PCDD/F,PCB, HxCBz,PAH, and PM emission factors for fireplace and woodstove combustion in the San Francisco Bay region

Emissions from residential fireplace and woodstove appliances burning fuels available from the San Francisco Bay area were sampled for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HxCBz), particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs, and the monosaccharide levoglucosan. Emission factors for these pollutants were determined, the first known characterization of this extent. Common California natural firewoods and manufactured artificial logs were tested under operating conditions intended to reflect domestic use patterns in the Bay area, which are primarily episodic burning for aesthetic reasons. Emission factors were determined by fuel type, fuel weight, mass emission rates, and energy output, highlighting differences between fuel and combustion facility type. Average PCDD/F emissions factors ranged from 0.25 to 1.4 ng toxic equivalency (TEQ)/kg of wood burned for natural wood fuels and 2.4 ng TEQ/kg for artificial logs. The natural wood emission factors are slightly lower than those which had been estimated for the U.S. inventory. Background-corrected PCBs emitted from woodstove/oak combustion (8370 ng/kg) are 3 orders of magnitude higher in mass than total PCDDs/Fs; however, their toxicity (0.014 ng TEQ/kg) is significantly lower. HxCBz emission factors varied from 13 to 990 ng/kg and were likely fuel- and appliance-specific. Relative PAH concentrations of particle-phase compounds and emission factors were consistent with others' findings. A total of 32 PAH compounds, ranging in concentration from 0.06 to 7 mg/kg, amounted to between 0.12 and 0.38% of the PM mass, depending on the wood and facility type. Preliminary analyses suggest relationships between wood combustion markers and PCDD/F levels.     

Emission factors, size distributions, and emission inventories of carbonaceous particulate matter from residential wood combustion in rural China

Published emission factors (EFs) often vary significantly, leading to high uncertainties in emission estimations. There are few reliable EFs from field measurements of residential wood combustion in China. In this study, 17 wood fuels and one bamboo were combusted in a typical residential stove in rural China to measure realistic EFs of particulate matter (PM), organic carbon (OC), and elemental carbon (EC), as well as to investigate the influence of fuel properties and combustion conditions on the EFs. Measured EFs of PM, OC, and EC (EF(PM), EF(OC), and EF(EC), respectively) were in the range of 0.38-6.4, 0.024-3.0, and 0.039-3.9 g/kg (dry basis), with means and standard derivation of 2.2 ± 1.2, 0.62 ± 0.64, and 0.83 ± 0.69 g/kg, respectively. Shrubby biomass combustion produced higher EFs than tree woods, and both species had lower EFs than those of indoor crop residue burning (p < 0.05). Significant correlations between EF(PM), EF(OC), and EF(EC) were expected. By using a nine-stage cascade impactor, it was shown that size distributions of PM emitted from tree biomass combustions were unimodal with peaks at a diameter less than 0.4 μm (PM(0.4)), much finer than the PM from indoor crop residue burning. Approximately 79.4% of the total PM from tree wood combustion was PM with a diameter less than 2.1 μm (PM(2.1)). PM size distributions for shrubby biomasses were slightly different from those for tree fuels. On the basis of the measured EFs, total emissions of PM, OC, and EC from residential wood combustion in rural China in 2007 were estimated at about 303, 75.7, and 92.0 Gg.     

Effect of fuels and domestic heating appliance types on emission factors of selected organic pollutants

This study reports on the first complex data set of emission factors (EFs) of selected pollutants from combustion of five fuel types (lignite, bituminous coal, spruce, beech, and maize) in six different domestic heating appliances of various combustion designs. The effect of fuel as well as the effect of boiler type was studied. In total, 46 combustion runs were performed, during which numerous EFs were measured, including the EFs of particulate matter (PM), carbon monoxide, polyaromatic hydrocarbons (PAH), hexachlorobenzene (HxCBz), polychlorinated dibenzo-p-dioxins and furans (PCDD/F), etc. The highest EFs of nonchlorinated pollutants were measured for old-type boilers with over-fire and under-fire designs and with manual stoking and natural draft. Emissions of the above-mentioned pollutants from modern-type boilers (automatic, downdraft) were 10 times lower or more. The decisive factor for emission rate of nonchlorinated pollutants was the type of appliance; the type of fuel plays only a minor role. Emissions of chlorinated pollutants were proportional mainly to the chlorine content in fuel, but the type of appliance also influenced the rate of emissions significantly. Surprisingly, higher EFs of PCDD/F from combustion of chlorinated bituminous coal were observed for modern-type boilers (downdraft, automatic) than for old-type ones. On the other hand, when bituminous coal was burned, higher emissions of HxCBz were found for old-type boilers than for modern-type ones.     

Emission of polycyclic aromatic hydrocarbons, toxicity, and mutagenicity from domestic cooking using sawdust briquettes, wood, and kerosene

Smoke samples, in both gas and particulate matter (PM) phases, of the three domestic stoves were collected using U.S. EPA modified method 5 and were analyzed for 17 PAH (HPLC-UV), acute toxicity (Microtox test), and mutagenicity (Amestest). The gas phase of smoke contributed > or = 95% of 17 PAH, > or = 96% of toxicity, and > or = 60% of mutagenicity. The highest emission factor of 17 PAH was from sawdust briquettes (260 mg/kg), but the highest emission of 11 genotoxic PAH was from kerosene (28 mg/kg). PM samples of kerosene smoke were not toxic. The total toxicity emission factor was the highest from sawdust, followed by kerosene and wood fuel. Smoke samples from the kerosene stove were not mutagenic. TA98 indicated the presence of both direct and indirect mutagenic activities in PM samples of sawdust and wood fuel but only direct mutagenic activities in the gas phase. TA100 detected only direct mutagenic activities in both PM and gas-phase samples. The higher mutagenicity emission factor was from wood fuel, 12 x 10(6) revertants/kg (TA100-S9) and 3.5 x 10(6) (TA98-S9), and lower from sawdust, 2.9 x 10(6) (TA100-S9) and 2.8 x 10(6) (TA98-S9). The low burning rate and high efficiency of a kerosene stove have resulted in the lowest PAH, toxicity, and mutagenicity emissions from daily cooking activities. The bioassays produced toxicity and mutagenicity results in correspondence with the PAH content of samples. The tests could be used for a quick assessment of potential health risks.     

Emission of PCDD/F, PCB, and HCB from combustion of firewood and pellets in residential stoves and boilers

To assess potential emissions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) from residential combustion of biofuels, experiments were performed in which various types of pellets and firewood were combusted in four types of stoves and boilers, with both full and reduced rates of air supply. Intermittent combustion of wood pellets resulted in emissions of 11 ng-(WHO-TEQ)/kg combusted fuel (dry weight). A modern, environmentally certified boiler yielded somewhat lower emissions of PCCD/F and PCB than a wood stove. Both gave <0.1 ng(WHO-TEQ)/m3n (1.3-6.5 ng(WHO-TEQ)/kg) and considerably lower emissions than an old boiler (7.0-13 ng(WHO-TEQ)/kg). No positive effect on emissions could be observed in full air combustion (simulating the use of a heat storage tank) compared to combustion with reduced air. Two of the wood combustion experiments included paper and plastic waste fuels. Chlorine-containing plastic waste gave rise to high emissions: ca. 310 ng(WHO-TEQ)/ kg over the whole combustion cycle. The homologue profiles of PCDD/Fs show characteristic differences between ashes and flue gas from combustions with different levels of air supply. These differences do not, however, seem to have any correlation to the relative amount of toxic congeners.     

Emission characteristics of carbonaceous particles from various residential coal-stoves in China

China is thought to be the most important contributor to the global burden of carbonaceous aerosols, and residential coal combustion is the greatest emission source of black carbon (BC). In the present study, two high-efficiency household coal-stoves are tested together with honeycomb-coal-briquettes and raw-coal-chunks of nine different coals. Coal-burning emissions are collected onto quartz fiber filters (QFFs) and analyzed by a thermal-optical transmittance (TOT) method. Emission factors (EFs) of particulate matter (PM), organic carbon (OC), and elemental carbon (EC) are systematically measured, and the average EFs are calculated by taking into account our previous data. For bituminous coal-briquette and -chunk, EFs of PM, OC, and EC are 7.33, 4.16, and 0.08 g/kg and 14.8, 5.93, and 3.81 g/kg, respectively; and for anthracite-briquette and -chunk, they are 1.21, 0.06, and 0.004 g/kg and 1.08, 0.10, and 0.007 g/kg, respectively. Annual estimates for PM, OC, and EC emissions in China are calculated for the years of 2000 and 2005 according to the EFs and coal consumptions, and the results are consistent with our previous estimates. Bituminous coal-chunk contributes 68% and 99% of the total OC and EC emissions from household coal burning, respectively. Additionally, a new model of Aethalometer (AE90) is introduced into the sampling system to monitor the real-time BC concentrations. On one hand, AE90 provides a set of EFs for optical BC in parallel to thermal-optical EC, and these two data are generally comparable, although BC/EC ratios vary in different coal/stove combinations. On the other hand, AE90 offers a chance to observe the variation of BC concentrations during whole burning cycles, which demonstrates that almost all BC emits into the flue during the initial period of 15 min after coal addition into household stoves.     

Emissions of polychlorinated dibenzodioxins and dibenzofurans and polychlorinated biphenyls from uncontrolled burning of garden and domestic waste (backyard burning)

To assess emissions of dioxins (chlorinated dibenzodioxins and dibenzofurans) and PCB from uncontrolled domestic combustion of waste ("backyard burning"), test combustions in barrels and open fires were monitored. The waste fuels used were garden waste, paper, paper and plastic packaging, refuse-derived fuel (RDF), PVC, and electronic scrap. Combustions including PVC and electronic scrap emitted several orders of magnitude more dioxins than the other waste fuels. Emissions from the other fuels had considerable variations, but the levels were difficult to relate to waste composition. Emission factors of PCDD/F and PCB from the backyard burning ranged from 2.2 to 13 000 ng (WHO-TEQ)/kg. The levels found in ash usually were less than 5% of the total. For assessment of total emissions of dioxins and PCB from backyard burning of low and moderately contaminated wastes, an emission factor range of 4-72 ng (WHO-TEQ)/kg is suggested. These figures implythat combusting waste in the backyard could contribute substantially to total emissions, even if the amounts of fuel involved are equivalent to just a few tenths of a percent of the amounts combusted in municipal waste incinerators.     

Aerostat sampling of PCDD/PCDF emissions from the Gulf oil spill in situ burns

Emissions from the in situ burning of oil in the Gulf of Mexico after the catastrophic failure of the Deepwater Horizon drilling platform were sampled for polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/PCDF). A battery-operated instrument package was lofted into the plumes of 27 surface oil fires over a period of four days via a tethered aerostat to determine and characterize emissions of PCDD/PCDF. A single composite sample resulted in an emission factor of 2.0 ng toxic equivalency (TEQ) per kg of carbon burned, or 1.7 ng TEQ per kg of oil burned, determined by a carbon balance method. Carbon was measured as CO(2) plus particulate matter, the latter of which has an emission factor of 0.088 kg/kg carbon burned. The average plume concentration approximately 200-300 m from the fire and about 75-200 m above sea level was <0.0002 ng TEQ/m(3).     

Effect of moisture, charge size, and chlorine concentration on PCDD/F emissions from simulated open burning of forest biomass

Loblolly pine (Pinus taeda) was combusted at different charge sizes, fuel moisture, and chlorine content to determine the effect on emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) as well as copollutants CO, PM, and total hydrocarbons. The experiments were performed in an enclosed chamber under conditions simulating open, prescribed burns of forest biomass. Burn progress was monitored through on line measurement of combustion gases and temperature while PCDD/F concentrations were determined by ambient sampling methods. PCDD/F toxic equivalency (TEQ) and total (tetra- to octa-CDD/F) emission factors were independent of charge size (1-10 kg) and moisture content (7-50%). However, the lower chlorinated, mono- to tri-CDD/F compounds were increased by poor combustion conditions: combustion efficiency lower than 0.919 was generally found when the moisture content was higher than 30%. The increase of fuel matrix chlorine from 0.04% to 0.8% using a brine bath resulted in about a 100-fold increase of PCDD/F to about 90 ng TEQ/kg of carbon burned, C(b). These emission factors were linearly dependent on Cl concentration in the biomass. PCDD 2,3,7,8-Cl-substituted congeners and homologue patterns were also influenced by the addition of chlorine resulting in emissions with a higher abundance of the most toxic congeners (TeCDD and PeCDD). When both chlorine and moisture content were increased in the fuel, a simultaneous effect of the two parameters was observed. The increased TEQ values expected from higher Cl concentrations were mitigated by the presence of water, giving MCE = 0.868, promoting formation of mono- to tri-PCDD/F, and lowering the TEQ value. Open burn simulations were used to study PCDD/F formation in different combustion conditions providing a mathematical correlation between PCDD/F emissions and chlorine and moisture content in the fuel.     

PCDD and PCDF emissions from simulated sugarcane field burning

The emissions from simulated sugarcane (Saccharum officinarum) field burns were sampled and analyzed for polychlorinated dibenzodioxins and dibenzofurans (PCDDs and PCDFs). Sugarcane leaves from Hawaii and Florida were burned in a manner simulating the natural physical dimensions and biomass density found during the practice of preharvest field burning. Eight composite burn tests consisting of 3-33 kg of biomass were conducted, some with replicate samplers. Emission factor calculations using sampled concentration and measured mass loss compared well to rigorous carbon balance methods commonly used in field sampling. The two sources of sugarcane had distinctive emission levels, as did tests on separate seasonal gatherings of the Florida sugarcane. The average emission factor for two tests of Hawaii sugarcane was 253 ng toxic equivalents (TEQ)/kg of carbon burned (ng TEQ/kg(Cb)) (rsd = 16%) and for two gatherings of Florida sugarcane was 25 ng TEQ/kg(Cb) (N = 4, rsd = 50%) and 5 ng TEQ/kg(Cb) (N = 2, rsd = 91%). The Hawaii sugarcane, as well as most of the Florida sugarcane, had emission values which were well above the value of 5 ng TEQ/kg(Cb) commonly attributed to biomass combustion. Application of this emission factor range to the amount of U.S. sugarcane fields burned suggests that this practice may be a relatively minor source of PCDDs and PCDFs in the U.S. national inventory, but the limited sample size and range of results make this conclusion tenuous.     

Retene emission from residential solid fuels in China and evaluation of retene as a unique marker for soft wood combustion

Retene (1-methyl-7-isopropylphenanthrene) is often used as a marker for softwood combustion and for polycyclic aromatic hydrocarbon (PAH) source apportionment. The emission factors of retene (EF(RET)s) from 11 crop residues, 27 firewood fuels, and 5 coals were measured using traditional rural Chinese stoves. Retene was measured in combustion emissions from all of the residential fuels tested and EF(RET)s varied significantly among the fuels due to the differences in fuel properties and combustion conditions. EF(RET)s for pine (0.34 ± 0.08 mg/kg) and larch (0.29 ± 0.22 mg/kg) were significantly higher than those of other wood types, including fir and cypress (0.081 ± 0.058 mg/kg). However, EF(RET)s for crop residues varied from 0.048 ± 0.008 to 0.37 ± 0.14 mg/kg and were not significantly lower than those for softwood (0.074 ± 0.026 to 0.34 ± 0.08 mg/kg). The EF(RET)s for coal were very high and ranged from 2.2 ± 1.5 (anthracite briquette) to 187 ± 113 mg/kg (raw bituminous chunk). EF(RET) was positively correlated with EFs of coemitted particulate matter (EF(PM)) and phenanthrene (EF(PHE)) for crop residue and coal, but not for wood. In addition, the ratios of EF(PHE)/EF(RET) and EF(PM)/EF(RET) for coals were much lower than those for crop residues and wood. These data suggest that retene is not a unique PAH marker for softwood combustion and that coal combustion, in particular, should be taken into account when retene is used for PAH source apportionment.     

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 of parent, nitro, and oxygenated polycyclic aromatic hydrocarbons from residential wood combustion in rural china

Residential wood combustion is one of the important sources of air pollution in developing countries. Among the pollutants emitted, parent polycyclic aromatic hydrocarbons (pPAHs) and their derivatives, including nitrated and oxygenated PAHs (nPAHs and oPAHs), are of concern because of their mutagenic and carcinogenic effects. In order to evaluate their impacts on regional air quality and human health, emission inventories, based on realistic emission factors (EFs), are needed. In this study, the EFs of 28 pPAHs (EF(PAH28)), 9 nPAHs (EF(PAHn9)), and 4 oPAHs (EF(PAHo4)) were measured for residential combustion of 27 wood fuels in rural China. The measured EF(PAH28), EF(PAHn9), and EF(PAHo4) for brushwood were 86.7 ± 67.6, 3.22 ± 1.95 × 10(-2), and 5.56 ± 4.32 mg/kg, which were significantly higher than 12.7 ± 7.0, 8.27 ± 5.51 × 10(-3), and 1.19 ± 1.87 mg/kg for fuel wood combustion (p < 0.05). Sixteen U.S. EPA priority pPAHs contributed approximately 95% of the total of the 28 pPAHs measured. EFs of pPAHs, nPAHs, and oPAHs were positively correlated with one another. Measured EFs varied obviously depending on fuel properties and combustion conditions. The EFs of pPAHs, nPAHs, and oPAHs were significantly correlated with modified combustion efficiency and fuel moisture. Nitro-naphthalene and 9-fluorenone were the most abundant nPAHs and oPAHs identified. Both nPAHs and oPAHs showed relatively high tendencies to be present in the particulate phase than pPAHs due to their lower vapor pressures. The gas-particle partitioning of freshly emitted pPAHs, nPAHs, and oPAHs was primarily controlled by organic carbon absorption.     

Reductions in emissions of carbonaceous particulate matter and polycyclic aromatic hydrocarbons from combustion of biomass pellets in comparison with raw fuel burning

Biomass pellets are emerging as a cleaner alternative to traditional biomass fuels. The potential benefits of using biomass pellets include improving energy utilization efficiency and reducing emissions of air pollutants. To assess the environmental, climate, and health significance of replacing traditional fuels with biomass pellets, it is critical to measure the emission factors (EFs) of various pollutants from pellet burning. However, only a few field measurements have been conducted on the emissions of carbon monoxide (CO), particulate matter (PM), and polycyclic aromatic hydrocarbons (PAHs) from the combustion of pellets. In this study, pine wood and corn straw pellets were burned in a pellet burner (2.6 kW), and the EFs of CO, organic carbon, elemental carbon, PM, and PAHs (EF(CO), EF(OC), EF(EC), EF(PM), and EF(PAH)) were determined. The average EF(CO), EF(OC), EF(EC), and EF(PM) were 1520 ± 1170, 8.68 ± 11.4, 11.2 ± 8.7, and 188 ± 87 mg/MJ for corn straw pellets and 266 ± 137, 5.74 ± 7.17, 2.02 ± 1.57, and 71.0 ± 54.0 mg/MJ for pine wood pellets, respectively. Total carbonaceous carbon constituted 8 to 14% of the PM mass emitted. The measured values of EF(PAH) for the two pellets were 1.02 ± 0.64 and 0.506 ± 0.360 mg/MJ, respectively. The secondary side air supply in the pellet burner did not change the EFs of most pollutants significantly (p > 0.05). The only exceptions were EF(OC) and EF(PM) for pine wood pellets because of reduced combustion temperatures with the increased air supply. In comparison with EFs for the raw pine wood and corn straw, EF(CO), EF(OC), EF(EC), and EF(PM) for pellets were significantly lower than those for raw fuels (p < 0.05). However, the differences in EF(PAH) were not significant (p > 0.05). Based on the measured EFs and thermal efficiencies, it was estimated that 95, 98, 98, 88, and 71% reductions in the total emissions of CO, OC, EC, PM, and PAHs could be achieved by replacing the raw biomass fuels combusted in traditional cooking stoves with pellets burned in modern pellet burners.     

Congener-specific composition of polychlorinated naphthalenes, coplanar PCBs, dibenzo-p-dioxins, and dibenzofurans in the Halowax series

Concentrations and congener compositions of polychlorinated naphthalenes (PCNs), coplanar polychlorinated biphenyls (Co-PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) were determined in seven Halowax (HW) preparations. In HW 1000 and 1031, low-chlorinated naphthalenes (CNs) and in HW 1051, highly chlorinated naphthalenes were dominant, whereas tri- through penta-CNs were major homologues in other Halowaxes. Concentrations of Co-PCBs were in the range of 2.0-2600 ng/g. CB 105 and 118 were dominant in all Halowaxes. Concentrations of PCDDs/DFs were in the range of 92-5900 ng/g. The 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in Halowaxes calculated from the amounts of PCNs, Co-PCBs, and PCDDs/DFs were in the range of 2800-220,000 ng-TEQ/g. PCNs accounted for most of the total TEQs in Halowaxes, and the contribution of PCDDs/DFs and Co-PCBs to total TEQs was less than 1/1000 that of PCNs. Congeners that most significantly contributed to TEQs were CN 69, 73, 70, and 63. Total TEQs roughly estimated from the Japanese production of technical PCNs, 210 kg-TEQ, was about half from technical PCBs, 440 kg-TEQ on average.     

Discrimination of aerial deposition sources of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran downwind from a pulp mill near Ketchikan, Alaska

Drinking water is supplied by individual roof-catchment systems for homes and businesses near a dissolving sulfite pulp mill (now closed) located just north of Ketchikan in southeast Alaska. This study was conducted to determine if polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) found in the sediments of the roof-catchment cisterns resulted from historical deposition of stack emissions from the pulp mill's multi-fuel power boilers. Fly ash from the power boilers had maximum total PCDD/F concentrations of 3.08 x 10(5)-3.10 x 10(6) ng/kg, which resulted from combustion of bleach plant wastewater sludge and saltwater-soaked wood waste. Cistern sediments had maximum total PCDD/F concentrations of 7.71 x 10(4) ng/kg. Potential sources of PCDDs/Fs in the cistern sediments were considered to be automobile exhaust, heating oil combustion, and private trash burning as well as pulp mill boiler emissions. Discriminant analysis was used to analyze differences between profiles of tetra through octa homologue classes of PCDDs/ Fs (defined as proportional contributions to total concentration) from different source terms. Homologue profiles of potential sources from Ketchikan included in this analysis were fly ash collected from the mill's power boilers and soils collected from background areas (areas with similar PCDD/F sources as the residences [e.g., auto exhaust and burn barrels] near the mill but beyond the zone of aerial deposition of emissions from the mill). Profiles for emissions from automobile exhaust, fertilizers, oil heating, residential trash burning, and residential wood heating were also included in the source "training" data set (for the discriminant analysis) using data from published literature. The classification rules developed from the discriminant analysis were applied to the following test media sampled at Ketchikan: roof-catchment cistern sediments and soils collected from areas in the vicinity of the mill's power boilers (i.e., nearby residential or commercial [developed] areas, on the mill property, and nearby forestlands). The homologue profiles of cistern sediment and nearby developed area soil samples were similar to background soils, whereas the profiles for the forestland soil samples (influenced by emissions from the mill but not other anthropogenic sources) closely matched the fly ash pattern. The homologue profiles of the emission sources from published data were more similar to one another than either background soils or fly ash. Soil samples from the mill property were classified as members of all source groups. On the basis of these analyses, the composition of PCDDs/Fs detected in the cistern sediments is typical of Ketchikan background conditions and not reflective of mill emissions.     

Wintertime organic aerosols in Christchurch and Auckland, New Zealand: contributions of residential wood and coal burning and petroleum utilization

Wintertime PM10 samples from two New Zealand cities (Christchurch and Auckland) have been characterized using gas chromatography - mass spectrometry for biomass burning tracers, hopanes, n-alkanes, fatty acids, n-alkanols and sugars. The aerosol samples of Christchurch, which were heavily influenced by residential wood and coal burning, showed substantially higher ambient concentrations for most of the organic compounds than those of Auckland, where major sources of aerosols were vehicular emissions and sea-salt. Mass ratios between the biomass burning tracers studied were found to be significantly different (e.g., beta-sitosterol to nssK+ ratios were more than three times higher in Christchurch than in Auckland), although levoglucosan to nssK+ ratios were similar at the both sites. We also estimated, for the first time using stereochemical configurations of hopanes, that 60% of fossil fuel emissions came from petroleum utilization with the remaining 40% being from coal burning in Christchurch. In contrast, contribution of coal burning was negligible in Auckland. Moreover, contributions of most biomass burning tracers to organic carbon (OC) were significantly higher in Christchurch than in Auckland. On the other hand, saccharides (excluding levoglucosan) and hopanes accounted for larger fractions of OC in Auckland. This study demonstrates that intensive wood and coal burning can significantly affect organic aerosol composition in an urban environment.     

On-road emissions of PCDDs and PCDFs from heavy duty diesel vehicles

This work characterized emission factors of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from on-road sampling of three heavy duty diesel vehicles (HDDVs) under experimental conditions of city and highway driving; idling operation; high (>400 ppm) and low (<5 ppm) sulfur (S) fuels; and high mileage and rebuilt engine testing. Emission factors, homologue profiles, and isomer patterns were compared to determine whether the experimental conditions had an impact on PCDD/F emissions, or whether these conditions were uninfluential in determining a fleet-representative emission factor. For a single HDDV tested under conditions of a high mileage engine, a newly rebuilt engine, and the newly rebuilt engine with low S diesel fuel, emission factors were 0.023 (+/- 0.022), 0.008 (+/- 0.002), and 0.016 (+/- 0.013) ng toxic equivalency (TEQ)/km, respectively. These results may infer some limited condition-specific differences in PCDD/F emissions, but these differences do not appear to have a significant effect on the HDDV emission factor. An older HDDV with mechanical fuel controls resulted in a single test value of 0.164 ng TEQ/km, significantly higher than all other results. Observed differences in emission factors, homologue profiles, and TEQ-related isomer patterns from this on-vehicle sampling and others' tunnel sampling suggest limitations in our present characterization of fleet PCDD/F emissions.     

Emission of oxygenated polycyclic aromatic hydrocarbons from indoor solid fuel combustion

Indoor solid fuel combustion is a dominant source of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) and the latter are believed to be more toxic than the former. However, there is limited quantitative information on the emissions of OPAHs from solid fuel combustion. In this study, emission factors of OPAHs (EF(OPAH)) for nine commonly used crop residues and five coals burnt in typical residential stoves widely used in rural China were measured under simulated kitchen conditions. The total EF(OPAH) ranged from 2.8 ± 0.2 to 8.1 ± 2.2 mg/kg for tested crop residues and from 0.043 to 71 mg/kg for various coals and 9-fluorenone was the most abundant specie. The EF(OPAH) for indoor crop residue burning were 1-2 orders of magnitude higher than those from open burning, and they were affected by fuel properties and combustion conditions, like moisture and combustion efficiency. For both crop residues and coals, significantly positive correlations were found between EFs for the individual OPAHs and the parent PAHs. An oxygenation rate, R(o), was defined as the ratio of the EFs between the oxygenated and parent PAH species to describe the formation potential of OPAHs. For the studied OPAH/PAH pairs, mean R(o) values were 0.16-0.89 for crop residues and 0.03-0.25 for coals. R(o) for crop residues burned in the cooking stove were much higher than those for open burning and much lower than those in ambient air, indicating the influence of secondary formation of OPAH and loss of PAHs. In comparison with parent PAHs, OPAHs showed a higher tendency to be associated with particulate matter (PM), especially fine PM, and the dominate size ranges were 0.7-2.1 μm for crop residues and high caking coals and <0.7 μm for the tested low caking briquettes.     

Emissions of chromium, copper, arsenic, and PCDDs/Fs from open burning of CCA-treated wood

Aged and weathered chromated copper arsenate (CCA) treated wood was burned in an open burn research facility to characterize the air emissions and residual ash. The objectives were to simulate, to the extent possible, the combustion of such waste wood as might occur in an open field or someone's backyard; to characterize the composition and particle size distribution (PSD) of the emitted fly ash; to determine the partitioning of arsenic, chromium, and copper between the fly ash and residual ash; and to examine the speciation of the CCA elements. This work reports preliminary air emission concentrations and estimated emission factors for total particulate matter, arsenic (As), chromium (Cr), copper (Cu), and polychlorinated dibenzodioxins/dibenzofurans (PCDD/F) totals and toxic equivalents (TEQs). The partitioning of As, Cr, and Cu between the emitted fly ash and residual ash is examined and thermochemical predictions from the literature are used to explain the observed behavior. Results indicate a unimodal fly ash PSD between 0.1 and 1.0 microm diameter. In addition to a large carbonaceous component, between 11 and 14% of the As present in the burned CCA treated wood was emitted with the air emissions, with the remainder present in the residual ash. In contrast, less than 1% of both the Cr and Cu present in the wood was emitted with the air emissions. PCDD/F levels were unremarkable, averaging 1.7 ng TEQ/kg of treated wood burned, a value typical for wood combustion. Scanning electron microscopy (SEM) was unable to resolve inorganic particles consisting of Cu, Cr, or As in the wood samples, but X-ray absorption fine structure (XAFS) spectroscopy confirmed that the oxidation states of the CCA elements in the wood were Cu2+, Cr3+, and As5+. SEM examination of the fly ash samples revealed some inorganic microcrystals within the mostly carbonaceous fly ash, while XAFS spectroscopy of the same samples showed that the oxidation states after combustion were mixed Cu+ and Cu2+, Cr3+, and mixed As3+ and As5+. Estimates of the ratios of the mixed oxidation states based on the XAFS spectra were As3+/(total As) = 0.8-0.9 and Cu+/(total Cu) = 0.65-0.7. The Cu and Cr present in the fly ash were determined to coexist predominantly in the two oxide phases CuCrO2 and CuCr2O4. These results indicate that the open burning of CCA-treated wood can lead to significant air emissions of the more toxic trivalent form of As in particle sizes that are most respirable.