Open-Path Fourier Transform Infrared Studies of Large-Scale Laboratory Biomass Fires

A series of nine large-scale, open fires was conducted in the Intermountain Fire Sciences Laboratory (IFSL) controlled-environment combustion facility. The fuels were pure pine needles or sagebrush or mixed fuels simulating forest-floor, ground fires; crown fires; broadcast burns; and slash pile burns. Mid-infrared spectra of the smoke were recorded throughout each fire by open path Fourier transform infrared (FTIR) spectroscopy at 0.12 cm−1 resolution over a 3 m cross-stack pathlength and analyzed to provide pseudocontinuous, simultaneous concentrations of up to 16 compounds. Simultaneous measurements were made of fuel mass loss, stack gas temperature, and total mass flow up the stack. The products detected are classified by the type of process that dominates in producing them. Carbon dioxide is the dominant emission of (and primarily produced by) flaming combustion, from which we also measure nitric oxide, nitrogen dioxide, sulfur dioxide, and most of the water vapor from combustion and fuel moisture. Carbon monoxide is the dominant emission formed primarily by smoldering combustion from which we also measure carbon dioxide, methane, ammonia, and ethane. A significant fraction of the total emissions is unoxidized pyrolysis products; examples are methanol, formaldehyde, acetic and formic acid, ethene (ethylene), ethyne (acetylene), and hydrogen cyanide. Relatively few previous data exist for many of these compounds and they are likely to have an important but as yet poorly understood role in plume chemistry. Large differences in emissions occur from different fire and fuel types, and the observed temporal behavior of the emissions is found to depend strongly on the fuel bed and product type

Fully quantum mechanical dynamic analysis of single-photon transport in a single-mode waveguide coupled to a traveling-wave resonator

We analyze the dynamics of single photon transport in a single-mode waveguide coupled to a micro-optical resonator using a fully quantum mechanical model. We examine the propagation of a single-photon Gaussian packet through the system under various coupling conditions. We review the theory of single photon transport phenomena as applied to the system and we develop a discussion on the numerical technique we used to solve for dynamical behavior of the quantized field. To demonstrate our method and to establish robust single photon results, we study the process of adiabatically lowering or raising the energy of a single photon trapped in an optical resonator under active tuning of the resonator. We show that our fully quantum mechanical approach reproduces the semi-classical result in the appropriate limit and that the adiabatic invariant has the same form in each case. Finally, we explore the trapping of a single photon in a system of dynamically tuned, coupled optical cavities.Comment: 24 pages, 10 figure

Empirical constraints on the nucleosynthesis of nitrogen

We derive empirical constraints on the nucleosynthetic yields of nitrogen by incorporating N enrichment into our previously developed and empirically tuned multizone galactic chemical evolution model. We adopt a metallicity-independent (‘primary’) N yield from massive stars and a metallicity-dependent (‘secondary’) N yield from AGB stars. In our model, galactic radial zones do not evolve along the observed [N/O]–[O/H] relation, but first increase in [O/H] at roughly constant [N/O], then move upward in [N/O] via secondary N production. By t ≈ 5 Gyr, the model approaches an equilibrium [N/O]–[O/H] relation, which traces the radial oxygen gradient. Reproducing the [N/O]–[O/H] trend observed in extragalactic systems constrains the ratio of IMF-averaged N yields to the IMF-averaged O yield of core-collapse supernovae. We find good agreement if we adopt |$y_\text{N}^\text{CC}/y_\text{O}^\text{CC}=0.024$| and |$y_\text{N}^\text{AGB}/y_\text{O}^\text{CC} = 0.062(Z/Z_\odot)$|⁠. For the theoretical AGB yields we consider, simple stellar populations release half their N after only ∼250 Myr. Our model reproduces the [N/O]–[O/H] relation found for Milky Way stars in the APOGEE survey, and it reproduces (though imperfectly) the trends of stellar [N/O] with age and [O/Fe]. The metallicity-dependent yield plays the dominant role in shaping the gas-phase [N/O]–[O/H] relation, but the AGB time-delay is required to match the stellar age and [O/Fe] trends. If we add ∼40 per cent oscillations to the star formation rate, the model reproduces the scatter in the gas phase [N/O]–[O/H] relation observed in external galaxies by MaNGA. We discuss implications of our results for theoretical models of N production by massive stars and AGB stars

Absolute calibration of the intramolecular site preference of 15N fractionation in tropospheric N2O by FT-IR spectroscopy

Nitrous oxide (N2O) plays important roles in atmospheric chemistry both as a greenhouse gas and in stratospheric ozone depletion. Isotopic measurements of N2O have provided an invaluable insight into understanding its atmospheric sources and sinks. The preference for 15N fractionation between the central and terminal positions (the “site preference”) is particularly valuable because it depends principally on the processes involved in N2O production or consumption, rather than the 15N content of the substrate from which it is formed. Despite the value of measurements of the site preference, there is no internationally recognized standard reference material of accurately known and accepted site preference, and there has been some lack of agreement in published studies aimed at providing such a standard. Previous work has been based on isotope ratio mass spectrometry (IRMS); in this work we provide an absolute calibration for the intramolecular site preference of 15N fractionation of working standard gases used in our laboratory by a completely independent technique—high-resolution Fourier transform infrared (FT-IR) spectroscopy. By reference to this absolute calibration, we determine the site preference for 25 samples of tropospheric N2O collected under clean air conditions to be 19.8‰ ± 2.1‰. This result is in agreement with that based on the earlier absolute calibration of Toyoda and Yoshida (Toyoda, S. and Yoshida, N. Anal. Chem. 1999, 71, 4711−4718) who found an average tropospheric site preference of 18.7‰ ± 2.2‰. We now recommend an interlaboratory exchange of working standard N2O gases as the next step to providing an international reference standard

Transport of NOX emissions from sugarcane fertilisation into the Great Barrier Reef Lagoon

The Great Barrier Reef World Heritage Area contains highly sensitive ecosystems that are threatened by the effects of anthropogenic activity including eutrophication. The nearby sugarcane plantations of tropical north Queensland are fertilised annually and there has been ongoing concern about the magnitude of the loss of applied nitrogen to the environment. Previous studies have considered the potential of rainwater run-off to deposit reactive nitrogen species into rivers and ultimately into the Great Barrier Reef Lagoon, but have neglected the possibility of transport via the atmosphere. This paper reports the results of a modelling study commissioned by Australia’s National Heritage Trust aimed at assessing whether or not atmospheric deposition of reactive nitrogen from Queensland’s sugarcane plantations posed a potential threat to the Great Barrier Reef Lagoon. Atmospheric dispersion modelling was undertaken using The Air Pollution Model, developed by Australia’s Commonwealth Scientific and Industrial Research Organisation. Despite the predominance of onshore southeasterly winds, the dispersion model results indicate that 9% of the time during the sugarcane fertilization season (in the modeled years 2001–2006) the meteorological conditions resulted in emissions from the coastal regions of north Queensland being transported out over the ocean around the Great Barrier Reef. The results suggest that there may be a greater efficiency for transport out over the reef during October than for November and December. For the 2 months that exhibited the greatest potential for transport of coastal pollution to the Great Barrier Reef, the modeled deposition of nitrogen oxides (NOX) into the Great Barrier Reef lagoon was less than 1% of the total emissions from the sugarcane plantations, but was not zero. Our model has a simple chemical scheme that does not cover the full chemistry of all reactive nitrogen compounds and so the results are only indicative of the potential levels of deposition. Nevertheless, our study shows that small amounts of NOX that originate from sugarcane fertilization may be transported and dry deposited into the Great Barrier Reef lagoon. Other pathways not included in the modeling scheme may provide a more efficient transport mechanism. Whilst modern practices for the application of fertilizer to sugarcane plantations have drastically reduced emissions, the potential efficiency of transport of pollutants via the atmosphere may be of concern for other more highly polluting agricultural industries

Emissions from Smoldering Combustion of Biomass Measured by Open-Path Fourier Transform Infrared Spectroscopy

Biomass samples from a diverse range of ecosystems were burned in the Intermountain Fire Sciences Laboratory open combustion facility. Midinfrared spectra of the nascent emissions were acquired at several heights above the fires with a Fourier transform infrared spectrometer (FTIR) coupled to an open multipass cell. In this report, the results from smoldering combustion during 24 fires are presented including production of carbon dioxide, carbon monoxide, methane, ethene, ethyne, propene, formaldehyde, 2-hydroxyethanal, methanol, phenol, acetic acid, formic acid, ammonia, hydrogen cyanide, and carbonyl sulfide. These were the dominant products observed, and many have significant influence on atmospheric chemistry at the local, regional, and global scale. Included in these results are the first optical, in situ measurements of smoke composition from fires in grasses, hardwoods, and organic soils. About one half of the detected organic emissions arose from fuel pyrolysis which produces white smoke rich in oxygenated organic compounds. These compounds deserve more attention in the assessment of fire impacts on the atmosphere. The compound 2-hydroxyethanal is a significant component of the smoke, and it is reported here for the first time as a product of fires. Most of the observed alkane and ammonia production accompanied visible glowing combustion. NH3 is normally the major nitrogen-containing emission detected from smoldering combustion of biomass, but from some smoldering organic soils, HCN was dominant. Tar condensed on cool surfaces below the fires accounting for ∼1% of the biomass burned, but it was enriched in N by a factor of 6–7 over the parent material, and its possible role in postfire nutrient cycling should be further investigated

Trace gas emissions from savanna fires in northern Australia

We present analyses of near‐infrared ground‐based Fourier transform infrared solar absorption spectra recorded from a site in Darwin, Northern Territory, Australia (12.4°S, 130.9°E) from August 2005 to June 2008. Total column amounts of carbon monoxide derived from these spectra show a very clear annual cycle, with evidence of transported pollution from Indonesian fires in 2006. Aerosol optical depth measurements from the same site show a similar annual cycle but without exceptional values in 2006, suggesting significant loss of aerosol loading in the transported and aged smoke. In addition, we report the first ever measurements by remote sensing solar Fourier transform infrared of emission ratios with respect to carbon monoxide for formaldehyde (0.022 ± 0.007), acetylene (0.0024 ± 0.0003), ethane (0.0020 ± 0.0003), and hydrogen cyanide (0.0018 ± 0.0003) from Australian savanna fires. These are derived from mid‐infrared spectra recorded through smoke plumes over Darwin on 20 separate days. The only previous measurements of emission ratios for formaldehyde and hydrogen cyanide from Australian savanna fires involved cryogenic trapping and storage of samples that were gathered in very fresh smoke. The results reported here are nearly an order of magnitude higher (but in agreement with laboratory studies), suggesting losses in the collection, storage, or transfer of the gases in the earlier measurements and/or chemical production of these reactive gases within the smoke plumes. Emission ratios for acetylene and ethane from this work are in broad agreement with other literature values

Nucleosynthesis signatures of neutrino-driven winds from proto-neutron stars: a perspective from chemical evolution models

We test the hypothesis that the observed first-peak (Sr, Y, Zr) and second-peak (Ba) s-process elemental abundances in low-metallicity Milky Way stars, and the abundances of the elements Mo and Ru, can be explained by a pervasive r-process contribution originating in neutrino-driven winds from highly-magnetic and rapidly rotating proto-neutron stars (proto-NSs). We construct chemical evolution models that incorporate recent calculations of proto-NS yields in addition to contributions from AGB stars, Type Ia supernovae, and two alternative sets of yields for massive star winds and core-collapse supernovae. For non-rotating massive star yields from either set, models without proto-NS winds underpredict the observed s-process peak abundances by $0.3$-$1\,\text{dex}$ at low metallicity, and they severely underpredict Mo and Ru at all metallicities. Models incorporating wind yields from proto-NSs with spin periods $P \sim 2$-$5\,\text{ms}$ fit the observed trends for all these elements well. Alternatively, models omitting proto-NS winds but adopting yields of rapidly rotating massive stars, with $v_{\rm rot}$ between $150$ and $300\,\text{km}\,\text{s}^{-1}$, can explain the observed abundance levels reasonably well for $\text{[Fe/H]}<-2$. These models overpredict [Sr/Fe] and [Mo/Fe] at higher metallicities, but with a tuned dependence of $v_{\rm rot}$ on stellar metallicity they might achieve an acceptable fit at all [Fe/H]. If many proto-NSs are born with strong magnetic fields and short spin periods, then their neutrino-driven winds provide a natural source for Sr, Y, Zr, Mo, Ru, and Ba in low-metallicity stellar populations. Conversely, spherical winds from unmagnetized proto-NSs overproduce the observed Sr, Y, and Zr abundances by a large factor.Comment: Accepted for publication in MNRA

Carbon dynamics in the western Arctic Ocean : insights from full-depth carbon isotope profiles of DIC, DOC, and POC

© The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 9 (2012): 1217-1224, doi:10.5194/bg-9-1217-2012.Arctic warming is projected to continue throughout the coming century. Yet, our currently limited understanding of the Arctic Ocean carbon cycle hinders our ability to predict how changing conditions will affect local Arctic ecosystems, regional carbon budgets, and global climate. We present here the first set of concurrent, full-depth, dual-isotope profiles for dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and suspended particulate organic carbon (POCsusp) at two sites in the Canada Basin of the Arctic Ocean. The carbon isotope composition of sinking and suspended POC in the Arctic contrasts strongly with open ocean Atlantic and Pacific sites, pointing to a combination of inputs to Arctic POCsusp at depth, including surface-derived organic carbon (OC), sorbed/advected OC, and OC derived from in situ DIC fixation. The latter process appears to be particularly important at intermediate depths, where mass balance calculations suggest that OC derived from in situ DIC fixation contributes up to 22% of POCsusp. As in other oceans, surface-derived OC is still a dominant source to Arctic POCsusp. Yet, we suggest that significantly smaller vertical POC fluxes in the Canada Basin make it possible to see evidence of DIC fixation in the POCsusp pool even at the bulk isotope level.The 2008 JOIS hydrographic program was supported by Fisheries and Oceans Canada, the Canadian International Polar Year Office, and the US National Science Foundation (OPP-0424864; lead-PI Andrey Proshutinsky)

Improving atmospheric CO\u3csub\u3e2\u3c/sub\u3e retrievals using line mixing and speed-dependence when fitting high-resolution ground-based solar spectra

A quadratic speed-dependent Voigt spectral line shape with line mixing (qSDV + LM) has been included in atmospheric trace-gas retrievals to improve the accuracy of the calculated CO2 absorption coefficients. CO2 laboratory spectra were used to validate absorption coefficient calculations for three bands: the strong 20013 ← 00001 band centered at 4850 cm−1, and the weak 30013 ← 00001 and 30012 ← 00001 bands centered at 6220 cm−1 and 6340 cm−1 respectively, and referred to below as bands 1 and 2. Several different line lists were tested. Laboratory spectra were best reproduced for the strong CO2 band when using HITRAN 2008 spectroscopic data with air-broadened widths divided by 0.985, self-broadened widths divided by 0.978, line mixing coefficients calculated using the exponential power gap (EPG) law, and a speed-dependent parameter of 0.11 used for all lines. For the weak CO2 bands, laboratory spectra were best reproduced using spectroscopic parameters from the studies by Devi et al. in 2007 coupled with line mixing coefficients calculated using the EPG law. A total of 132,598 high-resolution ground-based solar absorption spectra were fitted using qSDV + LM to calculate CO2 absorption coefficients and compared to fits that used the Voigt line shape. For the strong CO2 band, the average root mean square (RMS) residual is 0.49 ± 0.22% when using qSDV + LM to calculate the absorption coefficients. This is an improvement over the results with the Voigt line shape, which had an average RMS residual of 0.60 ± 0.21%. When using the qSDV + LM to fit the two weak CO2 bands, the average RMS residual is 0.47 ± 0.19% and 0.51 ± 0.20% for bands 1 and 2, respectively. These values are identical to those obtained with the Voigt line shape. Finally, we find that using the qSDV + LM decreases the airmass dependence of the column averaged dry air mole fraction of CO2 retrieved from the strong and both weak CO2 bands when compared to the retrievals obtained using the Voigt line shape