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Results for “quantitative limit of detection”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Determination of 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and -furans at the part per trillion level in United States beef fat using high-resolution gas chromatography/high-resolution mass spectrometry

As part of the U.S. EPA Dioxin Reassessment Program, the 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and furans were measured at part per trillion (ppt) levels in beef fat collected from slaughter facilities in the United States. This is the first statistically designed national survey of these compounds in the U.S. beef supply. Analyte concentrations were determined by high-resolution gas chromatography/high-resolution mass spectrometry, using isotope dilution methodology. Method limits of detection on a whole weight basis were 0.05 ppt for TCDD and 0.10 ppt for TCDF, 0.50 ppt for the pentas (PeCDDs/PeCDFs)/hexas (HxCDDs/HxCDFs)/heptas (HpCDDs/HpCDFs), and 3.00 ppt for the octas (OCDD/OCDF). Method detection and quantitation limits were established on the basis of demonstrated performance criteria utilizing fortified samples rather than by conventional signal-to-noise or variability of response methods. The background subtraction procedures developed for this study minimized the likelihood of false positives and increased the confidence associated with reported values near the detection limits. Mean and median values for each of the 2,3,7,8-Cl-substituted dioxins and furans are reported, along with the supporting information required for their interpretation. The mean toxic equivalence values for the samples are 0.35 ppt (nondetects = 0) and 0.89 ppt (nondetects = 1/2 LOD).

Benzofurans/analysis↗

Low level vapor verification of monomethyl hydrazine

The vapor scrubbing system and the coulometric test procedure for the low level vapor verification of monomethyl hydrazine (MMH) are evaluated. Experimental data on precision, efficiency of the scrubbing liquid, instrument response, detection and reliable quantitation limits, stability of the vapor scrubbed solution, and interference were obtained to assess the applicability of the method for the low ppb level detection of the analyte vapor in air. The results indicated that the analyte vapor scrubbing system and the coulometric test procedure can be utilized for the quantitative detection of low ppb level vapor of MMH in air.

Mehta, Narinder↗

The Second SeaWiFS HPLC Analysis Round-Robin Experiment (SeaHARRE-2)

Eight international laboratories specializing in the determination of marine pigment concentrations using high performance liquid chromatography (HPLC) were intercompared using in situ samples and a variety of laboratory standards. The field samples were collected primarily from eutrophic waters, although mesotrophic waters were also sampled to create a dynamic range in chlorophyll concentration spanning approximately two orders of magnitude (0.3 25.8 mg m-3). The intercomparisons were used to establish the following: a) the uncertainties in quantitating individual pigments and higher-order variables (sums, ratios, and indices); b) an evaluation of spectrophotometric versus HPLC uncertainties in the determination of total chlorophyll a; and c) the reduction in uncertainties as a result of applying quality assurance (QA) procedures associated with extraction, separation, injection, degradation, detection, calibration, and reporting (particularly limits of detection and quantitation). In addition, the remote sensing requirements for the in situ determination of total chlorophyll a were investigated to determine whether or not the average uncertainty for this measurement is being satisfied. The culmination of the activity was a validation of the round-robin methodology plus the development of the requirements for validating an individual HPLC method. The validation process includes the measurements required to initially demonstrate a pigment is validated, and the measurements that must be made during sample analysis to confirm a method remains validated. The so-called performance-based metrics developed here describe a set of thresholds for a variety of easily-measured parameters with a corresponding set of performance categories. The aggregate set of performance parameters and categories establish a) the overall performance capability of the method, and b) whether or not the capability is consistent with the required accuracy objectives.

Source record↗

A statistical analysis of gamma-ray bursts detected by the Konus Experiment on Venera 11 and 12

We discuss the advantages of using the V/V sub max method to test well-defined samples of gamma-ray bursts for the spatial uniformity of their parent population. We have applied the V/V sub max test to gamma ray bursts of duration longer than 1 second recorded by the Konus experiment aboard Venera 11 and 12. Based on a sample of 123 bursts, we find V/V sub max equals 0.46 plus or minus 0.03, consistent with a uniform distribution in space. We urge that experimenters give careful attention to the detection limit for each recorded gamma ray burst, and that quantitative data for burst properties and detection limits be published.

Schmidt, Maarten↗

Air Contamination Quantification by FTIR with Gas Cell

Air quality is of utmost importance in environmental studies and has many industrial applications such as aviators grade breathing oxygen (ABO) for pilots and breathing air for fire fighters. Contamination is a major concern for these industries as identified in MIL-PRF-27210, CGA G-4.3, CGA G-7.1, and NFPA 1989. Fourier Transform Infrared Spectroscopy (FTIR) is a powerful tool that when combined with a gas cell has tremendous potential for gas contamination analysis. Current procedures focus mostly on GC-MS for contamination quantification. Introduction of this topic will be done through a comparison of the currently used deterministic methods for gas contamination with those of FTIR gas analysis. Certification of the mentioned standards through the ISOIEC 17065 certifying body A2LA will be addressed followed by an evaluation of quality information such as the determinations of linearity and the limits of detection and quantitation. Major interferences and issues arising from the use of the FTIR for accredited work with ABO and breathing air will be covered.

Freischlag, Jason↗

High performance liquid chromatographic assay for the quantitation of total glutathione in plasma

A simple and widely used homocysteine HPLC procedure was applied for the HPLC identification and quantitation of glutathione in plasma. The method, which utilizes SBDF as a derivatizing agent utilizes only 50 microl of sample volume. Linear quantitative response curve was generated for glutathione over a concentration range of 0.3125-62.50 micromol/l. Linear regression analysis of the standard curve exhibited correlation coefficient of 0.999. Limit of detection (LOD) and limit of quantitation (LOQ) values were 5.0 and 15 pmol, respectively. Glutathione recovery using this method was nearly complete (above 96%). Intra-assay and inter-assay precision studies reflected a high level of reliability and reproducibility of the method. The applicability of the method for the quantitation of glutathione was demonstrated successfully using human and rat plasma samples.

Non-NASA Center↗

Multi-site modulation of flux during monolignol formation in loblolly pine (Pinus taeda)

Loblolly pine (Pinus taeda L.) cell suspension cultures secrete monolignols when placed in 8% sucrose/20 mM KI solution, and these were used to identify phenylpropanoid pathway flux-modulating steps. When cells were provided with increasing amounts of either phenylalanine (Phe) or cinnamic acid, cellular concentrations of immediate downstream products (cinnamic and p-coumaric acids, respectively) increased, whereas caffeic and ferulic acid pool sizes were essentially unaffected. Increasing Phe concentrations resulted in increased amounts of p-coumaryl alcohol relative to coniferyl alcohol. However, exogenously supplied cinnamic, p-coumaric, caffeic, and ferulic acids resulted only in increases in their intercellular concentrations, but not that of downstream cinnamyl aldehydes and monolignols. Supplying p-coumaryl and coniferyl aldehydes up to 40, 000-320,000-fold above the detection limits resulted in rapid, quantitative conversion into the monolignols. Only at nonphysiological concentrations was transient accumulation of intracellular aldehydes observed. These results indicate that cinnamic and p-coumaric acid hydroxylations assume important regulatory positions in phenylpropanoid metabolism, whereas cinnamyl aldehyde reduction does not serve as a control point. Copyright 1999 Academic Press.

NASA Discipline Plant Biology↗

Mineralogy and Geochemistry of Sedimentary Rocks and Eolian Sediments in Gale Crater, Mars: A Review After Six Earth Years of Exploration with Curiosity

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity was sent to Gale crater to study a sequence of ∼3.5 Ga old sedimentary rocks that, based on orbital visible and near- to short-wave infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence in the lower slopes of Mount Sharp in Gale crater preserves a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate, based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with instruments to examine the sedimentology and identify compositional changes in the stratigraphy. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer. CheMin measures loose sediment samples scooped from the surface and drilled rock powders, and the XRD provides quantitative mineralogy to a detection limit of ∼1 wt.% for crystalline phases. Curiosity has traversed>20 km since landing and has primarily been exploring an ancient lake environment fed by streams and groundwater. Of the 19 drilled rock samples analyzed by CheMin as of sol 2300 (January 2019), 15 are from fluvio-lacustrine deposits that comprise the Bradbury and Murray formations. Most of these samples were drilled from units that did not have a clear mineralogical signature from orbit. Results from CheMin demonstrate an astounding diversity in the mineralogy of these rocks that signifies geochemical variations in source rocks, transportation mechanisms, and depositional and diagenetic fluids. Most detrital igneous minerals are basaltic, but the discovery in a few samples of abundant silicate minerals that usually crystallize from evolved magmas on Earth remains enigmatic. Trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH in lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions in the lake waters themselves and/or in diagenetic fluids. Perhaps one of the biggest mysteries revealed by CheMin is the high abundance of X-ray amorphous materials (15–73 wt.%) in all samples drilled or scooped to date. CheMin has analyzed three modern eolian sands, which have helped constrain sediment transport and mineral segregation across the active Bagnold Dune Field. Ancient eolian sandstones drilled from the Stimson formation differ from modern eolian sands in that they contain abundant magnetite but no olivine, suggesting that diagenetic processes led to the alteration of olivine to release Fe(II) and precipitate magnetite. Fracture-associated halos in the Stimson and the Murray formations are evidence for complex aqueous processes long after the streams and lakes vanished from Gale crater. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

E.B. Rampe↗

Air Monitoring for Hazardous Gas Detection

The Hazardous Gas Detection Lab is involved in the design and development of instrumentation that can detect and quantify various hazardous gases. Traditionally these systems are designed for leak detection of the cryogenic gases used for the propulsion of the Shuttle and other vehicles. Mass spectrometers are the basis of these systems, which provide excellent quantitation, sensitivity, selectivity, response and limits of detection. Unfortunately, these systems are large, heavy and expensive. This feature limits the ability to perform gas analysis in certain applications. Smaller and lighter mass spectrometer systems could be used in many more applications primarily due to the portability of the system. Such applications would include air analysis in confined spaces, in-situ environmental analysis and emergency response. In general, system cost is lowered as size is reduced. With a low cost air analysis system, several systems could be utilized for monitoring large areas. These networked systems could be deployed at job-sites for worker safety, throughout a community for pollution warnings, or dispersed in a battlefield for early warning of chemical or biological threats. Presented will be information on the first prototype of this type of system. Included will be field trial data, with this prototype performing air analysis autonomously from an aircraft.

Arkin, C. Richard↗

An airborne compatible photofragmentation two-photon laser-induced fluorescence instrument for measuring background tropospheric levels of NO, NO(x), and NO2

The operating principle, design, and performance of a two-photon LIF (TP-LIF) sensor for simultaneous measurements of NO, NO(x) (NO + NO2), and NO2 are described. In this instrument, NO is first measured by direct spectroscopic TP-LIF detection; NO2 is converted to NO by photofragmentation using an XeF excimer laser operating at 353 nm; and the resulting NO is then detected quantitatively by TP-LIF. The detection limits of the instrument are found to be 3.5 parts per trillion by volume (pptv) of NO and 10 pptv for NO2, with integration times of 2 and 6 min, respectively. The in-flight performance of the instrument was evaluated during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 program in summer 1986, as reported by Gregory et al. (1990).

Sandholm, S. T.↗

Air Monitoring for Hazardous Gas Detection

The Hazardous Gas Detection Lab (HGDL) at Kennedy Space Center is involved in the design and development of instrumentation that can detect and quantify various hazardous gases. Traditionally these systems are designed for leak detection of the cryogenic gases used for the propulsion of the Shuttle and other vehicles. Mass spectrometers are the basis of these systems, which provide excellent quantitation, sensitivity, selectivity, response times and detection limits. A Table lists common gases monitored for aerospace applications. The first five gases, hydrogen, helium, nitrogen, oxygen, and argon are historically the focus of the HGDL.

Arkin, C. Richard↗

A Sensitive Quantitative Analysis of Abiotically Synthesized Short Homopeptides using Ultraperformance Liquid Chromatography and Time-of-Flight Mass Spectrometry

In the origins of life field understanding the abiotic polymerization of simple organic monomers (e.g., amino acids) into larger biomolecules (e.g., oligopeptides), remains a seminal challenge. Recently, preliminary observations showed a limited set of peptides formed in the presence of the plausible prebiotic phosphorylating agent, diamidophosphate (DAP), highlighting the need for an analytical tool to critically evaluate the ability of DAP to induce oligomerization of simple organics under aqueous conditions. However, performing accurate and precise, targeted analyses of short oligopeptides remains a distinct challenge in the analytical chemistry field. Here, we developed a new technique to detect and quantitate amino acids and their homopeptides in a single run using ultraperformance liquid chromatography-fluorescence detection/time of flight mass spectrometry. Over an 8-minute retention time window, 18 target analytes were identified and quantitated, 16 of which were chromatographically separated at, or near baseline resolution. Compound identity was confirmed by accurate mass analysis using a 10 ppm mass tolerance window. This method featured limits of detection < 5 nM (< 1 fmol on column) and limits of quantitation (LOQs) <15 nM (< 3 fmol on column). The LODs and LOQs were upwards of ∼28x and ∼788x lower, respectively, than previous methods for the same analytes, highlighting the quantifiable advantages of this new method. Both detectors provided good quantitative linearity (R(exp 2) > 0.985) for all analytes spanning concentration ranges ∼3 - 4 orders of magnitude. We performed a series of laboratory experiments to investigate DAP-mediated oligomerization of amino acids and peptides and analyzed experimental products with the new method. DAP readily polymerized amino acids and peptides under a range of simulated environmental conditions. This research underscores the potential of DAP to have generated oligopeptides on the primordial Earth, enhancing prebiotic chemical diversity and complexity at or near the origin of life.

Prebiotic Chemistry and Analytical Chemistry↗

Routine detection of Epstein-Barr virus specific T-cells in the peripheral blood by flow cytometry

The ability to detect cytomegalovirus-specific T-cells (CD4(+)) in the peripheral blood by flow cytometry has been recently described by Picker et al. In this method, cells are incubated with viral antigen and responding (cytokine producing) T-cells are then identified by flow cytometry. To date, this technique has not been reliably used to detect Epstein-Barr virus (EBV)-specific T-cells primarily due to the superantigen/mitogenic properties of the virus which non-specifically activate T-cells. By modifying culture conditions under which the antigens are presented, we have overcome this limitation and developed an assay to detect and quantitate EBV-specific T-cells. The detection of cytokine producing T-cells by flow cytometry requires an extremely strong signal (such as culture in the presence of PMA and ionomycin). Our data indicate that in modified culture conditions (early removal of viral antigen) the non-specific activation of T-cells by EBV is reduced, but antigen presentation will continue uninhibited. Using this method, EBV-specific T-cells may be legitimately detected using flow cytometry. No reduction in the numbers of antigen-specific T-cells was observed by the early removal of target antigen when verified using cytomegalovirus antigen (a virus with no non-specific T-cell activation properties). In EBV-seropositive individuals, the phenotype of the EBV-specific cytokine producing T-cells was evaluated using four-color flow cytometry and found to be CD45(+), CD3(+), CD4(+), CD45RA(-), CD69(+), CD25(-). This phenotype indicates the stimulation of circulating previously unactivated memory T-cells. No cytokine production was observed in CD4(+) T-cells from EBV-seronegative individuals, confirming the specificity of this assay. In addition, the use of four color cytometry (CD45, CD3, CD69, IFNgamma/IL-2) allows the total quantitative assessment of EBV-specific T-cells while monitoring the interference of EBV non-specific mitogenic activity. This method may have significant utility for the monitoring of the immune response to latent virus infection/reactivation.

Non-NASA Center↗

Determination of H2O and CO2 concentrations in fluid inclusions in minerals using laser decrepitation and capacitance manometer analysis

Water and carbon dioxide concentrations within individual and selected groups of fluid inclusions in quartz were analyzed by using laser decrepitation and quantitative capacitance manometer determination. The useful limit of detection (calculated as ten times the typical background level) is about 5 x 10(-10) mol of H2O and 5 x 10(-11) mol of CO2; this H2O content translates into an aqueous fluid inclusion approximately 25 micrometers in diameter. CO2/H2O determinations for 38 samples (100 separate measurements) have a range of H2O amounts of 5.119 x 10(-9) to 1.261 x 10(-7) mol; CO2 amounts of 7.216 x 10(-10) to 1.488 x 10(-8) mol, and CO2/H2O mole ratios of 0.011 to 1.241. Replicate mole ratio determinations of CO2/H2O for three identical (?) clusters of inclusions in quartz have average mole ratios of 0.0305 +/- 0.0041 1 sigma. Our method offers much promise for analysis of individual fluid inclusions, is sensitive, is selective when the laser energy is not so great as to melt the mineral (laser pits approximately 50 micrometers in diameter), and permits rapid analysis (approximately 1 h per sample analysis).

Water/analysis↗

Clear-Sky Remote Sensing in the Vicinity of Clouds: What Can Be Learned About Aerosol Changes?

Studies on aerosol direct and indirect effects require a precise separation of cloud-free and cloudy air. However, separation between cloud-free and cloudy areas from remotely-sensed measurements is ambiguous. The transition zone in the regions around clouds often stretches out tens of km, which are neither precisely clear nor precisely cloudy. We study the transition zone between cloud-free and cloudy air using MODerate-resolution Imaging Spectroradiometer (MODIS) and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) measurements. Both instruments show enhanced clear-sky reflectance (MODIS) and clear-sky backscatterer (CALIPSO) near clouds. Analyzing a large dataset of MODIS observations we examine the effect of three-dimensional (3D) radiative interactions between clouds and cloud-free areas, also known as a cloud adjacency effect. Comparing with CALIPSO clear-sky backscatterer measurements, we show that the cloud adjacency effect may be responsible for a large portion of the enhanced clear sky reflectance observed by MODIS. While aerosol particles are responsible for a large part of the near-cloud enhancements in CALIPSO observations, misidentified or undetected cloud particles are also likely to contribute. As a result, both the nature of these particles (cloud vs. aerosol) and the processes creating them need to be clarified using a quantitative assessment of remote sensing limitations in particle detection and identification. "The width and ubiquity of the transition zone near clouds imply that studies of-aerosol-cloud -interactions and aerosol direct radiative effects need to account for aerosol changes near clouds. Not accounted, these changes can cause systematic biases toward smaller aerosol radiative forcing. On the other hand, including aerosol products near clouds despite their uncertainties may overestimate aerosol radiative forcing. Therefore, there is an urgent need for developing methods that can assess and account for remote sensing challenges and thus allow for including the transition zone into the study. We describe a simple model that estimates the cloud-induced enhanced reflectances of cloud-free areas in the vicinity of clouds. The model assumes that the enhancement is due entirely to Rayleigh scattering and is therefore bigger at shorter wavelengths, thus creating a so-called apparent "bluing" of aerosols in remote sensing retrievals.

Marshak, Alexander↗

Clear-Sky Remote Sensing in the Vicinity of Clouds: What We Learned from MODIS and CALIPSO

Studies on aerosol direct and indirect effects require a precise separation of cloud-free and cloudy air. However, separation between cloud-free and cloudy areas from remotely-sensed measurements is ambiguous. The transition zone in the regions around clouds often stretches out tens of km, which are neither precisely clear nor precisely cloudy. We study the transition zone between cloud-free and cloudy air using MODerate-resolution Imaging Spectroradiometer (MODIS) and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) measurements. Both instruments show enhanced clear-sky reflectance (MODIS) and clear-sky backscatterer (CALIPSO) near clouds, Analyzing a large dataset of MODIS observations we examine the effect of three-dimensional (3D) radiative interactions between clouds and cloud-free areas, also known as a cloud adjacency effect. Comparing with CALIPSO clear-sky backscatterer measurements, we show that the cloud adjacency effect may be responsible for a large portion of the enhanced clear sky reflectance observed by MODIS. While aerosol particles are responsible for a large part of the near-cloud enhancements in CALIPSO observations, misidentified or undetected cloud particles are also likely to contribute. As a result, both the nature of these particles (cloud vs. aerosol) and the processes creating them need to be clarified using a quantitative assessment of remote sensing limitations in particle detection and identification. The width and ubiquity of the transition zone near clouds imply that studies of aerosol-cloud interactions and aerosol direct radiative effects need to account for aerosol changes near clouds. Not accounted, these changes can cause systematic biases toward smaller aerosol radiative forcing. On the other hand, including aerosol products near clouds despite their uncertainties may overestimate aerosol radiative forcing. Therefore, there is an urgent need for developing methods that can assess and account for remote sensing challenges and thus allow for including the transition zone into the study. We describe a simple model that estimates the cloud-induced enhanced reflectances of cloud-free areas in the vicinity of clouds. The model assumes that the enhancement is due entirely to Rayleigh scattering and is therefore bigger at shorter wavelengths, thus creating a so-called apparent "bluing" of aerosols in remote sensing retrievals.

Marshak, Alexander↗

Planar Rayleigh scattering results in helium-air mixing experiments in a Mach-6 wind tunnel

Planar Rayleigh scattering measurements with an argon-fluoride excimer laser are performed to investigate helium mixing into air at supersonic speeds. The capability of the Rayleigh scattering technique for flow visualization of a turbulent environment is demonstrated in a large-scale, Mach-6 facility. The detection limit obtained with the present setup indicates that planar, quantitative measurements of density can be made over a large cross-sectional area (5 cm x 10 cm) of the flow field in the absence of clusters.

Shirinzadeh, B.↗

Planar Rayleigh Scattering Results in Helium/Air Mixing Experiments in a Mach 6 Wind Tunnel

Planar Rayleigh scattering measurements using an ArF-excimer laser have been performed to investigate helium mixing into air at supersonic speeds. The capability of the Rayleigh scattering technique for flow visualization of a turbulent environment is demonstrated in a large-scale, Mach 6facility. The detection limit obtained with the present setup indicates that planar, quantitative measurements of density can be made over a large cross sectional area (5 cm by 10 cm) of the flow field in the absence of clusters.

Shirinzadeh, B.↗