Bacterial Emission Factors: A Foundation for the Terrestrial-Atmospheric Modeling of Bacteria Aerosolized by Wildland Fires.

Wildland fire is a major global driver in the exchange of aerosols between terrestrial environments and the atmosphere. This exchange is commonly quantified using emission factors or the mass of a pollutant emitted per mass of fuel burned. However, emission factors for microbes aerosolized by fire have yet to be determined. Using bacterial cell concentrations collected on unmanned aircraft systems over forest fires in Utah, USA, we determine bacterial emission factors (BEFs) for the first time. We estimate that 1.39 × 1010 and 7.68 × 1011 microbes are emitted for each Mg of biomass consumed in fires burning thinning residues and intact forests, respectively. These emissions exceed estimates of background bacterial emissions in other studies by 3-4 orders of magnitude. For the ∼2631 ha of similar forests in the Fishlake National Forest that burn each year on average, an estimated 1.35 × 1017 cells or 8.1 kg of bacterial biomass were emitted. BEFs were then used to parametrize a computationally scalable particle transport model that predicted over 99% of the emitted cells were transported beyond the 17.25 x 17.25 km model domain. BEFs can be used to expand understanding of global wildfire microbial emissions and their potential consequences to ecosystems, the atmosphere, and humans.

Seasonal Emission Factors from Rangeland Prescribed Burns in the Kansas Flint Hills Grasslands.

Operational-sized prescribed grassland burns at three mid-West U.S. locations and ten 1-ha-sized prescribed grassland burns were conducted in the Flint Hills of Kansas to determine emission factors and their potential seasonal effects. Ground-, aerostat-, and unmanned aircraft system-based platforms were used to sample plume emissions for a range of gaseous and particulate pollutants. The ten co-located, 1-ha-sized plots allowed for testing five plots in the spring and five in the late summer, allowing for control of vegetation type, biomass loading, climate history, and land use. The operational-sized burns provided a range of conditions under which to determine emission factors relevant to the Flint Hills grasslands. The 1-ha plots showed that emission factors for pollutants such as PM2.5 and BTEX (benzene, toluene, ethylbenzene, and xylene) were higher during the late summer than during the traditional spring burn season. This is likely due to increased biomass density and fuel moisture in the growing season biomass resulting in reduced combustion efficiency.

Chemistry and lung toxicity of particulate matter emitted from firearms.

Smoke emissions produced by firearms contain hazardous chemicals, but little is known if their properties change depending on firearm and ammunition type and whether such changes affect toxicity outcomes. Pulmonary toxicity was assessed in mice exposed by oropharyngeal aspiration to six different types of smoke-related particulate matter (PM) samples; (1) handgun PM, (2) rifle PM, (3) copper (Cu) particles (a surrogate for Cu in the rifle PM) with and without the Cu chelator penicillamine, (4) water-soluble components of the rifle PM, (5) soluble components with removal of metal ions, and (6) insoluble components of the rifle PM. Gun firing smoke PM was in the respirable size range but the chemical composition varied with high levels of Pb in the handgun and Cu in the rifle smoke. The handgun PM did not induce appreciable lung toxicity at 4 and 24 h post-exposure while the rifle PM significantly increased lung inflammation and reduced lung function. The same levels of pure Cu particles alone and the soluble components from the rifle fire PM increased neutrophil numbers but did not cause appreciable cellular damage or lung function changes when compared to the negative (saline) control. Penicillamine treated rifle PM or Cu, slightly reduced lung inflammation and injury but did not improve the lung function decrements. Chelation of the soluble metal ions from the rifle fire PM neutralized the lung toxicity while the insoluble components induced the lung toxicity to the same degree as the rifle PM. The results show that different firearm types can generate contrasting chemical spectra in their emissions and that the rifle PM effects were mostly driven by water-insoluble components containing high levels of Cu. These findings provide better knowledge of hazardous substances in gun firing smoke and their potential toxicological profile.

Wildland fire smoke alters the composition, diversity, and potential atmospheric function of microbial life in the aerobiome.

The atmosphere contains a diverse reservoir of microbes but the sources and factors contributing to microbial aerosol variability are not well constrained. To advance understanding of microbial emissions in wildfire smoke, we used unmanned aircraft systems to analyze the aerosols above high-intensity forest fires in the western United States. Our results show that samples of the smoke contained ~four-fold higher concentrations of cells (1.02 ± 0.26 × 105 m-3) compared to background air, with 78% of microbes in smoke inferred to be viable. Fivefold higher taxon richness and ~threefold enrichment of ice nucleating particle concentrations in smoke implies that wildfires are an important source of diverse bacteria and fungi as well as meteorologically relevant aerosols. We estimate that such fires emit 3.71 × 1014 microbial cells ha-1 under typical wildfire conditions in western US forests and demonstrate that wildland biomass combustion has a large-scale influence on the local atmospheric microbial assemblages. Given the long-range transport of wildfire smoke emissions, these results expand the concept of a wildfire's perimeter of biological impact and have implications to biogeography, gene flow, the dispersal of plant, animal, and human pathogens, and meteorology.

Characterization of emissions from burning methyl-bromide-treated crop biomass.

Alfalfa hay that was grown on a field treated with a methyl bromide and chloropicrin pesticide (at a 98/2 weight ratio) resulted in animal sickness, posing a disposal issue for the harvested feed. In consideration of disposal options, emissions and residues from burning treated and untreated alfalfa hay were sampled and analyzed to provide data for an assessment of potential health and environmental effects. Treated alfalfa hay was tested in parallel with untreated alfalfa in a controlled laboratory combustion facility. Results showed that about half of the bromine and chlorine in the treated hay was emitted and the remaining was retained in the ash. The alfalfa hay burned poorly, with modified combustion efficiencies, the ratio of CO2 to CO + CO2, below 0.89. The emission factor for PM2.5 was statistically higher for the untreated versus treated alfalfa but the PAHs were doubled in the treated alfalfa. The treated alfalfa had significantly more emissions of polychorinated dibenzodioxin/dibenzofuran than the untreated alfalfa by a factor of 10, but less polybrominated dibenzodioxin/dibenzofuran. The high Br concentration in the treated alfalfa biomass may have resulted in formation and emission of mixed halogen compounds which were unable to be analyzed for lack of standards. Comparison of volatile organic compound emissions were unremarkable with the exception of MeBr where emissions from the treated alfalfa were over 300 times higher than the untreated biomass. The potential complications due to emissions and permitting of an open burn or contained incinerator left options for landfilling and feedstock blending for handling the treated alfalfa. Implications: This paper illustrates the issues agricultural managers must deal with concerning the combustive disposal of contaminated crops. A method is presented whereby combustion of contaminated crops can be assessed for their suitability for disposal by open air or enclosed burning.

Analysis of emissions and residue from methods to improve efficiency of at-sea, in situ oil spill burns.

The combustion efficiency of simulated at-sea surface oil burns (in situ burns) was determined in a 63 m3 tank while testing varied boom configurations and air-assist nozzles in the presence and absence of waves. Combustion efficiencies of Alaska North Slope oil based on unburned carbon in the plume emissions ranged from 85% to 93% while values based on oil mass loss ranged from 89% to 99%. A four-fold variation in PM2.5 emission factors was observed from the test conditions. The most effective burns in terms of reduced emissions and post-burn residue concentration of total petroleum hydrocarbons were those that had high length to width boom ratios resulting in higher flame front surface area exposure to ambient air. The amount of oil mass lost was not related to any combustion efficiency parameters measured in the plume, representing a potential tradeoff between unburnt oil and air pollution.

Use of an unmanned aircraft system to quantify NO x emissions from a natural gas boiler.

Aerial emission sampling of four natural gas boiler stack plumes was conducted using an unmanned aerial system (UAS) equipped with a lightweight sensor-sampling system (the "Kolibri") for measurement of nitrogen oxide (NO), and nitrogen dioxide (NO2), carbon dioxide (CO2), and carbon monoxide (CO). Flights (n=22) ranged from 11 to 24min in duration at two different sites. The UAS was maneuvered into the plumes with the aid of real-time CO2 telemetry to the ground operators and, at one location, a second UAS equipped with an infrared-visible camera. Concentrations were collected and recorded at 1Hz. The maximum CO2, CO, NO, and NO2 concentrations in the plume measured were 10000, 7, 27, and 1.5 ppm, respectively. Comparison of the NO x emissions between the stack continuous emission monitoring systems and the UAS-Kolibri for three boiler sets showed an average of 5.6% and 3.5% relative difference for the run-weighted and carbon-weighted average emissions, respectively. To our knowledge, this is the first evidence of the accuracy performance of UAS-based emission factors against a source of known strength.

Characterization of M4 carbine rifle emissions with three ammunition types.

Muzzle emissions from firing an M4 carbine rifle in a semi-enclosed chamber were characterized for an array of compounds to provide quantitative data for future studies on potential inhalation exposure and rangeland contamination. Air emissions were characterized for particulate matter (PM) size distribution, composition, and morphology; carbon monoxide (CO); carbon dioxide (CO2); energetics; metals; polycyclic aromatic hydrocarbons; and methane. Three types of ammunition were used: a "Legacy" (Vietnam-era) round, the common M855 round (no longer fielded), and its variant, an M855 round with added potassium (K)-based salts to reduce muzzle flash. Average CO concentrations up to 1500 ppm significantly exceeded CO2 concentrations. Emitted particles were in the respirable size range with mass median diameters between 0.33 and 0.58 µm. PM emissions were highest from the M855 salt-added ammunition, likely due to incomplete secondary combustion in the muzzle blast caused by scavenging of combustion radicals by the K salt. Copper (Cu) had the highest emitted metal concentration for all three round formulations, likely originating from the Cu jacket on the bullet. Based on a mass balance analysis of each round's formulation, lead (Pb) was completely emitted for all three round types. This work demonstrated methods for characterizing emissions from gun firing which can distinguish between round-specific effects and can be used to initiate studies of inhalation risk and environmental deposition.

Characterizing emissions from open burning of military food waste and ration packaging compositions.

Emissions from open burning of military food waste and ration packaging compositions were characterized in response to health concerns from open burning disposal of waste, such as at military forward operating bases. Emissions from current and prototype Meals, Ready-to-Eat (MREs), and material options for their associated fiberboard packaging were quantified to assess contributions of the individual components. MREs account for 67-100% of the particulate matter (PM), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated dibenzo-p-dioxins and -furans (PCDDs/PCDFs) emissions when burned in unison with the current fiberboard container and liner. The majority of the particles emitted from these burns are of median diameter 2.5 µm (PM2.5). Metal emission factors were similar regardless of waste composition. Measurements of VOCs and PAHs indicate that targeted replacement of MRE components may be more effective in reducing emissions than variation of fiberboard-packaging types. Despite MRE composition variation, equivalent emission factors for PM, PAH, VOC, and PCDD/PCDF were seen. Similarly, for fiberboard packaging, composition variations exhibited essentially equivalent PM, PAH, VOC, and PCDD/PCDF emission factors amongst themselves. This study demonstrated a composition-specific analysis of waste burn emissions, assessing the impact of waste component substitution using military rations.

Improving post-detonation energetics residues estimations for the Life Cycle Environmental Assessment process for munitions.

The Life Cycle Environmental Assessment (LCEA) process for military munitions tracks possible environmental impacts incurred during all phases of the life of a munition. The greatest energetics-based emphasis in the current LCEA process is on manufacturing. A review of recent LCEAs indicates that energetics deposition on ranges from detonations and disposal during training is only peripherally examined through assessment of combustion products derived from closed-chamber testing or models. These assessments rarely report any measurable energetic residues. Field-testing of munitions for energetics residues deposition has demonstrated that over 30% of some energetic compounds remain after detonation, which conflicts with the LCEA findings. A study was conducted in the open environment to determine levels of energetics residue deposition and if combustion product results can be correlated with empirical deposition results. Energetics residues deposition, post-detonation combustion products, and fine aerosolized energetics particles following open-air detonation of blocks of Composition C4 (510 g RDX/block) were quantified. The deposited residues amounted to 3.6 mg of energetic per block of C4, or less than 0.001% of the original energetics. Aerial emissions of energetics were about 7% of the amount of deposited energetics. This research indicates that aerial combustion products analysis can provide a valuable supplement to energetics deposition data in the LCEA process but is insufficient alone to account for total residual energetics. This study demonstrates a need for the environmental testing of munitions to quantify energetics residues from live-fire training.

Mutagenicity and oxidative damage induced by an organic extract of the particulate emissions from a simulation of the deepwater horizon surface oil burns.

Emissions from oil fires associated with the "Deepwater Horizon" explosion and oil discharge that began on April 20, 2010 in the Gulf of Mexico were analyzed chemically to only a limited extent at the time but were shown to induce oxidative damage in vitro and in mice. To extend this work, we burned oil floating on sea water and performed extensive chemical analyses of the emissions (Gullett et al., Marine Pollut Bull, in press, ). Here, we examine the ability of a dichloromethane extract of the particulate material with an aerodynamic size ≤ 2.5 µm (PM2.5 ) from those emissions to induce oxidative damage in human lung cells in vitro and mutagenicity in 6 strains of Salmonella. The extract had a percentage of extractable organic material (EOM) of 7.0% and increased expression of the heme oxygenase (HMOX1) gene in BEAS-2B cells after exposure for 4 hr at 20 µg of EOM/ml. However, the extract did not alter mitochondrial respiration rate as measured by extracellular flux analysis. The extract was most mutagenic in TA100 +S9, indicative of a role for polycyclic aromatic hydrocarbons (PAHs), reflective of the high concentrations of PAHs in the emissions (1 g/kg of oil consumed). The extract had a mutagenicity emission factor of 1.8 ± 0.1 × 105 revertants/megajoulethermal in TA98 +S9, which was greater than that of diesel exhaust and within an order of magnitude of open burning of wood and plastic. Thus, organics from PM2.5 of burning oil can induce oxidative responses in human airway epithelial cells and are highly mutagenic. Environ. Mol. Mutagen. 58:162-171, 2017. © 2017 Wiley Periodicals, Inc.

Characterization of emissions and residues from simulations of the Deepwater Horizon surface oil burns.

The surface oil burns conducted by the U.S. Coast Guard from April to July 2010 during the Deepwater Horizon disaster in the Gulf of Mexico were simulated by small scale burns to characterize the pollutants, determine emission factors, and gather particulate matter for subsequent toxicity testing. A representative crude oil was burned in ocean-salinity seawater, and emissions were collected from the plume by means of a crane-suspended sampling platform. Emissions included particulate matter, aromatic hydrocarbons, polychlorinated dibenzodioxins/dibenzofurans, elements, and others, the sum of which accounted for over 92% by mass of the combustion products. The unburned oil mass was 29% of the original crude oil mass, significantly higher than typically reported. Analysis of alkanes, elements, and PAHs in the floating residual oil and water accounted for over 51% of the gathered mass. These emission factors, along with toxicity data, will be important toward examining impacts of future spill burning operations.

Emissions from prescribed burning of timber slash piles in Oregon.

Emissions from burning piles of post-harvest timber slash (Douglas fir) in Grande Ronde, Oregon were sampled using an instrument platform lofted into the plume using a tether- controlled aerostat or balloon. Emissions of carbon monoxide, carbon dioxide, methane, particulate matter (PM2.5), black carbon, ultraviolet absorbing PM, elemental/organic carbon, filter-based metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzodioxins/dibenzofurans (PCDD/PCDF), and volatile organic compounds (VOCs) were sampled to determine emission factors, the amount of pollutant formed per amount of biomass burned. The effect on emissions from covering the piles with polyethylene (PE) sheets to prevent fuel wetting versus uncovered piles was also determined. Results showed that the uncovered ("wet") piles burned with lower combustion efficiency and higher emission factors for VOCs, PM2.5, PCDD/PCDF, and PAHs. Removal of the PE prior to ignition, variation of PE size, and changing PE thickness resulted in no statistical distinction between emissions. Results suggest that dry piles, whether covered with PE or not, exhibited statistically significant lower emissions than wet piles due to better combustion efficiency.

A small, lightweight multipollutant sensor system for ground-mobile and aerial emission sampling from open area sources.

Characterizing highly dynamic, transient, and vertically lofted emissions from open area sources poses unique measurement challenges. This study developed and applied a multipollutant sensor and time-integrated sampler system for use on mobile applications such as vehicles, tethered balloons (aerostats) and unmanned aerial vehicles (UAVs) to determine emission factors. The system is particularly applicable to open area sources, such as forest fires, due to its light weight (3.5 kg), compact size (6.75 L), and internal power supply. The sensor system, termed "Kolibri", consists of sensors measuring CO2 and CO, and samplers for particulate matter (PM) and volatile organic compounds (VOCs). The Kolibri is controlled by a microcontroller which can record and transfer data in real time through a radio module. Selection of the sensors was based on laboratory testing for accuracy, response delay and recovery, cross-sensitivity, and precision. The Kolibri was compared against rack-mounted continuous emissions monitoring system (CEMs) and another mobile sampling instrument (the "Flyer") that has been used in over ten open area pollutant sampling events. Our results showed that the time series of CO, CO2, and PM2.5 concentrations measured by the Kolibri agreed well with those from the CEMs and the Flyer, with a laboratory- tested percentage error of 4.9%, 3%, and 5.8%, respectively. The VOC emission factors obtained using the Kolibri were consistent with existing literature values that relate concentration to combustion efficiency. The potential effect of rotor downwash on particle sampling was investigated in an indoor laboratory and the preliminary results suggested that its influence is minimal. Field application of the Kolibri sampling open detonation plumes indicated that the CO and CO2 sensors responded dynamically and their concentrations co-varied with emission transients. The Kolibri system can be applied to various challenging open area scenarios such as fires, lagoons, flares, and landfills.

Characterization of Emissions from Liquid Fuel and Propane Open Burns.

The effect of accidental fires are simulated to understand the response of items such as vehicles, fuel tanks, and military ordnance and to remediate the effects through re-design of the items or changes in operational procedures. The comparative combustion emissions of using jet propellant (JP-5) liquid fuel pools or a propane manifold grid to simulate the effects of accidental fires was investigated. A helium-filled tethered aerostat was used to maneuver an instrument package into the open fire plumes to measure CO, CO2, fine particulate matter (PM2.5), polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and elemental/organic/total carbon (EC/OC/TC). The results showed that all emissions except CO2 were significantly higher from JP-5 burns than from propane. The major portion of the PM mass from fires of both fuels was less than 1 µm in diameter and differed in carbon content. The PM2.5 emission factor from JP-5 burns (129 ± 23 g/kg Fuelc) was approximately 150 times higher than the PM2.5 emission factor from propane burns (0.89 ± 0.21 g/kg Fuelc). The PAH emissions as well as some VOCs were more than one hundred times higher for the JP-5 burns than the propane burns. Using the propane test method to study flammability responses, the environmental impact of PM2.5, PAHs, and VOCs would be reduced by 2300, 700, and 100 times per test, respectively.

Aerostat-based sampling of emissions from open burning and open detonation of military ordnance.

Emissions from open detonation (OD), open burning (OB), and static firing (SF) of obsolete military munitions were collected using an aerostat-lofted sampling instrument maneuvered into the plumes with remotely controlled tether winches. PM2.5, PM10, metals, volatile organic compounds (VOCs), energetics, and polyaromatic hydrocarbons (PAHs) were characterized from 121 trials of three different munitions (Composition B (hereafter, "Comp B"), V453, V548), 152 trials of five different propellants (M31A1E1, M26, SPCF, Arc 451, 452A), and 12 trials with static firing of ammonium perchlorate-containing Sparrow rocket motors. Sampling was conducted with operational charge sizes and under open area conditions to determine emission levels representative of actual disposal practices. The successful application of the tethered aerostat and sampling instruments demonstrated the ability to sample for and determine the first ever emission factors for static firing of rocket motors and buried and metal-cased OD, as well as the first measurements of PM2.5 for OB and for surface OD.

Emission factors from aerial and ground measurements of field and laboratory forest burns in the southeastern US: PM2.5, black and brown carbon, VOC, and PCDD/PCDF.

Aerial- and ground-sampled emissions from three prescribed forest burns in the southeastern U.S. were compared to emissions from laboratory open burn tests using biomass from the same locations. A comprehensive array of emissions, including PM2.5, black carbon (BC), brown carbon (BrC), carbon dioxide (CO2), volatile organic compounds (VOCs), and polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were sampled using ground-based and aerostat-lofted platforms for determination of emission factors. The PM2.5 emission factors ranged from 14 to 47 g/kg biomass, up to three times higher than previously published studies. The biomass type was the primary determinant of PM2.5, rather than whether the emission sample was gathered from the laboratory or the field and from aerial- or ground-based sampling. The BC and BrC emission factors ranged from 1.2 to 2.1 g/kg biomass and 1.0 to 1.4 g/kg biomass, respectively. A decrease in BC and BrC emission factors with decreased combustion efficiency was found from both field and laboratory data. VOC emission factors increased with decreased combustion efficiency. No apparent differences in averaged emission factors were observed between the field and laboratory for BC, BrC, and VOCs. The average PCDD/PCDF emission factors ranged from 0.06 to 4.6 ng TEQ/kg biomass.

Emissions from open burning of simulated military waste from forward operating bases.

Emissions from open burning of simulated military waste from forward operating bases (FOBs) were extensively characterized as an initial step in assessing potential inhalation exposure of FOB personnel and future disposal alternatives. Emissions from two different burning scenarios, so-called "burn piles/pits" and an air curtain burner/"burn box", were compared using simulated FOB waste from municipal and commercial sources. A comprehensive array of emissions was quantified, including CO(2), PM(2.5), volatile organic compounds (VOCs), polyaromatic hydrocarbons (PAHs), polychlorinated dibenzodioxins and -furans (PCDDs/PCDFs), polybrominated dibenzodioxins and -furans (PBDDs/PBDFs), and metals. In general, smoldering conditions in the burn box and the burn pile led to similar emissions. However, when the burn box underwent periodic waste charging to maintain sustained combustion, PM(2.5), VOCs, and PAH emissions dropped considerably compared to smoldering conditions and the overall burn pile results. The PCDD/PCDF and PBDD/PBDF emission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smoldering combustion in the burn piles.

Semivolatile and volatile organic compound emissions from wood-fired hydronic heaters.

Emissions including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), polyaromatic hydrocarbons (PAHs), and volatile organic compounds (VOCs), were sampled from different wood-fired hydronic heater (HH) technologies. Four commercially available HH technologies were studied: a single-stage conventional combustor with natural updraft, a three-stage downdraft combustion system, a bottom-fed pellet burner, and a two-stage heater with both a combustion and gasification chamber. The fuel consisted of three wood types (red oak, white pine, and white ash), one hardwood pellet brand, and one fuel mixture containing 95% red oak and 5% residential refuse by weight. The various HHs and fuel combinations were tested in a realistic homeowner fuel-charging scenario. Differences in emission levels were found between HH technologies and fuel types. PCDD/PCDF emissions ranged from 0.004 to 0.098 ng toxic equivalency/MJ(input) and PAHs from 0.49 to 54 mg/MJ(input). The former was increased by the presence of 5% by weight refuse. The white pine fuel had the highest PAH emission factor, while the bottom fed pellet burner had the lowest. The major VOCs emitted were benzene, acetylene, and propylene. The highest emissions of PAHs, VOCs, and PCDDs/PCDFs were observed with the conventional unit, likely due to the rapid changes in combustion conditions effected by the damper opening and closing.

Aerostat-lofted instrument and sampling method for determination of emissions from open area sources.

An aerostat-borne instrument and sampling method was developed to characterize air samples from area sources, such as emissions from open burning. The 10 kg battery-powered instrument system, termed "the Flyer", is lofted with a helium-filled aerostat of 4m nominal diameter and maneuvered by means of one or two tethers. The Flyer can be configured variously for continuous CO2 monitoring, batch sampling of semi-volatile organic compounds (SVOCs), volatile organic compounds (VOCs), black carbon, metals, and PM by size. The samplers are controlled by a trigger circuit to avoid unnecessary dilution from background sampling when not within the source plume. The aerostat/Flyer method was demonstrated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnance. A carbon balance approach was used to derive emission factors that showed excellent agreement with published values.