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

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

The Tropical Forest and Fire Emissions Experiment: Overview and Airborne Fire Emission Factor Measurements

The Tropical Forest and Fire Emissions Experiment (TROFFEE) used laboratory measurements followed by airborne and ground based field campaigns during the 2004 Amazon dry season to quantify the emissions from pristine tropical forest and several plantations as well as the emissions, fuel consumption, and fire ecology of tropical deforestation fires. The airborne campaign used an Embraer 110B aircraft outfitted with whole air sampling in canisters, mass-calibrated nephelometry, ozone by UV absorbance, Fourier transform infrared spectroscopy (FTIR), and proton-transfer mass spectrometry (PTR-MS) to measure PM(10), O(3), CO(2), CO, NO, NO(2), HONO, HCN, NH(3), OCS, DMS, CH(4), and up to 48 non-methane organic compounds (NMOC). The Brazilian smoke/haze layers extended to 2 - 3 km altitude, which is much lower than the 5 - 6 km observed at the same latitude, time of year, and local time in Africa in 2000. Emission factors (EF) were computed for the 19 tropical deforestation fires sampled and they largely compare well to previous work. However, the TROFFEE EF are mostly based on a much larger number of samples than previously available and they also include results for significant emissions not previously reported such as: nitrous acid, acrylonitrile, pyrrole, methylvinylketone, methacrolein, crotonaldehyde, methylethylketone, methylpropanal, \u27\u27 acetol plus methylacetate,\u27\u27 furaldehydes, dimethylsulfide, and C(1)-C(4) alkyl nitrates. Thus, we recommend these EF for all tropical deforestation fires. The NMOC emissions were similar to 80% reactive, oxygenated volatile organic compounds (OVOC). Our EF for PM(10) (17.8 +/- 4 g/kg) is similar to 25% higher than previously reported for tropical forest fires and may reflect a trend towards, and sampling of, larger fires than in earlier studies. A large fraction of the total burning for 2004 likely occurred during a two-week period of very low humidity. The combined output of these fires created a massive \u27\u27 mega-plume \u27\u27 \u3e 500 km across that we sampled on 8 September. The mega-plume contained high PM(10) and 10 - 50 ppbv of many reactive species such as O(3), NH(3), NO(2), CH(3)OH, and organic acids. This is an intense and globally important chemical processing environment that is still poorly understood. The mega-plume or \u27\u27 white ocean \u27\u27 of smoke covered a large area in Brazil, Bolivia, and Paraguay for about one month. The smoke was transported \u3e 2000 km to the southeast while remaining concentrated enough to cause a 3 - 4-fold increase in aerosol loading in the S (a) over tildeo Paulo area for several days

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

Airborne and Ground-Based Measurements of the Trace Gases and Particles Emitted by Prescribed Fires in the United States

We have measured emission factors for 19 trace gas species and particulate matter (PM2.5) from 14 prescribed fires in chaparral and oak savanna in the southwestern US, as well as conifer forest understory in the southeastern US and Sierra Nevada mountains of California. These are likely the most extensive emission factor field measurements for temperate biomass burning to date and the only published emission factors for temperate oak savanna fuels. This study helps to close the gap in emissions data available for temperate zone fires relative to tropical biomass burning. We present the first field measurements of the biomass burning emissions of glycolaldehyde, a possible precursor for aqueous phase secondary organic aerosol formation. We also measured the emissions of phenol, another aqueous phase secondary organic aerosol precursor. Our data confirm previous observations that urban deposition can impact the NOx emission factors and thus subsequent plume chemistry. For two fires, we measured both the emissions in the convective smoke plume from our airborne platform and the unlofted residual smoldering combustion emissions with our ground-based platform. The smoke from residual smoldering combustion was characterized by emission factors for hydrocarbon and oxygenated organic species that were up to ten times higher than in the lofted plume, including high 1,3-butadiene and isoprene concentrations which were not observed in the lofted plume. This should be considered in modeling the air quality impacts for smoke that disperses at ground level. We also show that the often ignored unlofted emissions can significantly impact estimates of total emissions. Preliminary evidence suggests large emissions of monoterpenes in the residual smoldering smoke. These data should lead to an improved capacity to model the impacts of biomass burning in similar temperate ecosystems

Competitive Replacement of Invasive Congeners May Relax Impact on Native Species: Interactions among Zebra, Quagga, and Native Unionid Mussels

Determining when and where the ecological impacts of invasive species will be most detrimental and whether the effects of multiple invaders will be superadditive, or subadditive, is critical for developing global management priorities to protect native species in advance of future invasions. Over the past century, the decline of freshwater bivalves of the family Unionidae has been greatly accelerated by the invasion of Dreissena. The purpose of this study was to evaluate the current infestation rates of unionids by zebra (Dreissena polymorpha) and quagga (D. rostriformis bugensis) mussels in the lower Great Lakes region 25 years after they nearly extirpated native unionids. In 2011–2012, we collected infestation data for over 4000 unionids from 26 species at 198 nearshore sites in lakes Erie, Ontario, and St. Clair, the Detroit River, and inland Michigan lakes and compared those results to studies from the early 1990s. We found that the frequency of unionid infestation by Dreissena recently declined, and the number of dreissenids attached to unionids in the lower Great Lakes has fallen almost ten-fold since the early 1990s. We also found that the rate of infestation depends on the dominant Dreissena species in the lake: zebra mussels infested unionids much more often and in greater numbers. Consequently, the proportion of infested unionids, as well as the number and weight of attached dreissenids were lower in waterbodies dominated by quagga mussels. This is the first large-scale systematic study that revealed how minor differences between two taxonomically and functionally related invaders may have large consequences for native communities they invade

Emissions of Formaldehyde, Acetic Acid, Methanol, and Other Trace Gases from Biomass Fires in North Carolina Measured by Airborne Fourier Transform Infrared Spectroscopy

Biomass burning is an important source of many trace gases in the global troposphere. We have constructed an airborne trace gas measurement system consisting of a Fourier transform infrared spectrometer (FTIR) coupled to a “flow-through” multipass cell (AFTIR) and installed it on a U.S. Department of Agriculture Forest Service King Air B-90. The first measurements with the new system were conducted in North Carolina during April 1997 on large, isolated biomass fire plumes. Simultaneous measurements included Global Positioning System (GPS); airborne sonde; particle light scattering, CO, and CO2; and integrated filter and canister samples. AFTIR spectra acquired within a few kilometers of the fires yielded excess mixing ratios for 10 of the most common trace gases in the smoke: water, carbon dioxide, carbon monoxide, methane, formaldehyde, acetic acid, formic acid, methanol, ethylene, and ammonia. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were each 2.5±1%. This is in excellent agreement with (and confirms the relevance of) our results from laboratory fires. However, these ratios are significantly higher than the emission ratios reported for these compounds in some previous studies of “fresh” smoke. We present a simple photochemical model calculation that suggests that oxygenated organic compounds should be included in the assessment of ozone formation in smoke plumes. Our measured emission factors indicate that biomass fires could account for a significant portion of the oxygenated organic compounds and HOx present in the tropical troposphere during the dry season. Our fire measurements, along with recent measurements of oxygenated biogenic emissions and oxygenated organic compounds in the free troposphere, indicate that these rarely measured compounds play a major, but poorly understood, role in the HOx, NOx, and O3 chemistry of the troposphere

A new outcome measure for LUTS: Symptoms of Lower Urinary Tract Dysfunction Research Network Symptom Index‐29 (LURN SI‐29) questionnaire

AimsTo develop a representative, self‐report assessment of lower urinary tract symptoms (LUTS) for men and women, the symptoms of Lower Urinary Tract Dysfunction Research Network Symptom Index‐29 (LURN SI‐29).MethodsWomen and men seeking treatment for LUTS at one of six academic medical centers in the US were assessed at baseline, 3‐month and 12‐month intervals. Twelve‐month data on 78 LURN SI‐29 items were analyzed among 353 women and 420 men using exploratory factor analysis (EFA), with factor structure confirmed using confirmatory factor analysis (CFA). Internal consistency, reliability, and validity of the five developed scales were evaluated by assessing correlations with the American Urological Association Symptom Index (AUA‐SI), the genitourinary pain index (GUPI), and the Pelvic Floor Distress Inventory‐20 (PFDI‐20), and by examining expected sex differences in scores.ResultsEFA results (n = 150 women; 150 men) produced an interpretable eight‐factor solution, with three of the factors comprised of dichotomous items addressing LUTS‐associated sensations. The remaining five factors, confirmed with CFA in an independent sample of 473 participants, produced five scales: incontinence, urgency, voiding difficulty, bladder pain, and nocturia. Subscales and total LURN SI‐29 scores were correlated as expected with AUA‐SI, GUPI, and PFDI‐20. LURN SI‐29 scores also performed as expected in differentiating men from women based upon clinically expected differences, with men reporting more voiding difficulties and nocturia, and women reporting more urgency and incontinence.ConclusionsThe LURN SI‐29 questionnaire has the potential to improve research and clinical outcome measurement for both men and women with LUTS.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/150585/1/nau24067.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150585/2/nau24067_am.pd