, Yassene; Yang, Juncong; Borchers, Christoph H

2015-12-01

An increasingly popular mass spectrometry-based quantitative approach for health-related research in the biomedical field involves the use of stable isotope-labeled standards (SIS) and multiple/selected reaction monitoring (MRM/SRM). To improve inter-laboratory precision and enable more widespread use of this 'absolute' quantitative technique in disease-biomarker assessment studies, methods must be standardized. Results/methodology: Using this MRM-with-SIS-peptide approach, we developed an automated method (encompassing sample preparation, processing and analysis) for quantifying 76 candidate protein markers (spanning >4 orders of magnitude in concentration) in neat human plasma. The assembled biomarker assessment kit - the 'BAK-76' - contains the essential materials (SIS mixes), methods (for acquisition and analysis), and tools (Qualis-SIS software) for performing biomarker discovery or verification studies in a rapid and standardized manner.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means.

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.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-01-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-09-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

Testing sequential extraction methods for the analysis of multiple stable isotope systems from a bone sample

NASA Astrophysics Data System (ADS)

Sahlstedt, Elina; Arppe, Laura

2017-04-01

Stable isotope composition of bones, analysed either from the mineral phase (hydroxyapatite) or from the organic phase (mainly collagen) carry important climatological and ecological information and are therefore widely used in paleontological and archaeological research. For the analysis of the stable isotope compositions, both of the phases, hydroxyapatite and collagen, have their more or less well established separation and analytical techniques. Recent development in IRMS and wet chemical extraction methods have facilitated the analysis of very small bone fractions (500 μg or less starting material) for PO43-O isotope composition. However, the uniqueness and (pre-) historical value of each archaeological and paleontological finding lead to preciously little material available for stable isotope analyses, encouraging further development of microanalytical methods for the use of stable isotope analyses. Here we present the first results in developing extraction methods for combining collagen C- and N-isotope analyses to PO43-O-isotope analyses from a single bone sample fraction. We tested sequential extraction starting with dilute acid demineralization and collection of both collagen and PO43-fractions, followed by further purification step by H2O2 (PO43-fraction). First results show that bone sample separates as small as 2 mg may be analysed for their δ15N, δ13C and δ18OPO4 values. The method may be incorporated in detailed investigation of sequentially developing skeletal material such as teeth, potentially allowing for the investigation of interannual variability in climatological/environmental signals or investigation of the early life history of an individual.

An isotope dilution capillary electrophoresis/tandem mass spectrometry (CE-MS/MS) method for the simultaneous measurement of choline, betaine, and dimethylglycine concentrations in human plasma.

PubMed

Forteschi, Mauro; Zinellu, Angelo; Assaretti, Stefano; Mangoni, Arduino A; Pintus, Gianfranco; Carru, Ciriaco; Sotgia, Salvatore

2016-10-01

Plasma concentrations of choline, betaine, and dimethylglycine provide valuable information on the flow of methyl groups in key biological processes, particularly during folate deficiency states. We developed a new method to simultaneously measure these analytes in human plasma. Following sample deproteinization using acetonitrile, an aliquot was evaporated to dryness under vacuum to be then taken up by water. Finally, analytes were separated by capillary electrophoresis and detected by electrospray ionization triple-quadrupole mass spectrometry, in multiple reaction monitoring mode, using two stable isotope-labeled internal standards. Linearity of the calibration curves of each analyte was good (R(2) > 0.99). Average limits of detection (LODs) and limits of quantification (LOQs) for choline, betaine, and dimethylglycine were, respectively, 0.43, 0.62, and 0.31 μmol/L and 1.52, 2.11, and 0.97 μmol/L. Mean recovery of three replicates of two spiked concentrations levels was close to 100 % for all of the analytes. Repeatability and intermediate precision, expressed as %RSD of measurements, were <9 %. The method, applied to measure analytes in samples from 30 patients with chronic kidney disease and 30 age- and sex-matched healthy controls, was able to detect differences between groups and the sexes.

Quantitative determination of four nitrofuran metabolites in meat by isotope dilution liquid chromatography-electrospray ionisation-tandem mass spectrometry.

PubMed

Mottier, Pascal; Khong, Seu-Ping; Gremaud, Eric; Richoz, Janique; Delatour, Thierry; Goldmann, Till; Guy, Philippe A

2005-03-04

A confirmatory method based on isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for the low-level determination of residues of four nitrofuran veterinary drugs in meat, e.g., furazolidone, furaltadone, nitrofurantoin, and nitrofurazone. The procedure entails an acid-catalysed release of protein-bound metabolites, followed by their in situ conversion into the 2-nitrobenzaldehyde (NBA) imine-type derivatives. Liquid-liquid extraction and clean-up on a polymeric solid phase extraction cartridge are then performed before LC-MS/MS analysis by positive electrospray ionisation (ESI) applying multiple reaction monitoring of three transition reactions for each compound. Reliable quantitation is obtained by using one deuterated analogue per analyte (d4-NBA derivative) as internal standard (IS). Validation of the method in chicken meat was conducted following the European Union (EU) criteria for the analysis of veterinary drug residues in foods. The decision limits (CCalpha) were 0.11-0.21 microg/kg, and the detection capabilities (CCbeta) 0.19-0.36 microg/kg, thus below the minimum required performance limit (MRPL) set at 1 microg/kg by the EU. The method is robust and suitable for routine quality control operations, and more than 200 sample injections were performed without excessive pollution of the mass spectrometer or loss of LC column performance.

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.

Method for isotopic analysis of chlorinated organic compounds

DOEpatents

Holt, Ben D.; Sturchio, Neil C.

1999-01-01

The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO.sub.2 and CuCl. The CO.sub.2 is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH.sub.3 I to form CH.sub.3 Cl, extracted and analyzed for chlorine isotope ratio.

Rapid extraction and assay of uranium from environmental surface samples

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

Barrett, Christopher A.; Chouyyok, Wilaiwan; Speakman, Robert J.

Extraction methods enabling faster removal and concentration of uranium compounds for improved trace and low-level assay are demonstrated for standard surface sampling material in support of nuclear safeguards efforts, health monitoring, and other nuclear analysis applications. A key problem with the existing surface sampling swipes is the requirement for complete digestion of sample and sampling matrix. This is a time-consuming and labour-intensive process that limits laboratory throughput, elevates costs, and increases background levels. Various extraction methods are explored for their potential to quickly and efficiently remove different chemical forms of uranium from standard surface sampling material. A combination of carbonatemore » and peroxide solutions is shown to give the most rapid and complete form of uranyl compound extraction and dissolution. This rapid extraction process is demonstrated to be compatible with standard inductive coupled plasma mass spectrometry methods for uranium isotopic assay as well as screening techniques such as x-ray fluorescence. The general approach described has application beyond uranium to other analytes of nuclear forensic interest (e.g., rare earth elements and plutonium) as well as heavy metals for environmental and industrial hygiene monitoring.« less

Isotopic tracing of perchlorate in the environment

USGS Publications Warehouse

Sturchio, Neil C.; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Jackson, W. Andrew; Baskaran, Mark

2012-01-01

Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 −concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

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.

THEORETICAL AND EXPERIMENTAL ASPECTS OF ISOTOPIC FRACTIONATION.

USGS Publications Warehouse

O'Neil, James R.

1986-01-01

Essential to the interpretation of natural variations of light stable isotope ratios is knowledge of the magnitude and temperature dependence of isotopic fractionation factors between the common minerals and fluids. These fractionation factors are obtained in three ways: (1) Semi-empirical calculations using spectroscopic data and the methods of statistical mechanics. (2) Laboratory calibration studies. (3) Measurements of natural samples whose formation conditions are well-known or highly constrained. In this chapter methods (1) and (2) are evaluated and a review is given of the present state of knowledge of the theory of isotopic fractionation and the fraction that influence the isotopic properties of minerals.

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.

Escherichia coli cell-free protein synthesis and isotope labeling of mammalian proteins.

PubMed

Terada, Takaho; Yokoyama, Shigeyuki

2015-01-01

This chapter describes the cell-free protein synthesis method, using an Escherichia coli cell extract. This is a cost-effective method for milligram-scale protein production and is particularly useful for the production of mammalian proteins, protein complexes, and membrane proteins that are difficult to synthesize by recombinant expression methods, using E. coli and eukaryotic cells. By adjusting the conditions of the cell-free method, zinc-binding proteins, disulfide-bonded proteins, ligand-bound proteins, etc., may also be produced. Stable isotope labeling of proteins can be accomplished by the cell-free method, simply by using stable isotope-labeled amino acid(s) in the cell-free reaction. Moreover, the cell-free protein synthesis method facilitates the avoidance of stable isotope scrambling and dilution over the recombinant expression methods and is therefore advantageous for amino acid-selective stable isotope labeling. Site-specific stable isotope labeling is also possible with a tRNA molecule specific to the UAG codon. By the cell-free protein synthesis method, coupled transcription-translation is performed from a plasmid vector or a PCR-amplified DNA fragment encoding the protein. A milligram quantity of protein can be produced with a milliliter-scale reaction solution in the dialysis mode. More than a thousand solution structures have been determined by NMR spectroscopy for uniformly labeled samples of human and mouse functional domain proteins, produced by the cell-free method. Here, we describe the practical aspects of mammalian protein production by the cell-free method for NMR spectroscopy. © 2015 Elsevier Inc. All rights reserved.

Pollution and Climate Effects on Tree-Ring Nitrogen Isotopes

NASA Astrophysics Data System (ADS)

Savard, M. M.; Bégin, C.; Marion, J.; Smirnoff, A.

2009-04-01

BACKGROUND Monitoring of nitrous oxide concentration only started during the last 30 years in North America, but anthropogenic atmospheric nitrogen has been significantly emitted over the last 150 years. Can geochemical characteristics of tree rings be used to infer past changes in the nitrogen cycle of temperate regions? To address this question we use nitrogen stable isotopes in 125 years-long ring series from beech specimens (Fagus grandifolia) of the Georgian Bay Islands National Park (eastern Ontario), and pine (Pinus strobus) and beech trees of the Arboretum Morgan near Montreal (western Quebec). To evaluate the reliability of the N stable isotopes in wood treated for removal of soluble materials, we tested both tree species from the Montreal area. The reproducibility from tree to tree was excellent for both pine and beech trees, the isotopic trends were strongly concordant, and they were not influenced by the heartwood-sapwood transition zone. The coherence of changes of the isotopic series observed for the two species suggests that their tree-ring N isotopic values can serve as environmental indicator. RESULTS AND INTERPRETATION In Montreal and Georgian Bay, the N isotopes show strong and similar parallel agreement (Gleichlaufigkeit test) with the climatic parameters. So in fact, the short-term isotopic fluctuations correlate directly with summer precipitation and inversely with summer and spring temperature. A long-term decreasing isotope trend in Montreal indicates progressive changes in soil chemistry after 1951. A pedochemical change is also inferred for the Georgian Bay site on the basis of a positive N isotopic trend initiated after 1971. At both sites, the long-term ^15N series correlate with a proxy for NOx emissions (Pearson correlation), and carbon-isotope ring series suggest that the same trees have been impacted by phytotoxic pollutants (Savard et al., 2009a). We propose that the contrasted long-term nitrogen-isotope changes of Montreal and Georgian Bay reflect deposition of NOx emissions from cars and coal-power plants, with higher proportions from coal burning in Georgian Bay (Savard et al., 2009b). This interpretation is conceivable because recent monitoring indicates that coal-power plant NOx emissions play an important role in the annual N budget in Ontario, but they are negligible on the Quebec side. CONCLUSION Interpretations of long tree-ring N isotopic series in terms of effects generated by airborne N-species have been previously advocated. Here we further propose that the contrasted isotopic trends obtained for wood samples from two regions reflect different regional anthropogenic N deposition combined with variations of climatic conditions. This research suggests that nitrogen tree-ring series may record both regional climatic conditions and anthropogenic perturbations of the N cycle. REFERENCES Savard, M.M., Bégin,C., Marion, J., Aznar, J.-C., Smirnoff, A., 2009a. Changes of Air Quality in an urban region as inferred from tree-ring width and stable isotopes. Chapter 9 in "Relating Atmospheric Source Apportionment to Vegetation Effects: Establishing Cause Effect Relationships" (A. Legge ed.). Elsevier, Amsterdam; doi: 10.1016/S1474-8177(08)00209x. Savard, M.M., Bégin, C., Smirnoff, A., Marion, J., Rioux-Paquette, E., 2009b. Tree-ring nitrogen isotopes reflect climatic effects and anthropogenic NOx emissions. Env. Sci. Tech (doi: 10.1021/es802437k).

Understanding key drivers controlling daily stable isotope variations in precipitation of Costa Rica, Central America

NASA Astrophysics Data System (ADS)

Sanchez-Murillo, Ricardo; Welsh, Kristin; Birkel, Christian; Esquivel-Hernández, Germain; Corrales-Salazar, Jose; Boll, Jan; Brooks, Erin; Roupsard, Olivier; Katchan, Irina; Arce-Mesén, Rafael; Soulsby, Chris; Araguás-Araguás, Luis

2015-04-01

Costa Rica is located on the Central American Isthmus, which receives direct moisture inputs from the Caribbean Sea and the Pacific Ocean. The relatively narrow, but high relief Central American land bridge is characterized by unique mountainous and lowland microclimates. However, only limited knowledge exists about the impact of relief and regional atmospheric circulation patterns on precipitation origin, transport, and isotopic composition in this tropical region. Therefore, the main scope of this study is to identify the key drivers controlling variations in meteoric waters of Costa Rica using stable isotopes based on daily sample collection for the year 2013. The monitoring sites comprise three strategic locations across Costa Rica: Heredia (Central Valley), Turrialba (Caribbean slope), and Caño Seco (South Pacific slope). Sporadic dry season rain is mostly related to isolated enriched events ranging from -5.8‰ d18O up to -0.9‰ d18O. By mid-May, the Intertropical Convergence Zone reaches Costa Rica resulting in a notable depletion in isotope ratios (up to -18.5‰ d18O). HYSPLIT back air mass trajectories indicate the strong influence on the origin and transport of precipitation of two main moisture transport mechanisms, the Caribbean Low Level Jet and the Colombian Low Level Jet as well as localized convection events. Multiple linear regression models constructed based on Random Forests of surface meteorological information and atmospheric sounding profiles suggest that Lifted Condensation Level and surface relative humidity are the main factors controlling isotopic variations. These findings diverge from the recognized 'amount effect' in monthly composite samples across the tropics. Understanding of stable isotope dynamics in tropical precipitation can be used to enhance catchment and groundwater modeling efforts in ungauged basins where scarcity of long-term monitoring data drastically limit current and future water resources management.

Source term estimates of radioxenon released from the BaTek medical isotope production facility using external measured air concentrations.

PubMed

Eslinger, Paul W; Cameron, Ian M; Dumais, Johannes Robert; Imardjoko, Yudi; Marsoem, Pujadi; McIntyre, Justin I; Miley, Harry S; Stoehlker, Ulrich; Widodo, Susilo; Woods, Vincent T

2015-10-01

BATAN Teknologi (BaTek) operates an isotope production facility in Serpong, Indonesia that supplies (99m)Tc for use in medical procedures. Atmospheric releases of (133)Xe in the production process at BaTek are known to influence the measurements taken at the closest stations of the radionuclide network of the International Monitoring System (IMS). The purpose of the IMS is to detect evidence of nuclear explosions, including atmospheric releases of radionuclides. The major xenon isotopes released from BaTek are also produced in a nuclear explosion, but the isotopic ratios are different. Knowledge of the magnitude of releases from the isotope production facility helps inform analysts trying to decide if a specific measurement result could have originated from a nuclear explosion. A stack monitor deployed at BaTek in 2013 measured releases to the atmosphere for several isotopes. The facility operates on a weekly cycle, and the stack data for June 15-21, 2013 show a release of 1.84 × 10(13) Bq of (133)Xe. Concentrations of (133)Xe in the air are available at the same time from a xenon sampler located 14 km from BaTek. An optimization process using atmospheric transport modeling and the sampler air concentrations produced a release estimate of 1.88 × 10(13) Bq. The same optimization process yielded a release estimate of 1.70 × 10(13) Bq for a different week in 2012. The stack release value and the two optimized estimates are all within 10% of each other. Unpublished production data and the release estimate from June 2013 yield a rough annual release estimate of 8 × 10(14) Bq of (133)Xe in 2014. These multiple lines of evidence cross-validate the stack release estimates and the release estimates based on atmospheric samplers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Source Term Estimates of Radioxenon Released from the BaTek Medical Isotope Production Facility Using External Measured Air Concentrations

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

Eslinger, Paul W.; Cameron, Ian M.; Dumais, Johannes R.

2015-10-01

Abstract Batan Teknologi (BaTek) operates an isotope production facility in Serpong, Indonesia that supplies 99mTc for use in medical procedures. Atmospheric releases of Xe-133 in the production process at BaTek are known to influence the measurements taken at the closest stations of the International Monitoring System (IMS). The purpose of the IMS is to detect evidence of nuclear explosions, including atmospheric releases of radionuclides. The xenon isotopes released from BaTek are the same as those produced in a nuclear explosion, but the isotopic ratios are different. Knowledge of the magnitude of releases from the isotope production facility helps inform analystsmore » trying to decide whether a specific measurement result came from a nuclear explosion. A stack monitor deployed at BaTek in 2013 measured releases to the atmosphere for several isotopes. The facility operates on a weekly cycle, and the stack data for June 15-21, 2013 show a release of 1.84E13 Bq of Xe-133. Concentrations of Xe-133 in the air are available at the same time from a xenon sampler located 14 km from BaTek. An optimization process using atmospheric transport modeling and the sampler air concentrations produced a release estimate of 1.88E13 Bq. The same optimization process yielded a release estimate of 1.70E13 Bq for a different week in 2012. The stack release value and the two optimized estimates are all within 10 percent of each other. Weekly release estimates of 1.8E13 Bq and a 40 percent facility operation rate yields a rough annual release estimate of 3.7E13 Bq of Xe-133. This value is consistent with previously published estimates of annual releases for this facility, which are based on measurements at three IMS stations. These multiple lines of evidence cross-validate the stack release estimates and the release estimates from atmospheric samplers.« less

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 drop pools may produce a similarly weaker kinetic effect.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

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.

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means. 3 figures.

Chemical and isotopic evolution of a layered eastern U.S. snowpack and its relation to stream-water composition

USGS Publications Warehouse

Shanley, J.B.; Kendall, C.; Albert, M.R.; Hardy, J.P.

1995-01-01

The chemical, isotopic, and morphologic evolution of a layered snowpack was investigated during the winter of 1993-94 at Sleepers River Research Watershed in Danville, Vermont. The snowpack was monitored at two small basins: a forested basin at 525 m elevation, and an agricultural basin at 292 m elevation. At each site, the snowpack morphology was characterized and individual layers were sampled seven times during the season. Nitrate and 8d18O profiles in the snowpack remained relatively stable until peak accumulation in mid-March, except near the snow surface, where rain-on-snow events caused water and nitrate movement down to impeding ice layers. Subsequently, water and nitrate moved more readily through the ripening snowpack. As the snowpack evolved, combined processes of preferential ion elution, isotopic fractionation, and infiltration of isotopically heavy rainfall caused the pack to become depleted in solutes and isotopically enriched. The release of nitrate and isotopically depleted water was reflected in patterns of nitrate concentrations and ??18O of meltwater and stream water. Results supported data from the previous year which suggested that streamflow in the forested basin during snowmelt was dominated by groundwater discharge.

Automated QA/QC Check for Beta-Gamma Coincidence Detector

DTIC Science & Technology

2007-09-01

of the ARSA, 222Rn gas can be introduced into the gas cell, along with the radioactive xenon isotopes. While this radon decays via alpha decay and...Explosion Monitoring Technologies 741 Figure 2. γ-singles spectrum from a 222Rn spike. The peaks are primarily from the radon daughter 214Pb with...National Laboratory (PNNL), can collect and detect several radioxenon isotopes. The ARSA is very sensitive to 133Xe, 131mXe, 133mXe, and 135Xe due to the

A New and Improved Carbon Dioxide Isotope Analyzer for Understanding Soil-Plant-Atmosphere Interactions

NASA Astrophysics Data System (ADS)

Huang, Y. W.; Berman, E. S.; Owano, T. G.; Verfaillie, J. G.; Oikawa, P. Y.; Baldocchi, D. D.; Still, C. J.; Gardner, A.; Baer, D. S.; Rastogi, B.

2015-12-01

Stable CO2 isotopes provide information on biogeochemical processes that occur at the soil-plant-atmosphere interface. While δ13C measurement can provide information on the sources of the CO2, be it photosynthesis, natural gas combustion, other fossil fuel sources, landfills or other sources, δ18O, and δ17O are thought to be determined by the hydrological cycling of the CO2. Though researchers have called for analytical tools for CO2 isotope measurements that are reliable and field-deployable, developing such instrument remains a challenge. The carbon dioxide isotope analyzer developed by Los Gatos Research (LGR) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This new and improved analyzer measures CO2 concentration as well as δ13C, δ18O, and δ17O from CO2 at natural abundance (150-2500 ppm). The laboratory precision is ±200 ppb (1σ) in CO2 at 1 s, with a long-term (2 min) precision of ±20 ppb. The 1-second precision for both δ13C and δ18O is 0.7 ‰, and for δ17O is 1.8 ‰. The long-term (2 min) precision for both δ13C and δ18O is 0.08 ‰, and for δ17O is 0.18 ‰. The instrument has improved precision, stability and user interface over previous LGR CO2 isotope instruments and can be easily programmed for periodic referencing and sampling from different sources when coupled with LGR's multiport inlet unit (MIU). We have deployed two of these instruments at two different field sites, one at Twitchell Island in Sacramento County, CA to monitor the CO2 isotopic fluxes from an alfalfa field from 6/29/2015-7/13/2015, and the other at the Wind River Experimental Forest in Washington to monitor primarily the oxygen isotopes of CO2 within the canopy from 8/4/2015 through mid-November 2015. Methodology, laboratory development and testing and field performance are presented.

EC comparison on the determination of 226Ra, 228Ra, 234U and 238U in water among European monitoring laboratories.

PubMed

Wätjen, U; Benedik, L; Spasova, Y; Vasile, M; Altzitzoglou, T; Beyermann, M

2010-01-01

In anticipation of new European requirements for monitoring radioactivity concentration in drinking water, IRMM organized an interlaboratory comparison on the determination of low levels of activity concentrations (about 10-100 mBq L(-1)) of the naturally occurring radionuclides (226)Ra, (228)Ra, (234)U and (238)U in three commercially available mineral waters. Using two or three different methods with traceability to the International System of Reference (SIR), the reference values of the water samples were determined prior to the proficiency test within combined standard uncertainties of the order of 3%-10%. An overview of radiochemical separation and measurement methods used by the 45 participating laboratories are given. The results of the participants are evaluated versus the reference values. Several of the participants' results deviate by more than a factor of two from the reference values, in particular for the radium isotopes. Such erroneous analysis results may lead to a crucial omission of remedial actions on drinking water supplies or to economic loss by an unjustified action. Copyright 2009 Elsevier Ltd. 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 a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method is applied to the analysis of NIST SRM 981, the measured lead isotope ratios are in good agreement with its certified values. This proves that the developed method is not only consistent with the conventional one by NIST SRM 981 but also enables measurement of the lead isotope ratios with higher precision. Copyright © 2017 Elsevier B.V. All rights reserved.

Equilibrium properties of dense hydrogen isotope gases based on the theory of simple fluids.

PubMed

Kowalczyk, Piotr; MacElroy, J M D

2006-08-03

We present a new method for the prediction of the equilibrium properties of dense gases containing hydrogen isotopes. The proposed approach combines the Feynman-Hibbs effective potential method and a deconvolution scheme introduced by Weeks et al. The resulting equations of state and the chemical potentials as functions of pressure for each of the hydrogen isotope gases depend on a single set of Lennard-Jones parameters. In addition to its simplicity, the proposed method with optimized Lennard-Jones potential parameters accurately describes the equilibrium properties of hydrogen isotope fluids in the regime of moderate temperatures and pressures. The present approach should find applications in the nonlocal density functional theory of inhomogeneous quantum fluids and should also be of particular relevance to hydrogen (clean energy) storage and to the separation of quantum isotopes by novel nanomaterials.

Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

PubMed

Centler, Florian; Heße, Falk; Thullner, Martin

2013-09-01

At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways. © 2013.

Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C-valine isotopic ratios in complex biological samples.

PubMed

Godin, Jean-Philippe; Breuillé, Denis; Obled, Christiane; Papet, Isabelle; Schierbeek, Henk; Hopfgartner, Gérard; Fay, Laurent-Bernard

2008-10-01

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision (13)C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure (13)C isotopic enrichment of underivatised amino acids (Asp, Thr-Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(delta(13)C) reported with this method was found to be below 1 per thousand . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (delta(13)C= -12.3 to 150.8 per thousand), the calculated root-mean-square (rms) of SD was 0.38 and 0.46 per thousand and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (delta(13)C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound (13)C-Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p>0.05). The results of this work indicate that the LC-IRMS was successful for high-precision (13)C isotopic measurements in tracer studies giving (13)C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio.

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 silica (opal, glass, chert). The DTIA method has wide ranging application for addressing fundamental problems across many disciplines in Earth and Planetary Sciences, including: paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies.

Comparing floral and isotopic paleoelevation estimates: Examples from the western United States

NASA Astrophysics Data System (ADS)

Hyland, E. G.; Huntington, K. W.; Sheldon, N. D.; Smith, S. Y.; Strömberg, C. A. E.

2016-12-01

Describing paleoelevations is crucial to understanding tectonic processes and deconvolving the effects of uplift and climate on environmental change in the past. Decades of work has gone into estimating past elevation from various proxy archives, particularly using modern relationships between elevation and temperature, floral assemblage compositions, or oxygen isotope values. While these methods have been used widely and refined through time, they are rarely applied in tandem; here we provide two examples from the western United States using new multiproxy methods: 1) combining clumped isotopes and macrofloral assemblages to estimate paleoelevations along the Colorado Plateau, and 2) combining oxygen isotopes and phytolith methods to estimate paleoelevations within the greater Yellowstone region. Clumped isotope measurements and refined floral coexistence methods from sites on the northern Colorado Plateau like Florissant and Creede (CO) consistently estimate low (< 2km) elevations through the Eocene/Oligocene, suggesting slower uplift and a south-north propagation of the plateau. Oxygen isotope measurements and C4 phytolith estimates from sites surrounding the Yellowstone hotspot consistently estimate moderate uplift (0.2-0.7km) propagating along the hotspot track, suggesting migrating dynamic topography associated with the region. These examples provide support for the emerging practice of using multiproxy methods to estimate paleoelevations for important time periods, and can help integrate environmental and tectonic records of the past.

Verification of Egg Farming Systems from The Netherlands and New Zealand Using Stable Isotopes.

PubMed

Rogers, Karyne M; van Ruth, Saskia; Alewijn, Martin; Philips, Andy; Rogers, Pam

2015-09-30

Stable isotopes were used to develop authentication criteria of eggs laid under cage, barn, free range, and organic farming regimens from The Netherlands and New Zealand. A training set of commercial poultry feeds and egg albumen from 49 poultry farms across The Netherlands was used to determine the isotopic variability of organic and conventional feeds and to assess trophic effects of these corresponding feeds and barn, free range, and organic farming regimens on corresponding egg albumen. A further 52 brands of New Zealand eggs were sampled from supermarket shelves in 2008 (18), 2010 (30), and 2014 (4) to characterize and monitor changes in caged, barn, free range, and organic egg farming regimens. Stable carbon (δ(13)C) and nitrogen (δ(15)N) isotopes of 49 commercial poultry feeds and their corresponding egg albumens reveals that Dutch poultry are fed exclusively on a plant-based feed and that it is possible to discriminate between conventional and organic egg farming regimens in The Netherlands. Similarly, it is possible to discriminate between New Zealand organic and conventional egg farming regimens, although in the initial screening in 2008, results showed that some organic eggs had isotope values similar to those of conventional eggs, suggesting hens were not exclusively receiving an organic diet. Dutch and New Zealand egg regimens were shown to have a low isotopic correlation between both countries, because of different poultry feed compositions. In New Zealand, both conventional and organic egg whites have higher δ(15)N values than corresponding Dutch egg whites, due to the use of fishmeal or meat and bone meal (MBM), which is banned in European countries. This study suggests that stable isotopes (specifically nitrogen) show particular promise as a screening and authentication tool for organically farmed eggs. Criteria to assess truthfulness in labeling of organic eggs were developed, and we propose that Dutch organic egg whites should have a minimum δ(15)N value of 4.8‰ to account for an organic plant derived diet. Monitoring of New Zealand egg isotopes over the past 7 years suggests that organic eggs should have a minimum δ(15)N value of 6.0‰, and eggs falling below this value should be investigated further by certification authorities.

Isotopic and elemental analysis of fish tissues for provenance determination

NASA Astrophysics Data System (ADS)

Zannella, Carmela; Adamo, Paola; Opper, Christine; Schwendinger, Susanne; Knezevic, Sara; Van den Oever, Sabrina; Tchaikovsky, Anastassiya; Zitek, Andreas; Prohaska, Thomas

2017-04-01

The reliable tracing of the productions flows of food products through the entire supply chain is an essential requirement for all types of food commodities qualified by origin, composition and quality. This is a minimum requirement to implement safety for the consumer, enhance consumer confidence and countervail fraudulent practices. One important food commodity is fish and fish products. Reliable methods to trace the origin of fish have become of high importance. The investigation focused on the identification of adequate geochemical marker in fish meat and the corresponding linkage to the ambient water. The Sr/Ca ratio along with the 87Sr/86Sr isotope ratio analyzed by (multi collector) inductively coupled plasma mass spectrometry (MC ICP-MS) proved to be the most potential tools in this respect. For the first time, a direct link of fish meat to water could be accomplished.In addition, fish hard parts (otoliths, fin rays, fish bones) were under investigation to reconstruct the habitat changes during the lifespan of a fishes life. Fish hard parts have the potential to serve as "life time recorder". Thus the spatial investigation of the elemental and isotopic composition can be used to monitor habitat changes with time. The spatially resolved data of hard tissues was collected by means of Laser Ablation Split Stream ICP-MS/MC ICP-MS. This work is accomplished within the scope of the project "CSI: TRACE YOUR FOOD".

Nuclear and isotopic techniques applied to supporting nutritional studies in East Asia and Pacific Countries: IAEA's contributions over 20 years.

PubMed

Kim, Seong-Ai; Miranda-da-Cruz, B; Mokhtar, Najat; Iyengar, Venkatesh

2004-01-01

The world's scientific community has recognized that isotopic techniques play a vital role in monitoring the effectiveness of nutrition intervention by providing precise data on absorption, bioavailablity and interaction of various micronutrients in a cost effective manner. The International Atomic Energy Agency (IAEA) has been supporting many such health related studies in Member States from developing countries using nuclear and isotopic methods for over 20 years. This report documents the Agency's support for a variety of projects in East Asia and Pacific countries to assess body composition, total energy expenditure, nutrient intake, osteoporosis, infection, vitamin and mineral bioavailability as well as food composition. The IAEA spent a total of 10,302,356 US dollars through Coordinated Research Projects (CRP) and Technical Cooperation Projects (TCP) over the past 20 years. Out of this only 2,732,802, US dollars or 26.5% was used by the East Asia and Pacific countries. While the participation of East Asia and Pacific countries was strong in CRPs and moderate in regional TCPs, they did not participate in national TCPs at all. The non-participation under national TCPs is a serious deficiency when compared with Latin American and African regions and therefore, more participation from the East Asia and Pacific countries in national TCPs is strongly encouraged in the future.

Molecular Medicine: Synthesis and In Vivo Detection of Agents for use in Boron Neutron Capture Therapy. Final Report

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

Kabalka, G. W.

2005-06-28

The primary objective of the project was the development of in vivo methods for the detection and evaluation of tumors in humans. The project was focused on utilizing positron emission tomography (PET) to monitor the distribution and pharamacokinetics of a current boron neutron capture therapy (BNCT) agent, p-boronophenylalanine (BPA) by labeling it with a fluorine-18, a positron emitting isotope. The PET data was then used to develop enhanced treatment planning protocols. The study also involved the synthesis of new tumor selective BNCTagents that could be labeled with radioactive nuclides for the in vivo detection of boron.

[Preparation and certification of mussel reference material for organochlorine pesticides and polychlorinated biphenyls using isotope dilution-high resolution mass spectrometry].

PubMed

Lu, Xianbo; Chen, Jiping; Wang, Shuqiu; Zou, Lili; Tian, Yuzeng; Ni, Yuwen; Su, Fan

2012-09-01

A method for the preparation and certification of the reference material of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in mussel tissue is described. The mussel tissue from Dalian Bay was frozen-dried, comminuted, sieved, homogenized, packaged, and sterilized by 60Co radiation sterilization in turn. The certified values for 18 OCPs and 16 PCBs were determined by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) using isotope dilution and internal standard quantitation techniques. The certified values were validated and given based on seven accredited laboratories, and these values are traceable to the SI (international system of units) through gravimetrically prepared standards of established purity and measurement intercomparisons. The certified values of PCBs and OCPs in mussel span 4 orders of magnitude with a relative uncertainty of about 10%. This material is a natural biological material with confirmed good homogeneity and stability, and it was approved as the grade "primary reference material" (GBW10069) in June 2012 in China. This reference material provided necessary quality control products for our country to implement the Stockholm Treaty on the monitoring of persistent organic pollutants (POPs). The material is intended to be used for the method validation and quality control in the determination of OCPs and PCBs in biota samples.

Identification and Quantification of Preterm Birth Biomarkers in Human Cervicovaginal Fluid by Liquid Chromatography/Tandem Mass Spectrometry

PubMed Central

Shah, Sumit J.; Yu, Kenneth H.; Sangar, Vineet; Parry, Samuel I.; Blair, Ian A.

2009-01-01

Spontaneous preterm birth (PTB) before 37 completed weeks of gestation resulting from preterm labor (PTL) is a leading contributor of perinatal morbidity and mortality. Early identification of at-risk women by reliable screening tests could alleviate this health issue; however, conventional methods such as obstetric history and clinical risk factors, uterine activity monitoring, biochemical markers, and cervical sonography for screening women at risk for PTB have proven unsuccessful in lowering the rate of PTB. Cervicovaginal fluid (CVF) might prove to be a useful, readily available biological fluid for identifying diagnostic PTB biomarkers. Human columnar epithelial endocervical-1 (End1) and vaginal (Vk2) cell secretomes were employed to generate a stable isotope labeled proteome (SILAP) standard to facilitate characterization and relative quantification of proteins present in CVF. The SILAP standard was prepared using stable isotope labeling by amino acids in cell culture (SILAC) of End1 and Vk2 through seven passages. The labeled secreted proteins from both cell lines were combined and characterized by liquid-chromatography-tandem mass spectrometry (LC-MS/MS). 1211 proteins were identified in the End1-Vk2 SILAP standard, with 236 proteins being consistently identified in each of the replicates analyzed. Individual proteins were found to contain < 0.5 % of the endogenous unlabeled forms. Identified proteins were screened to provide a set of fifteen candidates that have either previously been identified as potential PTB biomarkers or could be linked mechanistically to PTB. Stable isotope dilution LC-multiple reaction monitoring (MRM/MS) assays were then developed for conducting relative quantification of the fifteen candidate biomarkers in human CVF samples from term and PTB cases. Three proteins were significantly elevated in PTB cases (desmoplakin isoform 1, stratifin, and thrombospondin 1 precursor), providing a foundation for further validation in larger patient cohorts. PMID:19271751

Identification and quantification of preterm birth biomarkers in human cervicovaginal fluid by liquid chromatography/tandem mass spectrometry.

PubMed

Shah, Sumit J; Yu, Kenneth H; Sangar, Vineet; Parry, Samuel I; Blair, Ian A

2009-05-01

Spontaneous preterm birth (PTB) before 37 completed weeks of gestation resulting from preterm labor (PTL) is a leading contributor of perinatal morbidity and mortality. Early identification of at-risk women by reliable screening tests could alleviate this health issue; however, conventional methods such as obstetric history and clinical risk factors, uterine activity monitoring, biochemical markers, and cervical sonography for screening women at risk for PTB have proven unsuccessful in lowering the rate of PTB. Cervicovaginal fluid (CVF) might prove to be a useful, readily available biological fluid for identifying diagnostic PTB biomarkers. Human columnar epithelial endocervical-1 (End1) and vaginal (Vk2) cell secretomes were employed to generate a stable isotope labeled proteome (SILAP) standard to facilitate characterization and relative quantification of proteins present in CVF. The SILAP standard was prepared using stable isotope labeling by amino acids in cell culture (SILAC) of End1 and Vk2 through seven passages. The labeled secreted proteins from both cell lines were combined and characterized by liquid-chromatography-tandem mass spectrometry (LC-MS/MS). In total, 1211 proteins were identified in the End1-Vk2 SILAP standard, with 236 proteins being consistently identified in each of the replicates analyzed. Individual proteins were found to contain <0.5% of the endogenous unlabeled forms. Identified proteins were screened to provide a set of 15 candidates that have either previously been identified as potential PTB biomarkers or could be linked mechanistically to PTB. Stable isotope dilution LC-multiple reaction monitoring (MRM/MS) assays were then developed for conducting relative quantification of the 15 candidate biomarkers in human CVF samples from term and PTB cases. Three proteins were significantly elevated in PTB cases (desmoplakin isoform 1, stratifin, and thrombospondin 1 precursor), providing a foundation for further validation in larger patient cohorts.

Palaeoclimate signal recorded by stable isotopes in cave ice: a modeling approach

NASA Astrophysics Data System (ADS)

Perşoiu, A.; Bojar, A.-V.

2012-04-01

Ice accumulations in caves preserve a large variety of geochemical information as candidate proxies for both past climate and environmental changes, one of the most significant being the stable isotopic composition of the ice. A series of recent studies have targeted oxygen and hydrogen stable isotopes in cave ice as proxies for past air temperatures, but the results are far from being as straightforward as they are in high latitude and altitude glaciers and ice caps. The main problems emerging from these studies are related to the mechanisms of cave ice formation (i.e., freezing of water) and post-formation processes (melting and refreezing), which both alter the original isotopic signal in water. Different methods have been put forward to solve these issues and a fair understanding of the present-day link between stable isotopes in precipitation and cave ice exists now. However, the main issues still lays unsolved: 1) is it possible to extend this link to older ice and thus reconstruct past changes in air temperature?; 2) to what extent are ice dynamics processes modifying the original climatic signal and 3) what is the best method to be used in extracting a climatic signal from stable isotopes in cave ice? To respond to these questions, we have conducted a modeling experiment, in which a theoretical cave ice stable isotope record was constructed using present-day observations on stable isotope behavior in cave ice and ice dynamics, and different methods (presently used for both polar and cave glaciers), were used to reconstruct the original, known, isotopic values. Our results show that it is possible to remove the effects of ice melting and refreezing on stable isotope composition of cave ice, and thus reconstruct the original isotopic signal, and further the climatic one.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

Water isotope partitioning and ecohydrologic separation in mixed conifer forest explored with a centrifugation water extraction method

NASA Astrophysics Data System (ADS)

Bowers, W.; Mercer, J.; Pleasants, M.; Williams, D. G.

2017-12-01

Isotopic partitioning of water within soil into tightly and loosely bound fractions has been proposed to explain differences between isotopic water sources used by plants and those that contribute to streams and ground water, the basis for the "two water worlds" hypothesis. We examined the isotope ratio values of water in trees, bulk soil, mobile water collected from soil lysimeters, stream water, and GW at three different hillslopes in a mixed conifer forest in southeastern Wyoming, USA. Hillslopes differed in aspect and topographic position with corresponding differences in surface energy balance, snowmelt timing, and duration of soil moisture during the dry summer. The isotopic results support the partitioning of water within the soil; trees apparently used a different pool of water for transpiration than that recovered from soil lysimeters and the source was not resolved with the isotopic signature of the water that was extracted from bulk soil via cryogenic vacuum distillation. Separating and measuring the isotope ratios values in these pools would test the assumption that the tightly bound water within the soil has the same isotopic signature as the water transpired by the trees. We employed a centrifugation approach to separate water within the soil held at different tensions by applying stepwise increases in rotational velocity and pressures to the bulk soil samples. Effluent and the remaining water (cryogenically extracted) at each step were compared. We first applied the centrifugation method in a simple lab experiment using sandy loam soil and separate introductions of two isotopically distinct waters. We then applied the method to soil collected from the montane hillslopes. For the lab experiment, we predicted that effluents would have distinct isotopic signatures, with the last effluent and extracted water more closely representing the isotopic signature of the first water applied. For our field samples, we predicted that the isotopic signature of the water discharged in the last centrifuge step and final extraction would more closely represent the isotopic signature of water extracted from trees. Understanding the isotopic partitioning of water within soil is important for interpreting plant water isotope values within the context of the "two water worlds" hypothesis.

Method for isotopic analysis of chlorinated organic compounds

DOEpatents

Holt, B.D.; Sturchio, N.C.

1999-08-24

The present invention provides a method for preparing a VOC sample for carbon and chlorine isotope ratio analysis by mass spectrometer. A VOC sample is placed in a combustion tube and reacted with CuO to form CO{sub 2} and CuCl. The CO{sub 2} is then extracted and analyzed for the carbon isotope ratio. The CuCl is separated from the excess CuO and reacted with CH{sub 3}I to form CH{sub 3}Cl, extracted and analyzed for chlorine isotope ratio. 9 figs.

SAIL--stereo-array isotope labeling.

PubMed

Kainosho, Masatsune; Güntert, Peter

2009-11-01

Optimal stereospecific and regiospecific labeling of proteins with stable isotopes enhances the nuclear magnetic resonance (NMR) method for the determination of the three-dimensional protein structures in solution. Stereo-array isotope labeling (SAIL) offers sharpened lines, spectral simplification without loss of information and the ability to rapidly collect and automatically evaluate the structural restraints required to solve a high-quality solution structure for proteins up to twice as large as before. This review gives an overview of stable isotope labeling methods for NMR spectroscopy with proteins and provides an in-depth treatment of the SAIL technology.

Calcium isotope analysis by mass spectrometry.

PubMed

Boulyga, Sergei F

2010-01-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

Monitoring induced denitrification during managed aquifer recharge in an infiltration pond

NASA Astrophysics Data System (ADS)

Grau-Martínez, Alba; Folch, Albert; Torrentó, Clara; Valhondo, Cristina; Barba, Carme; Domènech, Cristina; Soler, Albert; Otero, Neus

2018-06-01

Managed aquifer recharge (MAR) is a well-known technique for improving water quality and increasing groundwater resources. Denitrification (i.e. removal of nitrate) can be enhanced during MAR by coupling an artificial recharge pond with a permeable reactive layer (PRL). In this study, we examined the suitability of a multi-isotope approach for assessing the long-term effectiveness of enhancing denitrification in a PRL containing vegetal compost. Batch laboratory experiments confirmed that the PRL was still able to enhance denitrification two years after its installation in the infiltration pond. At the field scale, changes in redox indicators along a flow path and below the MAR-PRL system were monitored over 21 months during recharge and non-recharge periods. Results showed that the PRL was still releasing non-purgeable dissolved organic carbon five years after its installation. Nitrate concentration coupled with isotopic data collected from the piezometer network at the MAR system indicated that denitrification was occurring in the saturated zone immediately beneath the infiltration pond, where recharged water and native groundwater mix. Furthermore, longer operational periods of the MAR-PRL system increased denitrification extent. Multi-isotope analyses are therefore proved to be useful tools in identifying and quantifying denitrification in MAR-PRL systems.

The effects of nitrogen pollutants on the isotopic signal (δ15N) of Ulva lactuca: Microcosm experiments.

PubMed

Orlandi, Lucia; Calizza, Edoardo; Careddu, Giulio; Carlino, Pasquale; Costantini, Maria Letizia; Rossi, Loreto

2017-02-15

Effects of two chemical forms of Nitrogen (NH 4 + and NO 3 - ) on δ 15 N in Ulva lactuca were analysed separately and in mixture at two concentrations. We assessed whether the δ 15 N values of U. lactuca discriminate between Nitrogen from synthetic fertilisers (inorganic) and from fresh cow manure (organic), and the isotopic ability of the macroalga to reflect Nitrogen concentrations. Isotopic signature and N content of the macroalga reflected different nitrogenous sources and their concentrations after 48h. The inorganic Nitrogen source (NH 4 NO 3 ) altered the isotopic values of the macroalgae more than Nitrogen from fresh cow manure (NO 3 - ). δ 15 N values observed in the mixed solution did not differ from those displayed in NH 4 NO 3 treatment alone. We conclude that stable isotope analysis of U. lactuca collected in an unpolluted site and experimentally submerged in sites suspected of being affected by disturbance is a useful tool for rapid monitoring of anthropogenic discharges of Nitrogen pollutants. Copyright © 2016 Elsevier Ltd. All rights reserved.

An optimized method for the accurate determination of patulin in apple products by isotope dilution-liquid chromatography/mass spectrometry.

PubMed

Seo, Miyeong; Kim, Byungjoo; Baek, Song-Yee

2015-07-01

Patulin, a mycotoxin produced by several molds in fruits, has been frequently detected in apple products. Therefore, regulatory bodies have established recommended maximum permitted patulin concentrations for each type of apple product. Although several analytical methods have been adopted to determine patulin in food, quality control of patulin analysis is not easy, as reliable certified reference materials (CRMs) are not available. In this study, as a part of a project for developing CRMs for patulin analysis, we developed isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC/MS/MS) as a higher-order reference method for the accurate value-assignment of CRMs. (13)C7-patulin was used as internal standard. Samples were extracted with ethyl acetate to improve recovery. For further sample cleanup with solid-phase extraction (SPE), the HLB SPE cartridge was chosen after comparing with several other types of SPE cartridges. High-performance liquid chromatography was performed on a multimode column for proper retention and separation of highly polar and water-soluble patulin from sample interferences. Sample extracts were analyzed by LC/MS/MS with electrospray ionization in negative ion mode with selected reaction monitoring of patulin and (13)C7-patulin at m/z 153→m/z 109 and m/z 160→m/z 115, respectively. The validity of the method was tested by measuring gravimetrically fortified samples of various apple products. In addition, the repeatability and the reproducibility of the method were tested to evaluate the performance of the method. The method was shown to provide accurate measurements in the 3-40 μg/kg range with a relative expanded uncertainty of around 1%.

Online analysis of chlorine stable isotopes in chlorinated ethylenes: an inter-laboratory study

NASA Astrophysics Data System (ADS)

Bernstein, Anat; Shouakar-Stash, Orfan; Hunkeler, Daniel; Sakaguchi-Söder, Kaori; Laskov, Christine; Aravena, Ramon; Elsner, Martin

2010-05-01

In the last decade, compound-specific stable isotopes analysis of groundwater pollutants became an important tool to identify different sources of the same pollutant and for tracking natural attenuating processes in the sub-surface. It has been shown that trends in the isotopic composition of the target compounds can shed light on in-situ processes that are otherwise difficult to track. Analytical methods of carbon, nitrogen and hydrogen were established and are by now frequently used for a variety of organic pollutants. Yet, the motivation of introducing analytical methods for new isotopes is emerging. This motivation is further enhanced, as advantages of using two or more stable isotopes for gaining better insight on degradation pathways are well accepted. One important element which demands the development of appropriate analytical methods is chlorine, which is found in various groups of organic pollutants, among them the chlorinated ethylenes. Chlorinated ethylenes are considered as high priority environmental pollutants, and the development of suitable chlorine isotope methods for this group of pollutants is highly desired. Ideally, stable isotope techniques should have the capability to determine the isotopic composition of and individual target compound in a non-pure mixture, without the requirement of a laborious off-line treatment. Indeed, in the last years two different concepts for on-line chlorine isotope analysis methods were introduced, by using either a standard quadrapole GC/MS (Sakaguchi-Söder et al., 2007) or by using a GC/IRMS (Shouakar-Stash et al., 2006). We present a comparison of the performances of two concepts, carried out in five different laboratories: Waterloo (GC/IRMS), Neuchâtel (GC/MS), Darmstadt (GC/MS), Tübingen (GC/MS) and Munich (GC/IRMS). This comparison was performed on pure trichloroethylene and dichloroethylene products of different manufactures, as well as trichloroethylene and dichloroethylene samples that were exposed to biodegradation. This study sets standards for further application of these techniques to distinguish sources and track degradation processes in the sub-surface.

On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations

PubMed Central

Lightfoot, Emma; O’Connell, Tamsin C.

2016-01-01

Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on) causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals’ homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific homeland should not be attempted. PMID:27124001

Quantification of soy protein using the isotope method (δ(13)C and δ(15)N) for commercial brands of beef hamburger.

PubMed

Ducatti, Rhani; de Almeida Nogueira Pinto, José Paes; Sartori, Maria Márcia Pereira; Ducatti, Carlos

2016-12-01

Hamburgers (beef patties) may be adulterated through the overuse of protein extenders. Among vegetables, soy protein is the best substitute for animal protein. These ingredients help to reduce the cost of producing a final product, and they maximize profits for fraudulent industries. Moreover, the ingestion of soy or other non-meat proteins by allergic individuals may present a health risk. In addition, monitoring by supervisory bodies is hampered by a lack of appropriate analytical methodologies. Within this context, the aim of this study was to determine and quantify the levels of added soy protein by determination of (15)N and (13)C stable isotopes. A total of 100 beef hamburger samples from 10 commercial brands were analyzed. Only three samples of the G brand were within the standards set the Brazilian legislation. The remaining 97 samples from 10 commercial brands contained >4% soy protein; therefore, they are adulterated and not in compliance with the current legislation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Isotopic imaging via nuclear resonance fluorescence with laser-based Thomson radiation

DOEpatents

Barty, Christopher P. J. [Hayward, CA; Hartemann, Frederic V [San Ramon, CA; McNabb, Dennis P [Alameda, CA; Pruet, Jason A [Brentwood, CA

2009-07-21

The present invention utilizes novel laser-based, high-brightness, high-spatial-resolution, pencil-beam sources of spectrally pure hard x-ray and gamma-ray radiation to induce resonant scattering in specific nuclei, i.e., nuclear resonance fluorescence. By monitoring such fluorescence as a function of beam position, it is possible to image in either two dimensions or three dimensions, the position and concentration of individual isotopes in a specific material configuration. Such methods of the present invention material identification, spatial resolution of material location and ability to locate and identify materials shielded by other materials, such as, for example, behind a lead wall. The foundation of the present invention is the generation of quasimonochromatic high-energy x-ray (100's of keV) and gamma-ray (greater than about 1 MeV) radiation via the collision of intense laser pulses from relativistic electrons. Such a process as utilized herein, i.e., Thomson scattering or inverse-Compton scattering, produces beams having diameters from about 1 micron to about 100 microns of high-energy photons with a bandwidth of .DELTA.E/E of approximately 10E.sup.-3.

High resolution monitoring system for IRE stack releases.

PubMed

Deconninck, B; De Lellis, C

2013-11-01

The main activity of IRE (Institute for Radio-Element) is radioisotope production of bulk (99)Mo and (131)I for medical application (diagnosis and therapy). Those isotopes are chemically extracted from HEU (High Enriched Uranium) targets activated in reactors. During this process, fission products are released from the targets, including noble gases isotopes (Xe and Kr). Like any nuclear plant, IRE has release limits which are given by the Belgium authority and moreover IRE is in the process of continuously reducing the level of its releases. To achieve this mission, the need of an accurate tool is necessary and IRE has developed a specific monitoring system using a high resolution detector in order to identify and accurately estimate its gaseous releases. This system has a continuous air sampling system in the plant main stack. The sampled gases cross charcoal cartridges where they are slowed down and concentrated for higher detection efficiency. In front of those cartridges is installed an HPGe detector with a detection chain connected to a specific analysis system allowing on-line spectrum analysis. Each isotope can be separately followed without interferences, especially during the production process where high activity can be released. Due to its conception, the system also allows to measure iodine isotopes by integration on the charcoal cartridges. This device is of great help for accurately estimate IRE releases and to help for understanding specific releases and their origin in the production or maintenance process. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

PubMed

Ikehata, Kei; Hirata, Takafumi

2013-01-01

We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

Method and apparatus for tritiated water separation

DOEpatents

Nelson, David A.; Duncan, James B.; Jensen, George A.

1995-01-01

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained.

Method and apparatus for tritiated water separation

DOEpatents

Nelson, D.A.; Duncan, J.B.; Jensen, G.A.

1995-09-19

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained. 1 fig.

Isotopic abundance in atom trap trace analysis

DOEpatents

Lu, Zheng-Tian; Hu, Shiu-Ming; Jiang, Wei; Mueller, Peter

2014-03-18

A method and system for detecting ratios and amounts of isotopes of noble gases. The method and system is constructed to be able to measure noble gas isotopes in water and ice, which helps reveal the geological age of the samples and understand their movements. The method and system uses a combination of a cooled discharge source, a beam collimator, a beam slower and magneto-optic trap with a laser to apply resonance frequency energy to the noble gas to be quenched and detected.

Quantification of multiple simultaneously occurring nitrogen flows in the euphotic ocean

NASA Astrophysics Data System (ADS)

Xu, Min Nina; Wu, Yanhua; Zheng, Li Wei; Zheng, Zhenzhen; Zhao, Huade; Laws, Edward A.; Kao, Shuh-Ji

2017-03-01

The general features of the N cycle in the sunlit region of the ocean are well known, but methodological difficulties have previously confounded simultaneous quantification of transformation rates among the many different forms of N, e.g., ammonium (NH4+), nitrite (NO2-), nitrate (NO3-), and particulate/dissolved organic nitrogen (PN/DON). However, recent advances in analytical methodology have made it possible to employ a convenient isotope labeling technique to quantify in situ fluxes among oft-measured nitrogen species within the euphotic zone. Addition of a single 15N-labeled NH4+ tracer and monitoring of the changes in the concentrations and isotopic compositions of the total dissolved nitrogen (TDN), PN, NH4+, NO2-, and NO3- pools allowed us to quantify the 15N and 14N fluxes simultaneously. Constraints expressing the balance of 15N and 14N fluxes between the different N pools were expressed in the form of simultaneous equations, the unique solution of which via matrix inversion yielded the relevant N fluxes, including rates of NH4+, NO2-, and NO3- uptake; ammonia oxidation; nitrite oxidation; DON release; and NH4+ uptake by bacteria. The matrix inversion methodology that we used was designed specifically to analyze the results of incubations under simulated in situ conditions in the euphotic zone. By taking into consideration simultaneous fluxes among multiple N pools, we minimized potential artifacts caused by non-targeted processes in traditional source-product methods. The proposed isotope matrix method facilitates post hoc analysis of data from on-deck incubation experiments and can be used to probe effects of environmental factors (e.g., pH, temperature, and light) on multiple processes under controlled conditions.

Limited occurrence of denitrification in four shallow aquifers in agricultural areas of the United States

USGS Publications Warehouse

Green, C.T.; Puckett, L.J.; Böhlke, J.K.; Bekins, B.A.; Phillips, S.P.; Kauffman, L.J.; Denver, J.M.; Johnson, H.M.

2008-01-01

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N2 from denitrification increases with age. Stable isotopes and excess N2 imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 μmol N L−1d−1, comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

PubMed Central

Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

2015-01-01

The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

Determining and quantifying specific sources of light alkane

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.

2015-12-01

Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

Rapidly assessing changes in bone mineral balance using natural stable calcium isotopes

PubMed Central

Morgan, Jennifer L. L.; Skulan, Joseph L.; Gordon, Gwyneth W.; Romaniello, Stephen J.; Smith, Scott M.; Anbar, Ariel D.

2012-01-01

The ability to rapidly detect changes in bone mineral balance (BMB) would be of great value in the early diagnosis and evaluation of therapies for metabolic bone diseases such as osteoporosis and some cancers. However, measurements of BMB are hampered by difficulties with using biochemical markers to quantify the relative rates of bone resorption and formation and the need to wait months to years for altered BMB to produce changes in bone mineral density large enough to resolve by X-ray densitometry. We show here that, in humans, the natural abundances of Ca isotopes in urine change rapidly in response to changes in BMB. In a bed rest experiment, use of high-precision isotope ratio MS allowed the onset of bone loss to be detected in Ca isotope data after about 1 wk, long before bone mineral density has changed enough to be detectable with densitometry. The physiological basis of the relationship between Ca isotopes and BMB is sufficiently understood to allow quantitative translation of changes in Ca isotope abundances to changes in bone mineral density using a simple model. The rate of change of bone mineral density inferred from Ca isotopes is consistent with the rate observed by densitometry in long-term bed rest studies. Ca isotopic analysis provides a powerful way to monitor bone loss, potentially making it possible to diagnose metabolic bone disease and track the impact of treatments more effectively than is currently possible. PMID:22652567

Evaluating the skills of isotope-enabled general circulation models against in situ atmospheric water vapor isotope observations

NASA Astrophysics Data System (ADS)

Steen-Larsen, H. C.; Risi, C.; Werner, M.; Yoshimura, K.; Masson-Delmotte, V.

2017-01-01

The skills of isotope-enabled general circulation models are evaluated against atmospheric water vapor isotopes. We have combined in situ observations of surface water vapor isotopes spanning multiple field seasons (2010, 2011, and 2012) from the top of the Greenland Ice Sheet (NEEM site: 77.45°N, 51.05°W, 2484 m above sea level) with observations from the marine boundary layer of the North Atlantic and Arctic Ocean (Bermuda Islands 32.26°N, 64.88°W, year: 2012; south coast of Iceland 63.83°N, 21.47°W, year: 2012; South Greenland 61.21°N, 47.17°W, year: 2012; Svalbard 78.92°N, 11.92°E, year: 2014). This allows us to benchmark the ability to simulate the daily water vapor isotope variations from five different simulations using isotope-enabled general circulation models. Our model-data comparison documents clear isotope biases both on top of the Greenland Ice Sheet (1-11‰ for δ18O and 4-19‰ for d-excess depending on model and season) and in the marine boundary layer (maximum differences for the following: Bermuda δ18O = 1‰, d-excess = 3‰; South coast of Iceland δ18O = 2‰, d-excess = 5‰; South Greenland δ18O = 4‰, d-excess = 7‰; Svalbard δ18O = 2‰, d-excess = 7‰). We find that the simulated isotope biases are not just explained by simulated biases in temperature and humidity. Instead, we argue that these isotope biases are related to a poor simulation of the spatial structure of the marine boundary layer water vapor isotopic composition. Furthermore, we specifically show that the marine boundary layer water vapor isotopes of the Baffin Bay region show strong influence on the water vapor isotopes at the NEEM deep ice core-drilling site in northwest Greenland. Our evaluation of the simulations using isotope-enabled general circulation models also documents wide intermodel spatial variability in the Arctic. This stresses the importance of a coordinated water vapor isotope-monitoring network in order to discriminate amongst these model behaviors.

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 warming and greenhouse gas emission scenario. Our results call for action to create an international pan-Arctic monitoring water vapor isotope network in order to improve future projections of Arctic climate.

Nitrous oxide production pathways in a partial nitritation-anammox reactor: Isotopic evidence for nitrous oxide production associated anaerobic ammonium oxidation?

NASA Astrophysics Data System (ADS)

Wunderlin, P.; Harris, E. J.; Joss, A.; Emmenegger, L.; Kipf, M.; Mohn, J.; Siegrist, H.

2014-12-01

Nitrous oxide (N2O) is a strong greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment N2O can be produced via several pathways. This study investigates the dynamics of N2O emissions from a nitritation-anammox reactor, and links its interpretation to the nitrogen and oxygen isotopic signature of the emitted N2O. A 400-litre single-stage nitritation-anammox reactor was operated and continuously fed with digester liquid. The isotopic composition of N2O emissions was monitored online with quantum cascade laser absorption spectroscopy (QCLAS; Aerodyne Research, Inc.; Waechter et al., 2008). Dissolved ammonium and nitrate were monitored online (ISEmax, Endress + Hauser), while nitrite was measured with test strips (Nitrite-test 0-24mgN/l, Merck). Table 1. Summary of experiments conducted to understand N2O emissions Experimental conditions O2[mgO2/L] NO2-[mgN/L] NH4+[mgN/L] N2O/NH4+[%] Normal operation <0.1 <0.5 10 0.6 Normal operation, high NH4+ <0.1 <0.5 100 6.1 High aeration 0.5 to 1.5 up to 50 10 and 50 4.9 NO2- addition (oxic) <0.1 <0.5 to 4 10 5.8 NO2- addition (anoxic) 0 <0.5 to 4 10 3.2 NH2OH addition <0.1 <0.5 10 2.5 Results showed that under normal operating conditions, the N2O isotopic site preference (SP = d15Nα - d15Nβ) was much higher than expected - up to 41‰ - strongly suggesting an unknown N2O production pathway, which is hypothesized to be mediated by anammox activity (Figure 1). A less likely explanation is that the SP of N2O was increased by partial N2O reduction by heterotrophic denitrification. Various experiments were conducted to further investigate N2O formation pathways in the reactor. Our data reveal that N2O emissions increased when reactor operation was not ideal, for example when dissolved oxygen was too high (Table 1). SP measurements confirmed that these N2O peaks were due to enhanced nitrifier denitrification, generally related to nitrite build-up in the reactor (Figure 1; Table 1). Overall, process control via online N2O monitoring was confirmed to be an ideal method to detect imbalances in reactor operation and regulate aeration, to ensure optimal reactor conditions and minimise N2O emissions. ReferencesWaechter H. et al. (2008) Optics Express, 16: 9239-9244. Wunderlin, P et al. (2013) Environmental Science & Technology 47: 1339-1348.

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.

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