Dennis Tabor

PCDD/F, PBDD/F, and PBDE Emissions from Open Burning of a Residential Waste Dump

This work reports on the first known field study determining emission factors for polychlorinated and polybrominated dibenzodioxins/dibenzofurans (P[C/B]DDs/Fs) and polybrominated diphenyl ethers (PBDEs) from open burning of domestic waste. Two burning waste dump sites in Mexico were sampled using high-volume samplers mounted to a mobile sampling boom. Concurrent measurements of CO and CO(2) allowed determination of emission factors via the carbon balance method. PCDD/F emission factors averaged 823 ng toxic equivalency (TEQ)/kg C(burned) (N = 8, 68% relative standard deviation, RSD), a value at least five times higher than those from previous tests with domestic waste burned in barrels and approximately 2000 times higher than those from stacks of modern municipal waste combustors. These emission factors appear to be related to combustion quality, as conditions conducive to smoldering combustion, rather than flaming combustion, resulted in higher emission factors. Emissions of 40 PBDE congeners, likely originating from brominated flame retardants, averaged 724 mug/kg C(burned) (RSD = 96%) and had congener patterns similar to those of reported atmospheric sampling. Emissions of PBDDs/Fs were similar in magnitude to their chlorinated counterparts, averaging 470 ng TEQ/kg C(burned) (RSD = 105%), and may originate as reaction products of PBDE combustion or as thermally desorbed impurities from the PBDE flame retardant.

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.

Same-Sample Determination of Ultratrace Levels of Polybromodiphenylethers, Polybromodibenzo-p-dioxins/Furans, and Polychlorodibenzo-p-dioxins/Furans from Combustion Flue Gas

The analytical method used for determination of polychlorinated dibenzo-p-dioxins and -furans (PCDDs/Fs) emissions from municipal waste combustors (MWCs) and other stationary sources was modified and validated to additionally allow for analysis of ultratrace levels of polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and -furans (PBDDs/Fs) from a common flue gas sample. Potential methodological problems related to physicochemical properties of brominated compounds, including UV- and temperature-induced debromination and degradation, were addressed. The selection of solvents, optimization of extraction time, and adaptation of the cleanup and fractionation steps increased mean recoveries of (13)C(12)-labeled PBDE and PBDD/F isotope dilution surrogates about 18% and 25%, respectively. The customary liquid chromatography isolation of PBDEs and PBDDs/Fs was replaced by optimization of high-resolution gas chromatography to separate target PBDFs (2,3,7,8-Br-substituted) from potentially interfering PBDEs before mass spectroscopic identification. The optimized method allowed quantitative determination of 56 mono- through decabromodiphenylether congeners, 15 congeners of 2,3,7- and 2,3,7,8-Br-substituted tri- to octabromodibenzo-p-dioxins and -furans, and all 210 polychlorinated dibenzo-p-dioxins and -furans present in the flue gas at levels of picogram to microgram per normalized cubic meter.

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 combustors 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.

Toxicity comparison of chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in industrial source samples by HRGC/HRMS and enzyme immunoassay.

Limited information is available on the applicability of polychlorinated dibenzo-p-dioxin/furan (PCDD/F) toxicity assays to their brominated counterparts: polybrominated dibenzo-p-dioxins/furans (PBDDs/Fs). We estimated the toxicity of mixtures of chlorinated, brominated, and mixed bromochloro-dioxins and -furan (PBCDDs/Fs) laboratory standards using a chemically-activated luciferase gene expression cell bioassay (CALUX). The relative effects potency (REP) values obtained were comparable to the World Health Organization (WHO) toxic equivalency factors (TEFs) and in agreement with the concept of additive congener toxicity of mixtures of dioxins and furans. Enzyme immunoassay (EIA)-based toxic equivalents (TEQs), however, showed overestimation for PCDDs/Fs (0-4 orders of magnitudes higher) and underestimation for PBDDs/Fs (0-1 orders of magnitude lower) when compared to high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS)-based TEQ calculation (using WHO TEFs) in samples from an industrial source line. No correlation was found between the EIA and the HRGC/HRMS data, which could be attributed to differences in homologue-specific cross-reactivity responses, sample matrix type, and presence of other compounds competing for antibody binding in the immunoassay.

PBDDs/Fs and PCDDs/Fs in the raw and clean flue gas during steady state and transient operation of a municipal waste combustor.

Concentrations of polybrominated dibenzo-p-dioxins, and -dibenzofurans (PBDDs/Fs) and polychlorinated dibenzo-p-dioxins, and -dibenzofurans (PCDDs/Fs), were determined in the pre- and post-air pollution control system (APCS) flue gas of a municipal waste combustor (MWC). Operational transients of the combustor were found to considerably increase levels of PBDDs/Fs and PCDDs/Fs compared to steady state operation, both for the raw and clean flue gas; ΣPBDDs/Fs increased from 72.7 to 700 pg dscm(-1) in the raw, pre-APCS gas and from 1.45 to 9.53 pg dscm(-1) in the post-APCS flue gas; ΣPCDDs/Fs increased from 240 to 960 ng dscm(-1) in the pre-APCS flue gas, and from 1.52 to 16.0 ng dscm(-1) in the post-APCS flue gas. The homologue profile of PBDDs/Fs and PCDDs/Fs in the raw flue gas (steady state and transients) was dominated by hexa- and octa-isomers, while the clean flue gas homologue profile was enriched with tetra- and penta-isomers. The efficiency of the APCS for PBDD/F and PCDD/F removal was estimated as 98.5% and 98.7%, respectively. The cumulative TEQ(PCDD/F+PBDD/F) from the stack was dominated by PCDD/F: the TEQ of PBDD/F contributed less than 0.1% to total cumulative toxic equivalency of MWC stack emissions.

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.

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.

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.

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.