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NASA NTRS2009

The First Detection of [O IV] from an Ultraluminous X-ray Source with Spitzer. I. Observational Results for Holmberg II ULX

We presen the first Spitzer Infrared Spectrograph (IRS) observations of the [O IV] 25.89 um emission line detected from the ultraluminous X-ray source (ULX) in Holmberg II. This line is a well established signature of high excitation usually associated with AGN. Its detection suggests that the ULX has a strong impact on the surrounding gas. A Spitzer high resolution spectral map shows that the [O IV] is coincident with the X-ray position of the ULX. The ratios of the [O IV] to lower ionization lines are similar to those observed in AGN, suggesting that a strong UV and X-ray source is responsible for the, photoionization. The best XMM-Newton data is used to model the X-ray band which is then extrapolated into the UV. We perform infrared and ultraviolet photometry, and use its previously published optical and radio data to construct the full SED for the ULX and its companion. The preferred model to describe the SED includes an accretion disk which dominates the soft X-rays but contributes little at UV and optical wavelengths. The optical counterpart is consistent with a B supergiant as previously suggested in other studies. The bolometric luminosity of the ULX suggests the presence of an intermediate-mass black hole with mass >85 M for sub-Eddington accretion or, alternatively, a stellar-mass black hole that is accreting at super-Eddington rates. In a follow-up second paper we perform detailed photoionization modeling of the infrared lines in order to constrain the bolometric luminosity of the ULX.

Berghea, C. T.↗

NASA NTRS2010

Chandra High Resolution Spectroscopy of the Circumnuclear Matter in the Broad Line Radio Galaxy, 3C 445

We present evidence for X-ray line emitting and absorbing gas in the nucleus of the Broad-Line Radio Galaxy (BLRG), 3C445. A 200 ks Chandra LETG observation of 3C 445 reveals the presence of several highly ionized emission lines in the soft X-ray spectrum, primarily from the He and H-like ions of O, Ne, Mg and Si. Radiative recombination emission is detected from O VII and O VIII, indicating that the emitting gas is photoionized. The He-like emission appears to be resolved into forbidden and intercombination line components, which implies a high density of greater than 10(sup 10) cm(sup -3), while the lines are velocity broadened with a mean width of 2600 km s(sup -1). The density and widths of the ionized lines indicate an origin of the gas on sub-parsec scales in the Broad Line Region (BLR). The X-ray continuum of 3C 445 is heavily obscured by a photoionized absorber of column density N(sub H) = 2 x 10(sup 23) cm(sup -2) and ionization parameter log xi = 1.4 erg cm s(sup -1). However the view of the X-ray line emission is unobscured, which requires the absorber to be located at radii well within any parsec scale molecular torus. Instead we suggest that the X-ray absorber in 3C 445 may be associated with an outflowing, but clumpy accretion disk wind, with an observed outflow velocity of approximately 10000 km s(sup -1).

Reeves, J. N.↗

NASA NTRS2012

Role of Massive Stars in the Evolution of Primitive Galaxies

An important factor controlling galaxy evolution is feedback from massive stars. It is believed that the nature and intensity of stellar feedback changes as a function of galaxy mass and metallicity. At low mass and metallicity, feedback from massive stars is mainly in the form of photoionizing radiation. At higher mass and metallicity, it is in stellar winds. IZw 18 is a local blue, compact dwarf galaxy that meets the requirements for a primitive galaxy: low halo mass greater than 10(exp 9)Msun, strong photoionizing radiation, no galactic outflow, and very low metallicity,log(O/H)+12=7.2. We will describe the properties of massive stars and their role in the evolution of IZw 18, based on analysis of ultraviolet images and spectra obtained with HST.

Heap, Sara↗

NASA NTRS2012

Solar Flare Impacts on Ionospheric Electrodynamics

The sudden increase of X-ray and extreme ultra-violet irradiance during flares increases the density of the ionosphere through enhanced photoionization. In this paper, we use model simulations to investigate possible additional contributions from electrodynamics, finding that the vertical E X B drift in the magnetic equatorial region plays a significant role in the ionosphere response to solar flares. During the initial stage of flares, upward E X B drifts weaken in the magnetic equatorial region, causing a weakened equatorial fountain effect, which in turn causes lowering of the peak height of the F2 region and depletion of the peak electron density of the F2 region. In this initial stage, total electron content (TEC) enhancement is predominantly determined by solar zenith angle control of photoionization. As flares decay, upward E X B drifts are enhanced in the magnetic equatorial region, causing increases of the peak height and density of the F2 region. This process lasts for several hours, causing a prolonged F2-region disturbance and TEC enhancement in the magnetic equator region in the aftermath of flares. During this stage, the global morphology of the TEC enhancement becomes predominantly determined by these perturbations to the electrodynamics of the ionosphere.

Qian, Liying↗

NASA NTRS2011

The Spectroscopic Evolution of the Symbiotic-like Recurrent Nova V407 Cygni During Its 2010 Outburst. 2. The Circumstellar Environment and the Aftermath

The nova outburst of V407 Cyg in 2010 Mar. 10 was the first observed for this star but its close resemblance to the well known symbiotic-like recurrent nova RS Oph suggests that it is also a member of this rare type of Galactic novae. The nova was the first detected at gamma-ray energies and is the first known nova explosion for this system. The extensive multiwavelength coverage of this outburst makes it an ideal comparison with the few other outbursts known for similar systems. We extend our previous analysis of the Mira and the expanding shock from the explosion to detail the time development of the photoionized Mira wind, circumstellar medium, and shocked circumstellar environment to derive their physical parameters and how they relate to large scale structure of the environment, extending the previous coverage to more than 500 days after outburst. We use optical spectra obtained at high resolution with the Nordic Optical Telescope (NOT) (R approx. =.45000 to 65000) and medium resolution Ondrejov Observatory (R approx. = 12000) data and compare the line variations with publicly available archival measurements at 30 GHz OVNR and at X-rays with Swift during the first four months of the outburst, through the end of the epoch of strong XR emission. We use nebular diagnostics and high resolution profile variations to derive the densities and locations of the extended emission. We find that the higher the ionization and/or the higher the excitation energy, the more closely the profiles resemble the He II/Ca V-type high velocity shock profile discussed in Paper I. This also accounts for the comparative development of the [N II] and [O III] isoelectronic transitions: the [O III] 4363A profile does not show the low velocity peaks while the excited [N II] 5754A does. If nitrogen is mainly N(+3) or higher in the shock, the upper state of the [N II] nebular lines will contribute but if the oxygen is O(+2) then this line is formed by recombination, masking the nebular contributor, and the lower states are collisionally quenched but emit from the low density surroundings. Absorption lines of Fe-peak ions formed in the Mira wind were visible as P Cyg profiles at low velocity before Day 69, around the time of the X-ray peak and we identified many absorption transitions without accompanying emission for metal lines. The H Balmer lines showed strong P Cyg absorption troughs that weakened during the 2010 observing period, through Day 128. The Fe-peak line profiles and flux variations were different for permitted and forbidden transitions: the E1 transitions were not visible after Day 128 but had shown a narrow peak superimposed on an extended (200 km/s) blue wing, while the M1 and E2 transitions persisted to Day 529, the last observation, and showed extended redshifted wings up of the same velocity. We distinguish the components from the shock, the photoionized environment, and the chromosphere and inner Mira wind using spectra taken more than one year after outburst. The multiple shells and radiative excitation phenomenology are similar to those recently cited for GRBs and SNIa .

Shore, S. N.↗

NASA NTRS2019

A Comprehensive Chandra Study of the Disk Wind in the Black Hole Candidate 4U 1630-472

The mechanisms that drive disk winds are a window into the physical processes that underlie the disk. Stellar-mass black holes are an ideal setting in which to explore these mechanisms, in part because their outbursts span a broad range in mass accretion rate. We performed a spectral analysis of the disk wind found in six Chandra/HETG observations of the black hole candidate 4U 1630−472, covering a range of luminosities over two distinct spectral states. We modeled both wind absorption and extended wind re-emission components using PION, a selfconsistent photoionized absorption model. In all but one case, two photoionization zones were required in order to obtain acceptable fits. Two independent constraints on launching radii, obtained via the ionization parameter formalism and the dynamical broadening of the re-emission, helped characterize the geometry of the wind. The innermost wind components (r ≃ 10(sup 2-3)GM/c(exp 2)) tend toward small volume filling factors, high ionization, densities up to n ≃ 10(sup 15-16) cm(exp -3), and outflow velocities of ∼0.003c. These small launching radii and large densities require magnetic driving, as they are inconsistent with numerical and analytical treatments of thermally driven winds. Outer wind components (r ≃ 10(exp 5)GM/c(exp 2)) are significantly less ionized and have filling factors near unity. Their larger launching radii, lower densities (n ≃ 10(exp 12) cm(exp -3)), and outflow velocities (∼0.0007c) are nominally consistent with thermally driven winds. The overall wind structure suggests that these components may also be part of a broader MHD outflow and perhaps better described as magneto-thermal hybrid winds.

Black hole physics↗

NASA NTRS2020

Origins of X-ray Line Emissions in Circinus X-1 at Very Low X-ray Flux

Accretion conditions and morphologies of X-ray transients containing neutron stars are still poorly understood. Circinus X-1 is an enigmatic case where we observe X-ray flux changes covering four orders of magnitude. We observed Circinus X-1 several times at its very lowest X-ray flux using the high-energy transmission grating spectrometer on board the Chandra X-ray Observatory. At a flux of 1.8 ´ 10-11 erg cm−2 s−1 we observed a single 1.6 keV blackbody spectrum. The observed continuum luminosity of 1035 erg s−1 is about two orders of magnitude too low to explain the observed photoionized luminosity, suggesting a much more complex structure of the X-ray source that is partially or entirely obscured, as had been previously suggested. This affects most emissions from the accretion disk, including previously observed accretion-disk coronal line emissions. Instead, the strongest observed photoionized lines are blueshifted by about ∼400 km s−1, and we suggest that they originate in the ionized wind of a B5Ia supergiant companion, supporting a previous identification. The neutron star in Cir X-1 is very young and should have a high magnetic field. At the observed luminosity, the emission radius of the blackbody is small enough to be associated with the accretion hot spot as the X-ray-emitting region. The small emission radius then points to a field strength below 1012 G, which would be consistent with the observation of occasional type I X-ray bursts at high magnetic fields. We discuss Cir X-1 in the context of being a high-mass X-ray binary, with some emphasis on a possible Be-star X-ray binary nature.

N S Schulz↗

NASA NTRS2021

Modeling Magnetic Disk Wind State Transitions in Black Hole X-Ray Binaries

We analyze three prototypical black hole X-ray binaries, 4U 1630–472, GRO J1655–40, and H1743–322, in an effort to systematically understand the intrinsic state transition of the observed accretion disk winds between wind-on and wind-off states by utilizing state-of-the-art Chandra/HETGS archival data from multi-epoch observations. We apply our magnetically driven wind models in the context of magnetohydrodynamic(MHD)calculations to constrain(1)their global density slope(p),(2)their density (n17) at the foot point of the inner most launching radius, and(3)the abundances of heavier elements(AFe,S,Si). Incorporating the MHD winds into xstar photoionization calculations in a self-consistent manner, we create a library of synthetic absorption spectra given the observed X-ray continua. Our analysis clearly indicates a characteristic bimodal transition of multi-ion X-ray winds; i.e., the wind density gradient is found to steepen(fro mp∼1.2–1.4 to∼1.4–1.5)while its density normalization declines as the source transitions from the wind-onto the wind-off state. The model implies that the ionized wind remains physically present even in the wind-off state, despite its apparent absence in the observed spectra. Super solar abundances for heavier elements are also favored. Our global multi-ion wind models, taking into account soft X-ray ions as well as Fe K absorbers, show that the internal wind condition plays an important role in wind transitions besides photoionization changes. Simulated XRISM/Resolve and Athena/X-IFU spectra are presented to demonstrate a high fidelity of the multi-ion wind model for a better understanding of these powerful ionized winds in the coming decades

Keigo Fukumura↗

NASA NTRS2023

The Variable Detection of Atmospheric Escape around the Young, Hot Neptune AU Mic b

Photoevaporation is a potential explanation for several features within exoplanet demographics. Atmospheric escape observed in young Neptune-sized exoplanets can provide insight into and characterize which mechanisms drive this evolution and at what times they dominate. AU Mic b is one such exoplanet, slightly larger than Neptune (4.19 R ⊕ ). It closely orbits a 23 Myr pre-main-sequence M dwarf with an orbital period of 8.46 days. We obtained two visits of AU Mic b at Lyα with Hubble Space Telescope (HST)/Space Telescope Imaging Spectrograph. One flare within the first HST visit is characterized and removed from our search for a planetary transit. We present a nondetection in our first visit, followed by the detection of escaping neutral hydrogen ahead of the planet in our second visit. The outflow absorbed ∼30% of the star’s Lyα blue wing 2.5 hr before the planet’s white-light transit. We estimate that the highest-velocity escaping material has a column density of 10 13.96 cm −2 and is moving 61.26 km s −1 away from the host star. AU Mic b’s large high-energy irradiation could photoionize its escaping neutral hydrogen in 44 minutes, rendering it temporarily unobservable. Our time-variable Lyα transit ahead of AU Mic b could also be explained by an intermediate stellar wind strength from AU Mic that shapes the escaping material into a leading tail. Future Lyα observations of this system will confirm and characterize the unique variable nature of its Lyα transit, which, combined with modeling, will tune the importance of stellar wind and photoionization.

Exoplanets↗

DOE OSTI2017

Detection Identification and Quantification of Keto-Hydroperoxides in Low-Temperature Oxidation.

Keto-hydroperoxides are reactive partially oxidized intermediates that play a central role in chain-branching reactions during the low-temperature oxidation of hydrocarbons. In this Perspective, we outline how these short lived species can be detected, identified, and quantified using integrated experimental and theoretical approaches. The procedures are based on direct molecular-beam sampling from reactive environments, followed by mass spectrometry with single-photon ionization, identification of fragmentation patterns, and theoretical calculations of ionization thresholds, fragment appearance energies, and photoionization cross sections. Using the oxidation of neo-pentane and tetrahydrofuran as examples, the individual steps of the experimental approaches are described in depth together with a detailed description of the theoretical efforts. For neo-pentane, the experimental data are consistent with the calculated ionization and fragment appearance energies of the keto-hydroperoxide, thus adding confidence to the analysis routines and the employed levels of theory. For tetrahydrofuran, multiple keto-hydroperoxide isomers are possible due to the presence of nonequivalent O 2 addition sites. Despite this additional complexity, the experimental data allow for the identification of two to four keto-hydroperoxides. Mole fraction profiles of the keto-hydroperoxides, which are quantified using calculated photoionization cross sections, are provided together with estimated uncertainties as function of the temperature of the reactive mixture and can serve as validation targets for chemically detailed mechanisms.

Hansen, Nils↗

DOE OSTI2021

Shake loss intensities in x-ray photoelectron spectroscopy: Theory, experiment, and atomic composition accuracy for MgO and related compounds

The relative intensities of XPS core levels, scaled by their photoionization cross sections, are regularly used to determine sample atomic composition. Cross sections, however, give the intensity to all possible final states for the core ionizations, not just to the main peak. This includes all intrinsic satellite structure (shake states and, for open shell systems, the different ionic multiplets). In practice, for solids, this is usually experimentally impossible to determine accurately because such a satellite structure sits on the inelastically scattered electron background and cannot be easily separated. Therefore, usually, only the intensity of the main peak is used. This limits the ultimate possible accuracy of XPS composition determination. The purpose of the present paper is to examine the contributions that a theoretical analysis of losses of intensity can make to improve quantitation. For an MgO single crystal, we show that the correct stoichiometry of 1:1 can be recovered using the theoretical analysis of the experimental MgO peak ratio intensities. For materials with a sufficient bandgap for the XPS main peaks to be separated from the scattered background, the intensity of main peaks can often be accurately determined. Thus, if one uses theory to calculate that fraction of the total intensity lost from a main peak into all its satellite structure, the intensity of just main peaks could then be used to more accurately determine relative atom % composition. This work tests this approach using a single crystal MgO (50% Mg, 50% O) standard. Ab initio electronic structure theory of representative MgO clusters is used to determine Hartree–Fock wave functions for the ground state and final ionized states corresponding to the main Mg 2p and O1s XPS peaks of the oxide. The sudden approximation, SA, is used to determine the fractional losses from these main peaks to shake satellites, which is found to be greater for O1s than Mg2p. This results in predicted “apparent composition” for stoichiometric MgO of 55.2% Mg, 44.8% O instead of the true 50% Mg, 50% O. Equivalent theory for CaO results in a predicted apparent Ca value of 53.4%. Experimentally, using Mg2s or 2p intensity ratio to O1s, we find values between 52.2% and 56.0% Mg using two crystals and four different instrument electron pass energies. The average value of the measurements is 54.5% Mg when corrected for the presence of an adventitious carbon overlayer and slight surface hydroxide. Though this agreement with theory may be somewhat fortuitous, given the potential experimental errors, which are fully discussed, it is similar to that in our earlier study on LiF. We also present preliminary experimental data on Mg(OH) 2 and MgSO 4 , which show a similar trend of apparently higher than 50% Mg, but we have no theory values. We are not yet able to experimentally test for validation of the difference between apparent composition for MgO (55.2% Mg) and CaO (53.4% Ca), owing to significant carbonate formation at the surface of the single crystal CaO. Here, an important conclusion is that the theoretical determination of shake losses, obtained with ab initio wavefunctions and the SA, is likely to be a useful way to calibrate the accuracy and reliability of compositions obtained from XPS intensities and merits further study.

47 OTHER INSTRUMENTATION↗

DOE OSTI2017

A Simple Method for Improving the Spatial Resolution in Infrared Laser Ablation Mass Spectrometry Imaging

In mass spectrometry imaging of tissues, the size of structures that can be distinguished is determined by the spatial resolution of the imaging technique. Here, the spatial resolution of IR laser ablation is markedly improved by increasing the distance between the laser and the focusing lens. As the distance between the laser and the lens is increased from 1 to 18 m, the ablation spot size decreases from 440 to 44 μm. This way, only the collimated center of the divergent laser beam is directed on the focusing lens, which results in better focusing of the beam. Part of the laser energy is lost at longer distance, but this is compensated by focusing of the radiation to a smaller area on the sample surface. The long distance can also be achieved by a set of mirrors, between which the radiation travels before it is directed to the focusing lens and the sample. This method for improving the spatial resolution can be utilized in mass spectrometry imaging of tissues by techniques that utilize IR laser ablation, such as laser ablation electrospray ionization, laser ablation atmospheric pressure photoionization, and matrix-assisted laser desorption electrospray ionization. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2017

On the SIMS Ionization Probability of Organic Molecules

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α{sup +}) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10{sup −5}. Our lab has developed a method for the direct determination of α{sup +} in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C{sub 24}H{sub 12}), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C{sub 60} cluster projectiles is of the order of 10{sup −3}, with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2019

Design and Evaluation of a Gas Chromatograph-Atmospheric Pressure Chemical Ionization Interface for an Exactive Orbitrap Mass Spectrometer

Various separation and mass spectrometric (MS) techniques have furthered our ability to study complex mixtures, and the desire to measure every analyte in a system is of continual interest. For many complex mixtures, such as the total molecular content of a cell, it is becoming apparent that no one single separation technique or analysis is likely to achieve this goal. Therefore, having a variety of tools to measure the complexity of these mixtures is prudent. Orbitrap MSs are broadly used in systems biology studies due to their unique performance characteristics. However, GC-Orbitraps have only recently become available, and instruments that can use gas chromatography (GC) cannot use liquid chromatography (LC) and vice versa. This limits small molecule analyses, such as those that would be employed for metabolomics, lipidomics, or toxicological studies. Thus, a simple, temporary interface was designed for a GC and Thermo Scientific™ Ion Max housing unit. This interface enables either GC or LC separation to be used on the same MS, an Exactive™ Plus Orbitrap, and utilizes an atmospheric pressure chemical ionization (APCI) source. The GC-APCI interface was tested against a commercially available atmospheric pressure photoionization (APPI) interface for three types of analytes that span the breadth of typical GC analyses: fatty acid methyl esters (FAMEs), polyaromatic hydrocarbons (PAHs), and saturated hydrocarbons. The GC-APCI-Orbitrap had similar or improved performance to the APPI and other reported methods in that it had a lower limit of quantitation, better signal to noise, and lower tendency to fragment analytes. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2014

Radiative recombination data for tungsten ions: II. W{sup 47+}–W{sup 71+}

New radiative recombination and photoionization cross sections, radiative recombination rate coefficients, and radiated power loss rate coefficients are presented for 23 tungsten impurity ions in plasmas. We consider ions from W{sup 47+} to W{sup 71+} that are of importance to fusion studies for ITER and for experiments using electron beam ion traps. The calculations are fully relativistic and all significant multipoles of the radiative field are taken into account. The Dirac–Fock method is used to compute the electron wavefunctions. Radiative recombination rates and radiated power loss rates are found using the relativistic Maxwell–Jüttner distribution of the continuum electron velocity. The total radiative recombination cross sections are given in the electron energy range from 1 eV to ∼80keV. Partial cross sections for ground and excited states are approximated by an analytical expression involving five fit parameters. Radiative recombination rates and radiated power loss rates are calculated in the temperature range from 10{sup 4}K to 10{sup 9}K. The total radiative recombination rates are approximated by another analytical expression with four fit parameters.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2024

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

Additional chain-branching pathways in the low-temperature oxidation of branched alkanes

Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C 8 H 14 O 4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C 8 H 16 O 5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C 8 H 16 O 5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O 2 addition, intramolecular isomerization, and OH release; C 8 H 14 O 4 species are proposed to result from subsequent reactions of C 8 H 16 O 5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. Furthermore, the results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine

This paper identifies classes of cool flame intermediates from n-heptane low-temperature oxidation in a jet-stirred reactor (JSR) and a motored cooperative fuel research (CFR) engine. The sampled species from the JSR oxidation of a mixture of n-heptane/O 2 /Ar (0.01/0.11/0.88) were analyzed using a synchrotron vacuum ultraviolet radiation photoionization (SVUV-PI) time-of-flight molecular-beam mass spectrometer (MBMS) and an atmospheric pressure chemical ionization (APCI) Orbitrap mass spectrometer (OTMS). The OTMS was also used to analyze the sampled species from a CFR engine exhaust. Approximately 70 intermediates were detected by the SVUV-PI-MBMS, and their assigned molecular formulae are in good agreement with those detected by the APCI-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar to those produced in an ideal reactor, i.e., a JSR. The products can be classified by species with molecular formulae of C 7 H 14 O x (x = 0–5), C 7 H 12 O x (x = 0–4), C 7 H 10 O x (x = 0–4), C n H 2n (n = 2–6), C n H 2n-2 (n = 4–6), C n H 2n+2 O (n = 1–4), C n H 2n O (n = 1–6), C n H 2n-2 O (n = 2–6), C n H 2n-4 O (n = 4–6), C n H 2n+2 O 2 (n = 0–4, 7), C n H 2n O 2 (n = 1–6), C n H 2n-2 O 2 (n = 2–6), C n H 2n-4 O 2 (n = 4–6), and C n H 2n O 3 (n = 3–6). The identified intermediate species include alkenes, dienes, aldehyde/keto compounds, olefinic aldehyde/keto compounds, diones, cyclic ethers, peroxides, acids, and alcohols/ethers. Reaction pathways forming these intermediates are proposed and discussed herein. Finally, these experimental results are important in the development of more accurate kinetic models for n-heptane and longer-chain alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗