Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH_3OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH_3OOH with CF_3O− clustering chemistry. CH_3OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H_2O is ±80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H_2O is estimated to be better than ±40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements

Ionization-induced asymmetric self-phase modulation and universal modulational instability in gas-filled hollow-core photonic crystal fibers

We study theoretically the propagation of relatively long pulses with ionizing intensities in a hollow-core photonic crystal fiber filled with a Raman-inactive gas. Due to photoionization, previously unknown types of asymmetric self-phase modulation and `universal' modulational instabilities existing in both normal and anomalous dispersion regions appear. We also show that it is possible to spontaneously generate a plasma-induced continuum of blueshifting solitons, opening up new possibilities for pushing supercontinuum generation towards shorter and shorter wavelengths.Comment: 5 pages, 4 figure

How variable is mixing efficiency in the abyss?

Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 47 (2020): e2019GL086813, doi: 10.1029/2019GL086813.Mixing efficiency is an important turbulent flow property in fluid dynamics, whose variability potentially affects the large‐scale ocean circulation. However, there are several confusing definitions. Here we compare and contrast patch‐wise versus bulk estimates of mixing efficiency in the abyss by revisiting data from previous extensive field surveys in the Brazil Basin. Observed patch‐wise efficiency is highly variable over a wide range of turbulence intensity. Bulk efficiency is dominated by rare extreme turbulence events. In the case where enhanced near‐bottom turbulence is thought to be driven by breaking of small‐scale internal tides, the estimated bulk efficiency is 20%, close to the conventional value of 17%. On the other hand, where enhanced near‐bottom turbulence appears to be convectively driven by hydraulic overflows, bulk efficiency is suggested to be as large as 45%, which has implications for a further significant role of overflow mixing on deep‐water mass transformation.TI is a JSPS Overseas Research Fellow. LS, KLP, and JMT acknowledge support from the U.S. National Science Foundation and Office of Naval Research. The authors express their gratitude to Ali Mashayek and an anonymous reviewer for their useful comments on the original manuscript. Data used in this study is available from the Woods Hole Open Access Server (https://hdl.handle.net/1912/25456).2020-09-2

Enhanced diapycnal diffusivity in intrusive regions of the Drake Passage

Author Posting. © American Meteorological Society, 2016. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Physical Oceanography 46 (2016): 1309-1321, doi:10.1175/JPO-D-15-0068.1.Direct measurements of oceanic turbulent parameters were taken upstream of and across Drake Passage, in the region of the Subantarctic and Polar Fronts. Values of turbulent kinetic energy dissipation rate ε estimated by microstructure are up to two orders of magnitude lower than previously published estimates in the upper 1000 m. Turbulence levels in Drake Passage are systematically higher than values upstream, regardless of season. The dissipation of thermal variance χ is enhanced at middepth throughout the surveys, with the highest values found in northern Drake Passage, where water mass variability is the most pronounced. Using the density ratio, evidence for double-diffusive instability is presented. Subject to double-diffusive physics, the estimates of diffusivity using the Osborn–Cox method are larger than ensemble statistics based on ε and the buoyancy frequency.This work was supported by grants from the U.S. National Science Foundation.2016-10-0

Evaluating salt-fingering theories

Author Posting. © Sears Foundation for Marine Research, 2008. This article is posted here by permission of Sears Foundation for Marine Research for personal use, not for redistribution. The definitive version was published in Journal of Marine Research 66 (2008): 413-440, doi:10.1357/002224008787157467.The NATRE fine- and microstructure data set is revisited to test salt-finger amplitude theories. Dependences of the mixing efficiency Γ, microscale buoyancy Reynolds number Re and thermal Cox number CxT on 5-m density ratio Rρ and gradient Richardson number Ri are examined. The observed mixing efficiency is too high to be explained by linear fastest-growing fingers but can be reproduced by wavenumbers 0.5-0.9 times lower than the fastest-growing wavenumber. Constraining these fingers with a hybrid wave/finger Froude number or a finger Reynolds number cannot reproduce the observed trends with Rρ or Ri, respectively. This suggests that background shear has no influence on finger amplitudes. Constraining average amplitudes of these lower-wavenumber fingers with finger Richardson number Rif ~ 0.2 reproduces the observed dependence of Re and CxT on density ratio Rρ and Ri at all but the lowest observed density ratio (Rρ = 1.3). Separately relaxing the assumptions of viscous control, dominance of a single mode and tall narrow fingers does not explain the difference between theory and data at low Rρ for a critical Rif ~ 0.2.We gratefully acknowledge the support of the Office of Naval Research (grant N00014-04-1-0212) and Natural Sciences and Engineering Research Council of Canada

Quantification of diastolic dysfunction via the age dependence of diastolic function — Impact of insulin resistance with and without type 2 diabetes

AbstractBackgroundThe alarming prevalence of heart failure with preserved ejection fraction requires quantification of diastolic dysfunction (DDF). Myocardial diastolic velocity E′ implies that age is the most important determinant. We tested the hypothesis that age allows for quantification of DDF and assessment of the structural and metabolic determinants in patients with and without type 2 diabetes (D).MethodsThis prospective, cross-sectional study assessed cardiovascular, metabolic and ultrasound data in 409 consecutive patients (Diabetes Center, Bogenhausen-Munich) between 20 and 90years without known cardiac disease and either with (n=204) or without D but with common prevalence of cardiovascular risk factors, including a subgroup of healthy individuals (H, n=94).ResultsIn H, E′ related to age as: E′norm=−0.163∗years+19.69 (R2=0.77, p<0.0001). According to this 1% reduction by annual physiologic aging, DDF was quantitated as E′−E′ norm. Compared to nondiabetics, D patients were older, had greater BMI, lower E′, more cardiovascular risk and greater DDF. In nondiabetics, grading of DDF by E−E′norm correlated with grading by filling pressure E/E′. Determinants of DDF by multivariate analysis included pulse wave velocity, diastolic blood pressure and the triglyceride/HDL ratio (a marker of insulin resistance) in nondiabetics and in D the same risk factors in reverse sequence and heart rate. Neither left atrial size nor left ventricular mass had significant impact.ConclusionsThe physiological impact of age on myocardial function consists of a 1% annual reduction in E′ and enables precise quantification of diastolic dysfunction thereby unmasking the importance of metabolic risk for DDF

Vertical kinetic energy and turbulent dissipation in the ocean

© The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geophysical Research Letters 42 (2015): 7639–7647, doi:10.1002/2015GL065043.Oceanic internal waves are closely linked to turbulence. Here a relationship between vertical wave number (kz) spectra of fine-scale vertical kinetic energy (VKE) and turbulent dissipation ε is presented using more than 250 joint profiles from five diverse dynamic regimes, spanning latitudes between the equator and 60°. In the majority of the spectra VKE varies as inline image. Scaling VKE with inline image collapses the off-equatorial spectra to within inline image but underestimates the equatorial spectrum. The simple empirical relationship between VKE and ε fits the data better than a common shear-and-strain fine-scale parameterization, which significantly underestimates ε in the two data sets that are least consistent with the Garrett-Munk (GM) model. The new relationship between fine-scale VKE and dissipation rate can be interpreted as an alternative, single-parameter scaling for turbulent dissipation in terms of fine-scale internal wave vertical velocity that requires no reference to the GM model spectrum.National Science Foundation Grant Numbers: OCE-0728766, OCE-0425361, OCE-0424953, OCE-1029722, OCE-0622630, OCE-1030309, OCE-1232962, and Office of Naval Research Grant Number: N00014-10-1031

Construction and Assembly of the Wire Planes for the MicroBooNE Time Projection Chamber

In this paper we describe how the readout planes for the MicroBooNE Time Projection Chamber were constructed, assembled and installed. We present the individual wire preparation using semi-automatic winding machines and the assembly of wire carrier boards. The details of the wire installation on the detector frame and the tensioning of the wires are given. A strict quality assurance plan ensured the integrity of the readout planes. The different tests performed at all stages of construction and installation provided crucial information to achieve the successful realisation of the MicroBooNE wire planes.Comment: 24 pages, 22 figures, accepted for publication as Technical Report in JINS

Why do models overestimate surface ozone in the Southeast United States

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx  ≡  NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°  ×  0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer