Gas and particle emissions from rifle and pistol firing.

Emissions were sampled from firing an M4 carbine rifle and a M9 (military issue of Beretta 75 FS 9 mm pistol) to develop sampling methods and assess potential exposures and range contamination issues. Breech and muzzle emissions were sampled from the rifle when firing M855A1 ammunition (lead (Pb)-free slugs) in single- and triple-shot burst mode and from single pistol shots when firing 9 mm XM1152 ammunition (not Pb-free). Emissions were sampled for carbon monoxide (CO), carbon dioxide (CO2), methane, hydrogen cyanide, ammonia, particulate matter by size, polycylic aromatic hydrocarbons, and volatile organics. Analyses on the particles included elemental composition, size distribution, carbon composition (black, total, organic, and elemental carbon), and particle composition and morphology. Emission concentrations from both the rifle and pistol were characterized by CO/CO2 ratios between, approximately, 1/1 and 2/1, respectfully, indicating incomplete carbon oxidation. The initial particle size distribution was dominated in number by particles smaller than 40 nm but the high particle concentrations led to rapid agglomeration. The abundance of CO and metals of inhalable particle size are noteworthy and indicate that further assessment of exposure would determine potential inhalation health hazards, particularly in indoor firing ranges.

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.

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.

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.

Characterization of the particulate emissions from the BP Deepwater Horizon surface oil burns.

Sampling of the smoke plumes from the BP Deepwater Horizon surface oil burns led to the unintentional collection of soot particles on the sail of an instrument-bearing, tethered aerostat. This first-ever plume sampling from oil burned at an actual spill provided an opportunistic sample from which to characterize the particles' chemical properties for polycyclic aromatic hydrocarbons (PAHs), organic carbon, elemental carbon, metals, and polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) and physical properties for size and nanostructure. Thermal-optical analyses indicated that the particulate matter was 93% carbon with 82% being refractory elemental carbon. PAHs accounted for roughly 68µg/g of the PM filter mass and 5mg/kg oil burned, much lower than earlier laboratory based studies. Microscopy indicated that the soot is distinct from more common soot by its aggregate size, primary particle size, and nanostructure. PM-bound metals were largely unremarkable but PCDD/PCDF formation was observed, contrary to other's findings. Levels of lighter PCDD/PCDF and PAH compounds were reduced compared to historical samples, possibly due to volatilization or photo-oxidation.

14th congress of combustion by-products and their health effects-origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources.

The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the "Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources". The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

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.

Global emissions of trace gases, particulate matter, and hazardous air pollutants from open burning of domestic waste.

The open burning of waste, whether at individual residences, businesses, or dump sites, is a large source of air pollutants. These emissions, however, are not included in many current emission inventories used for chemistry and climate modeling applications. This paper presents the first comprehensive and consistent estimates of the global emissions of greenhouse gases, particulate matter, reactive trace gases, and toxic compounds from open waste burning. Global emissions of CO2 from open waste burning are relatively small compared to total anthropogenic CO2; however, regional CO2 emissions, particularly in many developing countries in Asia and Africa, are substantial. Further, emissions of reactive trace gases and particulate matter from open waste burning are more significant on regional scales. For example, the emissions of PM10 from open domestic waste burning in China is equivalent to 22% of China's total reported anthropogenic PM10 emissions. The results of the emissions model presented here suggest that emissions of many air pollutants are significantly underestimated in current inventories because open waste burning is not included, consistent with studies that compare model results with available observations.

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.

Quality control for sampling of PCDD/PCDF emissions from open combustion sources.

Both long duration (>6h) and high temperature (up to 139°C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m(3) sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6h of ambient air sampling (171 m(3)) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145°C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87°C; increasing the volume fourfold reduced this temperature to 73°C.

Emissions from small-scale burns of simulated deployed U.S. military waste.

U.S. military forces have historically relied on open burning as an expedient method of volume reduction and treatment of solid waste during the conflicts in Afghanistan and Iraq. This study is the first effort to characterize a broad range of pollutants and their emission factors during the burning of military waste and the effects that recycling efforts, namely removing plastics, might have on emissions. Piles of simulated military waste were constructed, burned, and emissions sampled at the U.S. Environmental Protection Agency (EPA) Open Burn Testing Facility (OBTF), Research Triangle Park, NC. Three tests contained polyethylene terephthalate (PET #1 or PET) plastic water bottles and four did not. Emission factors for polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), particulate matter (PM(10), PM(2.5)), polychlorinated and polybrominated dioxins/furans (PCDD/F and PBDD/F), and criteria pollutants were determined and are contained within. The average PCDD/F emission factors were 270 ng-toxic equivalency (TEQ) per kg carbon burned (ng-TEQ/kg Cb), ranging from 35 to 780 ng-TEQ/kg Cb. Limited testing suggests that targeted removal of plastic water bottles has no apparent effect on reducing pollutants and may even promote increased emissions.

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.

Effect of 2,4-dichlorophenoxyacetic acid (2,4-D) on PCDD/F emissions from open burning of biomass.

To understand the effect of leaf-surface pesticides on emissions of PCDD/F during biomass burns, nine combustion experiments simulating the open burning of biomass were conducted. Needles and branches of Pinus taeda (Loblolly pine) were sprayed with the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) at 1 and 10 times the manufacturer's recommended application concentration. The biomass was then dried overnight, burned in an open burn test facility, and emission samples were collected, analyzed, and compared against emission samples from burning untreated biomass. Blank tests and analysis of PCDD/F in the raw biomass were also performed. Emission results from burning a water-sprayed control show a ~20-fold increase in PCDD/F levels above that of the raw biomass alone, implicating combustive formation versus simple volatilization. Results from burns of pine branches sprayed with pesticide showed a statistically significant increase in the PCDD/F TEQ emissions when burning biomass at ten times the recommended pesticide concentration (from 0.22 to 1.14 ng TEQ/kg carbon burned (C(b)), both ND = 0). Similarly, a 150-fold increase in the total PCDD/F congener mass (tetra- to octa-chlorinated D/F) above that of the control was observed (from 52 to 7800 ng/kg C(b)), confirming combustive formation of PCDD/F from 2,4-D. More replicate testing is needed to evaluate effects at lower pesticide concentrations.

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.

Emissions from open burning of used agricultural pesticide containers.

Emissions from simulated open burning of used agricultural pesticide containers were sampled for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), polycyclic aromatic hydrocarbon compounds (PAHs), and particle matter (PM(10) and PM(2.5)). Clean high density polyethylene (HDPE) containers, containers with trace pesticide, and triple-rinsed containers were burned separately in an open combustion facility and their emissions compared. Two common chlorinated pesticides were used: 2,4-dichlorophenoxyacetic acid (2,4-D) and 1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine (atrazine). PCDD/PCDF emission factors ranged from 0.1 to 24ng toxic equivalents (TEQ)/kg C burned with a mean and median of 4.9 and 1.9ng TEQ/kgC burned, respectively. In a limited number of trials, the trace 2,4-D in the HDPE container led to a statistically significant increase in PCDD/PCDF formation compare to all other conditions. Residual atrazine did not lead to more PCDD/PCDF than the unrinsed 2,4-D container. Total (16 compounds) PAH emission factors varied from 1.5 to 6.7mg/kgC burned. These limited data suggest that rinsing the 2,4-D container prior to burning reduces both PCDD/PCDF and PAH emissions. Nine PM(2.5) emission factors ranged from 9 to 35mg/gC burned and ten PM(10) values ranged from 6 to 43mg/gC burned. Neither pesticide appeared to have any effect on PM concentration.

Open burning of household waste: Effect of experimental condition on combustion quality and emission of PCDD, PCDF and PCB.

Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100 kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire--"stirring"--promotes better combustion (as evidenced by lower CO/CO(2) ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning - while still highly variable - tends to be greater in the later (smoldering) phases of burning when the CO/CO(2) ratio increases.

Near-real-time combustion monitoring for PCDD/PCDF indicators by GC-REMPI-TOFMS.

The boiler exit flue gas of a municipal waste combustor was sampled to evaluate an online monitoring system for chlorobenzene congeners as indicators of polychlorinated dibenzodioxin and dibenzofuran (PCDD/PCDF) concentrations. Continuous measurements of chlorobenzene congeners using gas chromatography coupled to a resonance-enhanced multiphoton ionization - time-of-flight mass spectrometry (GC-REMPI-TOFMS) system were compared over 5-min periods with conventional sampling methods for PCDD/PCDF. Three pairs of values were taken every hour over a period of three days to characterize the combustor's response to transient operating conditions (shutdowns and startups). Isolation of specific chlorobenzene congeners from other same-mass compounds was accomplished by using a GC column separator ahead of the REMPI-TOFMS. The 50-fold variation of PCDD/PCDF concentration was paralleled by similar changes in monitored compounds of 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4,5-tetrachlorobenzene. A correlation of R = 0.85 and 0.89 was established between 40 pairs of simultaneous 5-min GC-REMPI-TOFMS measurements of 1,2,4-trichlorobenzene and 5 min conventional sampling and analysis for the TEQ and Total measures of PCDD/PCDF, respectively. The GC-REMPI-TOFMS system can be used to provide frequent measures of correlative PCDD/PCDF concentration thereby allowing for an understanding of measures to minimize PCDD/PCDF formation and develop operational feedback to limit emissions.

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.