Absolute Concentration Measurements Research Articles

Velocity And Concentration Measurements Of Supersonic Underexpanded Jets

The release of high-speed gas jets due to a tank leakage can pose a substantial safety hazard, as it can give rise to flammable, explosive, or toxic mixtures. Hence, understanding jet dispersion in real-world conditions is crucial for designing effective safety measures. Existing targeted or traceable studies provide velocity field data, but limitations in source-driven-pressures, nozzle geometries, or cross-flow conditions restrict their representativeness under real conditions. Indeed, an exhaustive experimental dataset for supersonic underexpanded gas jet dispersion under the influence of an Atmospheric Boundary Layer (ABL) is currently lacking. As part of a collaboration with the CEA, the von Karman Institute is continuing research efforts towards the development of high quality nonintrusive, optical measurement techniques for the characterization of the velocity and the concentration of a supersonic underexpanded jet submitted to different cross-flow conditions. The research explicitly targets measurements far from the release point within the self-similar region. Such measurements have already been tried on a supersonic jet without cross-flow and with a uniform velocity low-speed cross-flow [2], but never under the influence of an ABL. By filling this gap, the objective of the present work is to further improve the dispersion characterization by combining different techniques, such as Laser Mie Scattering and Light Extinction Spectroscopy (LES). To evaluate the dispersion within the self-similar region up to x/D ≈ 100, a significant FOV 1 is required. Therefore, Large-Scale Particle Image Velocimetry (LS-PIV) has been adapted and successfully applied to measure the velocity field. Prominent results have been obtained and comparable to standard PIV measurements. The pronounced variation in velocity magnitude observed while transitioning from the potential core to the self-similar region requires collecting multiple datasets to cover the broad spectrum of velocities comprehensively. A Mie scattering theory-based technique has been used to retrieve a relative concentration field. It is a non-intrusive technique that operates on the same experimental images produced by the LS-PIV campaign, assuming that light scattered by particles within a specific volume is proportional to the number of particles within this volume. The algorithm for concentration retrieval was adapted from and consequently improved for the present case. Discrepancies in the scaled concentration evolution among different nozzle diameters highlighted the necessity for refining the technique. This emphasizes accurately determining the reference concentration in a region free from intricate phenomena such as multiple scattering. The absolute and independent concentration measurement is done via Light Extinction Spectroscopy (LES). The LES technique measures the transmittance spectrum T of a collimated light beam passing through the particle-laden flow. This method has successfully been applied to several types of flows with similar seeding particles and concentration quantities (e.g. PSD 2 ). The extrapolation of absolute concentration parameters relies on the regularized solution of an ill-conditioned inverse problem. This solution is derived using the transmittance recorded during the test as the primary input parameter. The system to solve exhibits high sensitivity to small perturbations, making it challenging to employ numerical techniques confidently. Due to the substantial impact of minor perturbations in initial conditions on the system solution, a meticulous adaptation of the technique to the demands of compressible flows is necessary and still ongoing. The setup consists of a Deuterium-Tungsten Halogen UV-NIR light source emitting a divergent beam of light towards a 90◦ off-axis parabolic mirror, which collimates and deviates it into a beam to the jet. After passing through the jet, the resulting attenuated light beam goes into a collector mirror, redirecting it into a composite grating spectrometer UV-NIR with a 200 − 1100 nm wavelength range with 0.5 nm optical resolution. The results will examine the dispersion pattern and feature in terms of velocity and concentration of a supersonic underexpanded jet produced by an upstream tank with total pressure ranging from 5 to 9 bar without cross-flows. The latter will provide a foundation for successive studies on supersonic underexpanded jets subjected to an ABL.

Comparing novel small-angle x-ray scattering approaches for absolute size and number concentration measurements of spherical SiO2 particles to established methods

Biomedical analytical applications, as well as the industrial production of high-quality nano- and sub-micrometre particles, require accurate methods to quantify the absolute number concentration of particles. In this context, small-angle x-ray scattering (SAXS) is a powerful tool to determine the particle size and concentration traceable to the Système international d’unités (SI). Therefore, absolute measurements of the scattering cross-section must be performed, which require precise knowledge of all experimental parameters, such as the electron density of solvent and particles, whereas the latter is often unknown. Within the present study, novel SAXS-based approaches to determine the size distribution, density and number concentrations of sub-micron spherical silica particles with narrow size distributions and mean diameters between 160 nm and 430 nm are presented. For the first-time traceable density and number concentration measurements of silica particles are presented and current challenges in SAXS measurements such as beam-smearing, poorly known electron densities and moderately polydisperse samples are addressed. In addition, and for comparison purpose, atomic force microscopy has been used for traceable measurements of the size distribution and single particle inductively coupled plasma mass spectrometry with the dynamic mass flow approach for the accurate quantification of the number concentrations of silica particles. The possibilities and limitations of the current approaches are critically discussed in this study.

Technical note: In situ U–Th–He dating by 4He ∕ 3He laser microprobe analysis

Abstract. In situ U–Th–He geochronology is a potentially disruptive technique that combines laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with laser microprobe noble gas mass spectrometry. Despite its potential to revolutionize (detrital) thermochronology, in situ U–Th–He dating is not widely used due to persistent analytical challenges. A major issue is that current in situ U–Th–He dating approaches require that the U, Th, and He measurements are expressed in units of molar concentration, in contrast with conventional methods, which use units of molar abundance. Whereas molar abundances can be reliably determined by isotope dilution, accurate concentration measurements are not so easy to obtain. In the absence of matrix-matched U–Th concentration standards and accurate He ablation pit measurements, the required molar concentration calculations introduce an uncertainty that is higher than the conventional method, an uncertainty that is itself difficult to accurately quantify. We present a solution to this problem by using proton-induced 3He as a proxy for ablation pit volume and by pairing samples with a standard of known U–Th–He age. Thus, the U–Th–He age equation can be solved using relative rather than absolute concentration measurements. Pilot experiments show that the new method produces accurate results. However, it is prone to overdispersion, which is attributed to gradients in the proton fluence. These gradients can be measured, and their effect can be removed by fixing the geometry of the sample and the standard during the proton irradiation.

Review of recent advances in frequency-domain near-infrared spectroscopy technologies [Invited

Over the past several decades, near-infrared spectroscopy (NIRS) has become a popular research and clinical tool for non-invasively measuring the oxygenation of biological tissues, with particular emphasis on applications to the human brain. In most cases, NIRS studies are performed using continuous-wave NIRS (CW-NIRS), which can only provide information on relative changes in chromophore concentrations, such as oxygenated and deoxygenated hemoglobin, as well as estimates of tissue oxygen saturation. Another type of NIRS known as frequency-domain NIRS (FD-NIRS) has significant advantages: it can directly measure optical pathlength and thus quantify the scattering and absorption coefficients of sampled tissues and provide direct measurements of absolute chromophore concentrations. This review describes the current status of FD-NIRS technologies, their performance, their advantages, and their limitations as compared to other NIRS methods. Significant landmarks of technological progress include the development of both benchtop and portable/wearable FD-NIRS technologies, sensitive front-end photonic components, and high-frequency phase measurements. Clinical applications of FD-NIRS technologies are discussed to provide context on current applications and needed areas of improvement. The review concludes by providing a roadmap toward the next generation of fully wearable, low-cost FD-NIRS systems.

Water vapor in hydrogen flames measured by time-resolved collisional dephasing of the pure-rotational N2 CARS signal

We present a novel diagnostic technique to probe water vapor (H2O) concentration in hydrogen (H2) combustion environments via the time-resolved measurement of the collisional dephasing of the pure-rotational coherent anti-Stokes Raman scattering (CARS) signal of nitrogen (N2). The rotational Raman coherence of the N2 molecules, induced by the interaction with the pump and Stokes laser fields, dephases on a timescale of hundreds of picoseconds (ps), mostly due to inelastic collisions with other molecules in atmospheric flames. In the spatial region of H2 flames where H2O is present in appreciable amount, it introduces a faster dephasing of the N2 coherence than the other major combustion species do: we use time-resolved femtosecond/picosecond (fs/ps) CARS to deduce the H2O mole fraction from the dephasing effect of its inelastic collisions with N2. The proof-of-principle is demonstrated in a laminar H2/air diffusion flame, performing sequential measurements of the collisional dephasing of the N2 CARS signal up to 360 ps. We measure the temperature and the relative O2/N2 and H2/N2 concentrations at a short probe delay, and input the results in the time-domain model to extract the H2O mole fraction from the signal decay, thus measuring the whole scalar flow fields across the flame front. We furthermore present single-shot simultaneous thermometry and absolute concentration measurements in the turbulent TU Darmstadt/DLR Stuttgart canonical ‘H3 flame’ performed by dual-probe CARS measurements obtained with a polarization separation approach. This allows us to probe the molecular coherence simultaneously at ∼20 and ∼250 ps on the basis of a single-laser-shot, and record the resulting signals in two distinct detection channels of our unique polarization-sensitive coherent imaging spectrometer. The proposed technique allows for measuring the absolute concentrations of all the major species of H2 flames, thus providing a full characterization of the flow composition, as well as of the temperature field.

Mid-infrared absorption spectroscopic sensor for simultaneous and in-situ measurements of ammonia, water and temperature

A mid-infrared laser-based absorption sensor is developed for in-situ and simultaneous detection of ammonia, water and temperature for selective catalytic reduction (SCR) exhaust monitoring. The sensor used a quantum cascade laser (QCL) to target the NH3 line at 1103.45 cm−1 and a distributed-feedback (DFB) laser for H2O concentration and temperature by exploiting the line pair at 4029.52 cm−1 and 4029.78 cm−1. The time-division multiplexing (TDM) strategy was implemented to fulfill the H2O and temperature measurement with direct absorption spectroscopy (DAS) and the absolute concentration measurement of NH3 by calibration-free wavelength modulation spectroscopy (CF-WMS). All the experiments were conducted in a test chamber with a controlled temperature range of 296–673 K and pressure of 1 atm. The NH3 sensor was validated to achieve the detection limit of 7 ppb at the integration time of 100 s. The temperature measurement was also verified to show an uncertainty less than 3.5 %. We further performed the multi-parameter (NH3, H2O and temperature) measurement under the static condition and gas flowing condition, respectively. Our sensor successfully captured the time-varying species concentrations and temperature with a time resolution of 2.3 s, which is promising for SCR monitoring in terms of accuracy, sensitivity, and time response.

EDNA-based detection of the invasive crayfish Pacifastacus leniusculus in streams with a LAMP assay using dependent replicates to gain higher sensitivity

LAMP assays are becoming increasingly popular in the field of invasive species detection but are still underused in eDNA-based monitoring. Here, we propose a LAMP assay designed to detect the North American crayfish species Pacifastacus leniusculus in water samples from streams. The presence of P. leniusculus was detected through this new LAMP assay in all but one of the nine sites sampled. No correlation was found between ddPCR absolute concentration measurements and the number of LAMP-positive technical replicates. However, we showed that using dependent technical replicates could significantly enhance the detection sensitivity of the LAMP assay. Applied to other assays, it could improve sensitivity and thus allow for a more efficient use of eDNA-based LAMP assays for invasive species detection in aquatic ecosystems.

Cascaded coherent anti‐Stokes Raman scattering for high‐sensitivity number density determination in the gas phase

AbstractCascaded coherent anti‐Stokes Raman scattering (CARS) signals can be efficiently generated from CARS signals when propagating collinearly with the pump/Stokes and probe beams. This effect can be seen as the CARS beam acting as the probe beam and being inelastically scattered a ‘second time’ from the Raman coherence induced along the focus of the pump/Stokes beam axis. Although much weaker, this additionally scattered signal co‐propagates with the CARS signal and may complicate the analysis of the CARS spectrum used for diagnostics in the gas phase. In particular, the occurrence of the cascaded CARS process needs to be taken into account analysing minor spectral signatures at relatively high number density of scattering molecules. Here we show how polarization control can be employed to generate CARS and cascaded CARS signals with orthogonal linear polarization and how, in this way, the cascaded CARS signals can be efficiently suppressed. However, instead of rejecting this signal, we collect both the generated CARS and cascaded CARS signals on the same detector frame, and we explore the use of these counterparts for absolute concentration measurements of the Raman‐active species. The cascaded CARS signal has exponential‐order higher sensitivity to the number density of the scattering molecules in the mixture. We demonstrate that the ratio of the CARS and the cascaded CARS signals is independent of the probe pulse energy in use, which can be a promising approach for wide‐range absolute concentration measurements in gas‐phase media.

Simultaneous H/D/T and 3He/4He absolute concentration measurements with an optical Penning gauge on JET

The Optical Penning (or Species-Selective Penning) Gauge technique is used for the measurement of the H2/D2/T2 fuel isotopic composition and He/D2 concentration in the neutralized particle exhaust of fusion devices. An Optical Penning detection system has already been used in JET during its first deuterium-tritium campaigns (DTE1) and has been chosen by ITER. Recent improvements to the sub-divertor diagnostic suite as well as the optical instrumentation, in preparation for the next DT campaign, have improved the optical throughput of the measurement and enabled 3He/D2 detection down to 0.1 %. For the first time, the 3He/4He isotopic ratio can be measured simultaneously with the H/D/T ratio. This technique is of particular interest for ion cyclotron resonance frequency (ICRF) heating scenarios.

Detailed experimental and kinetic modeling study of toluene/C2 pyrolysis in a single-pulse shock tube

Abstract A combined experimental and kinetic modeling study is carried out to explore the influences of acetylene and ethylene addition on the species formation from toluene pyrolysis. Experiments are conducted separately with four different argon-diluted binary toluene/C2 mixtures in a single pulse shock tube at a nominal pressure of 20 bar over a temperature range of 1150−1650 K. All the experimental mixtures contain about 100 ppm toluene and different amounts of C2 fuels (50, 216, 459 ppm acetylene and 516 ppm ethylene). Species concentrations as a function of the temperature are probed from the post-shock gas mixtures and analyzed through the gas chromatography/gas chromatography-mass spectrometry techniques. A kinetic model is developed, which successfully predicts the absolute species concentration measurements as well as the changes brought by the varied fuel compositions. With the neat fuel decomposition profiles as a reference, both fuel components exhibit increased reactivity in the pyrolysis of all studied binary mixtures, indicating the existence of obvious synergistic effects. In particular, such effects become more remarkable when increasing the initial acetylene concentration. This essentially results from the addition-elimination reaction of a toluene fuel radical and a C2 fuel molecule leading to a C9 molecule and a hydrogen atom. Indene is identified as the predominant C9 product in all studied cases, and its peak concentrations sharply increase with the initial acetylene contents in toluene-acetylene pyrolysis. On the other hand, indane, produced from the addition-elimination reaction between benzyl and ethylene, is only detected at trace levels in toluene/ethylene pyrolysis. This indicates a relatively weaker interaction between benzyl and ethylene, compared to that of benzyl and acetylene. Apart from the increased concentrations of hydrogen atoms and C9 aromatics, interactions between toluene and C2 fuels also directly result in a reduced level of C7 radicals in the reaction system. Overall, PAH species can be divided into two groups according to the way their peak concentrations varying with the initial fuel compositions. For those largely depending on benzyl reactions, such as bibenzyl, biphenylmethane, fluorene and phenanthrene, the peak concentrations decrease with the added C2 fuels. In contrast, increasing trends are observed in the peak concentrations of the PAHs which rely on indenyl as a precursor, including naphthalene, methyl-indene, benzofulvene and acenaphthalene.

Validation of the BD FACSPresto system for the measurement of CD4 T-lymphocytes and hemoglobin concentration in HIV-negative and HIV-positive subjects

This study aimed to compare the performance of the BD FACSPresto system with the conventional standard-of-care technologies for the measurement of absolute CD4 count (AbsCD4), CD4 percentage (CD4%) and total hemoglobin concentration (Hb) in capillary and venous blood samples of HIV-negative and HIV-positive subjects. A total of 1304 participants were included in this prospective cohort study. Both venous and capillary blood samples were analyzed using the BD FACSPresto system and the results were compared against the BD FACSCalibur for enumerating AbsCD4 and CD4% and Sysmex XT-4000i hematology analyzer for determining Hb levels. Method comparison studies were performed using Deming regression and Bland–Altman plots. The Deming regression analyses comparing the accuracy of the BD FACSPresto system with the reference standard technologies demonstrated a significant linear correlation between the AbsCD4, CD4%, and Hb values generated by the two platforms. The 95% CI of the slopes for AbsCD4, CD4%, and Hb levels were 0.94–0.99, 0.99–1.01 and 0.86–0.93, respectively (P < 0.001). Bland–Altman plots for AbsCD4, CD4%, and Hb levels demonstrated close agreement between the BD FACSPresto system and the reference standards for all study participants. The performance and accuracy of BD FACSPresto system was comparable to the reference standard technologies. The BD FACSPresto system can be used interchangeably with BD FACSCalibur platform for CD4 and Sysmex XT-4000i hematology analyzer for Hb concentrations in resource-limited settings thus, improving accessibility to point-of-care testing services.

Time-Dependent Apparent Increase in dd-cfDNA Percentage in Clinically Stable Patients Between One and Five Years Following Kidney Transplantation.

Donor-derived cell-free DNA (dd-cfDNA) is reportedly a valuable tool for graft surveillance following kidney transplantation (KTx). Possible changes in dd-cfDNA(%) reference values over time have not been evaluated. For long-term monitoring after KTx, changes in host cfDNA might represent a biasing factor in dd-cfDNA(%) determinations. Plasma samples were obtained (n = 929) 12-60 months after engraftment in a cross-sectional cohort of 303 clinically stable KTx recipients. Total cfDNA(copies/mL), dd-cfDNA(%), and dd-cfDNA(copies/mL) were determined using droplet-digital PCR. Stability of threshold values in these stable KTx recipients over time was assessed by 80th, 85th, and 90th quantile regression. Upper percentiles of total cfDNA showed a significant decline of -1902, -3589, and -4753 cp/mL/log(month) (P = 0.014, <0.001, and 0.017, respectively), resulting in increasing dd-cfDNA(%) percentiles by 0.25, 0.46, and 0.72%/log(month) (P = 0.04, 0.001, and 0.002, respectively), with doubling of the 85th percentile value by 5 years. In contrast, dd-cfDNA(cp/mL) was stable during the observation period (P = 0.52, 0.29, and 0.39). In parallel increasing white blood cell counts and decreasing tacrolimus concentrations over time were observed. After 5 years, the median total cfDNA was still 1.6-fold (P < 0.001) higher in KTx recipients than in healthy controls (n = 135) and 1.4-fold (P < 0.001) higher than patients with other medical conditions (n = 364). The time-dependent decrease of host cfDNA resulted in an apparent increase of dd-cfDNA fraction in stable KTx patients. For long-term surveillance, measurement of absolute dd-cfDNA concentrations appears to be superior to percentages to minimize false positive results.

Measurement of Absolute Concentration at the Subcellular Scale.

The concentration of a pharmaceutical drug or bioactive metabolite within the target organelle influences the effects elicited by the drug or metabolite. Although the relative concentrations of many compounds of interest within subcellular compartments have been measured, measurements of absolute concentrations in the organelle remain elusive. In this Perspective, we discuss a significant advance in using nano secondary ion mass spectrometry (nanoSIMS) to measure the absolute concentration of a 13C-labeled metabolite within secretory vesicles, as reported by Thomen et al. in the April issue of ACS Nano.

Spatiotemporal Subcellular Characterization of Absolute NADH Concentration Over the Dynamic Course of Metaphase, Anaphase, Telophase and Cytokinesis using the Phasor Approach to FLIM

Absolute concentration measurements of free and bound nicotinamide adenine dinucleotide hydride (NADH) using the phasor approach to fluorescence lifetime imaging microscopy (phasor FLIM) is a powerful method for discerning metabolic robustness in living cells with subcellular resolution. Cell cycle and metabolism are at the forefront of ongoing cancer research to explore new targets for cancer therapeutics. A key feature of cancer cells is continual mitotic division. Completion of mitosis ends with the progression of cells through metaphase, anaphase, telophase and cytokinesis. Each of these phases last approximately 3 minutes, presenting a large challenge for researchers to assess metabolism at these stages using available biochemical approaches. Using the phasor FLIM paired with Digital Frequency Domain (DFD) FLIM hardware, we spatiotemporally measure the absolute concentration of NADH (a measure of metabolic robustness) and free/bound NADH ratio (a measure of metabolic mode) in individual mitochondria of cells progressing from metaphase through cytokinesis. Our timelapse FLIM measurements of HeLa cells characterize the metabolic heterogeneity of mitochondria metabolism based on spatial location at the cell equator or spindle poles during the temporal progression of cells from metaphase through cytokinesis. We observe mitochondria NADH concentration and free/bound NADH at the spindle equator and pole correlate in early metaphase, but diverge starting late metaphase to early anaphase coinciding with onset of anaphase cell elongation. Our subcellular NADH FLIM analysis results support the existence of a spatiotemporal specific mechanism for mitochondria function during the course of cell division. Supported by NIGMS P41GM103540 to EG and MD.

2D-Infrared Spectroscopy of Proteins in Water: Using the Solvent Thermal Response as an Internal Standard.

Ultrafast two-dimensional infrared (2D-IR) spectra can now be obtained in a matter of seconds, opening up the possibility of high-throughput screening applications of relevance to the biomedical and pharmaceutical sectors. Determining quantitative information from 2D-IR spectra recorded on different samples and different instruments is however made difficult by variations in beam alignment, laser intensity, and sample conditions. Recently, we demonstrated that 2D-IR spectroscopy of the protein amide I band can be performed in aqueous (H2O) rather than deuterated (D2O) solvents, and we now report a method that uses the magnitude of the associated thermal response of H2O as an internal normalization standard for 2D-IR spectra. Using the water response, which is temporally separated from the protein signal, to normalize the spectra allows significant reduction of the impact of measurement-to-measurement fluctuations on the data. We demonstrate that this normalization method enables creation of calibration curves for measurement of absolute protein concentrations and facilitates reproducible difference spectroscopy methodologies. These advances make significant progress toward the robust data handling strategies that will be essential for the realization of automated spectral analysis tools for large scale 2D-IR screening studies of protein-containing solutions and biofluids.

A Wide-Range and Calibration-Free Spectrometer Which Combines Wavelength Modulation and Direct Absorption Spectroscopy with Cavity Ringdown Spectroscopy.

A wide-range, calibration-free tunable diode laser spectrometer is established by combining wavelength modulation and direct absorption spectroscopy (WM-DAS) with continuous wave cavity ringdown spectroscopy (CW-CRDS). This spectrometer combines the benefits of absolute concentration measurements, wide range, and high speed, using WM-DAS with enhanced noise reduction in CW-CRDS. The accurate baseline ringdown time, τ0, is calculated by the absorption peak (measured by WM-DAS) and the ringdown time containing gas absorption information (measured by CW-CRDS at the center wavelength of the spectral line). The gas concentration is obtained without measuring τ0 in real time, thus, greatly improving the measuring speed. A WM-DAS/CW-CRDS spectrometer at 1.57 μm for CO detection was assembled for experimental validation of the multiplexing scheme over a concentration ranging from 4 ppm to 1.09% (0.1 MPa, 298 K). The measured concentration of CO at 6374.406 cm−1 shows that the dynamic range of this tunable diode laser absorption spectrometer is extendable up to five orders of magnitude and the corresponding precision is improved. The measurement speed of this spectrometer can extend up to 10 ms, and the detection limit can reach 35 ppb within 25 s.

A new method to quantify mineral dust and other aerosol species from aircraft platforms using single-particle mass spectrometry

Abstract. Single-particle mass spectrometry (SPMS) instruments characterize the composition of individual aerosol particles in real time. Their fundamental ability to differentiate the externally mixed particle types that constitute the atmospheric aerosol population enables a unique perspective into sources and transformation. However, quantitative measurements by SPMS systems are inherently problematic. We introduce a new technique that combines collocated measurements of aerosol composition by SPMS and size-resolved absolute particle concentrations on aircraft platforms. Quantitative number, surface area, volume, and mass concentrations are derived for climate-relevant particle types such as mineral dust, sea salt, and biomass burning smoke. Additionally, relative ion signals are calibrated to derive mass concentrations of internally mixed sulfate and organic material that are distributed across multiple particle types. The NOAA Particle Analysis by Laser Mass Spectrometry (PALMS) instrument measures size-resolved aerosol chemical composition from aircraft. We describe the identification and quantification of nine major atmospheric particle classes, including sulfate–organic–nitrate mixtures, biomass burning, elemental carbon, sea salt, mineral dust, meteoric material, alkali salts, heavy fuel oil combustion, and a remainder class. Classes can be sub-divided as necessary based on chemical heterogeneity, accumulated secondary material during aging, or other atmospheric processing. Concentrations are derived for sizes that encompass the accumulation and coarse size modes. A statistical error analysis indicates that particle class concentrations can be determined within a few minutes for abundances above ∼10 ng m−3. Rare particle types require longer sampling times. We explore the instrumentation requirements and the limitations of the method for airborne measurements. Reducing the size resolution of the particle data increases time resolution with only a modest increase in uncertainty. The principal limiting factor to fast time response concentration measurements is statistically relevant sampling across the size range of interest, in particular, sizes D &lt; 0.2 µm for accumulation-mode studies and D &gt; 2 µm for coarse-mode analysis. Performance is compared to other airborne and ground-based composition measurements, and examples of atmospheric mineral dust concentrations are given. The wealth of information afforded by composition-resolved size distributions for all major aerosol types represents a new and powerful tool to characterize atmospheric aerosol properties in a quantitative fashion.

Effects of flame-plane wall impingement on diesel combustion and soot processes

This work aims to assess the effects of flame-wall impingement on the combustion and soot processes of diesel flames. For this work, experimental measurements were performed in a constant-volume combustion chamber (CVCC) at ambient conditions that are representative of compression-ignition engines. The characteristics of impinging and free flames were compared at two identical ambient and injector conditions (20.8 kg/m3 ambient density, 6 MPa ambient pressure, 1000 K bulk temperature, 15 and 10 vol% ambient O2 concentration, and 100 MPa injection pressure). To simulate flame-wall impingement, a flat plane steel wall, normal to the injector axis, was initially placed at 53 mm from nozzle, but was varied from 53 to 35 mm during the experiments. Under the test conditions of this work, it was found that wall impingement resulted in lower soot temperature and soot content, in addition to a loss of momentum for the wall jet. The results also revealed that decreasing impingement distance from the nozzle resulted in reduced soot temperature and soot level for the wall jet. The reduced soot content observed for the wall jet appeared to be mainly driven by enhanced mixing. Flame transparency modeling was also performed to assess the uncertainties of two-color measurements for flame-plane wall impingement. The analysis indicated that the derived soot temperature and concentration values would be affected by the actual temperature profiles, rendering the technique useful to reveal trends, but not reliable for absolute soot concentration measurements.

Longer Repetition Time Proton MR Spectroscopy Shows Increasing Hippocampal and Parahippocampal Metabolite Concentrations with Aging.

Previous magnetic resonance spectroscopy (MRS) studies have concluded that hippocampal and parahippocampal metabolite concentrations remain stable during healthy adult aging. However, these studies used short repetition times (TR ≤ 2seconds), which lead to incomplete longitudinal magnetization recovery, and thus, heavily T1 -weighted measurements. It is important to accurately characterize brain metabolites changes with age to enable appropriate interpretations of MRS findings in the context of neurodegenerative diseases. Our goal was to assess hippocampal brain metabolite concentrations in a large cohort of diversely aged healthy volunteers using a longer TR of 4 seconds. Left hippocampal MR spectra were collected from 38 healthy volunteers at 3T. Absolute metabolite concentrations were determined for total N-acetyl-aspartate (tNAA), total creatine (tCr), total choline (tCho), glutamate and glutamine (Glx), and myoinositol (mI). Individual partial correlations between each metabolite with age were assessed using demographic information and voxel compartmentation as confounders. Hippocampal tNAA, tCr, tCho, and mI all increased with age (NAA: R2 = .17, P = .041; tCr: R2 = .45, P = .0002; tCho: R2 = .37, P = .001; mI: R2 = .44, P = .0003). There were no relationships between age and signal to noise ratio, linewidth, or scan date, indicating the correlations were not confounded by spectral quality. Furthermore, we did not observe a trend with age in the voxel tissue compartmentations. We observed increases in hippocampal/parahippocampal metabolite concentrations with age, a finding that is in contrast to previous literature. Our findings illustrate the importance of using a sufficiently long TR in MRS to avoid T1 -relaxation effects influencing the measurement of absolute metabolite concentrations.

An Improved Method for Measuring Absolute Metabolite Concentrations in Small Biofluid or Tissue Samples.

The measurement of absolute metabolite concentrations in small samples remains a significant analytical challenge. This is particularly the case when the sample volume is only a few microliters or less and cannot be determined accurately via direct measurement. We previously developed volume determination with two standards (VDTS) as a method to address this challenge for biofluids. As a proof-of-principle, we applied VDTS to NMR spectra of polar metabolites in the hemolymph (blood) of the tiny yet powerful genetic model Drosophila melanogaster. This showed that VDTS calculation of absolute metabolite concentrations in fed versus starved Drosophila larvae is more accurate than methods utilizing normalization to total spectral signal. Here, we introduce paired VDTS (pVDTS), an improved VDTS method for biofluids and solid tissues that implements the statistical power of paired control and experimental replicates. pVDTS utilizes new equations that also include a correction for dilution errors introduced by the variable surface wetness of solid samples. We then show that metabolite concentrations in Drosophila larvae are more precisely determined and logically consistent using pVDTS than using the original VDTS method. The refined pVDTS workflow described in this study is applicable to a wide range of different tissues and biofluids.