The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Control of PCDD/PCDF emissions from refuse-derived fuel combustors

This paper presents preliminary results of performance tests conducted at the Mid-Connecticut Refuse-Derived Fuel Facility in February 1989. The objectives of these performance tests were to evaluate the effects of combustion and flue gas cleaning process conditions on air pollution emissions and residue properties.     

PCB, PCDF, and PCDD exposure following a transformer fire: Chicago

On September 28, 1983, an electrical fire in a transformer vault resulted in the loss of 15 gallons of transformer oil composed of 65% PCBs (Aroclor 1260) and 35% trichlorobenzene and forced the precautionary evacuation of a major Chicago office building. A square foot wipe sample of soot on the vault ceiling contained 28,000 ng total TCDFs, 3,800 ng 2,3,7,8-TCDF, 40,000 ng PCDFs, 33,000 ng HxCDFs, 11,200 ng HpCDFs, 1,238 ng OCDFs, 314 ng HpCDDs, and 127 ng OCDDs. No PCDFs or PCDDs were detected in the blood (detection limit 3–40 ppt) of two fire fighters hospitalized with smoke inhalation nor of two office employees similarly exposed.     

PCDD, PCDF, AND PCB concentrations in human milk from two areas in Finland

Concentrations of 17 toxic 2,3,7,8-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and of 36 polychlorinated biphenyl congeners (PCBs) were analyzed from 167 randomly sampled human milk samples from Southern (77 samples) and Eastern (90) Finland. The level of PCDD/Fs and PCBs in human milk in Southern Finland was about 25% higher than those from Eastern Finland. The level of PCDD/Fs in human milk in Finland was the same as in Sweden, 30–50 % lower than in milk from Central Europe but about 45% higher than values from Norway or Russia. The PCB concentrations in Southern Finland were at the same level as in the Netherlands, and in Eastern Finland at the same level as in Norway. The levels of PCDD/Fs and PCBs decreased with increasing number of children: the third child was exposed to about 70% of the amount of PCDD/Fs and PCBs as compared with the first child, and the eighth to tenth child to about 20%. The congener patterns of PCDD/Fs and PCBs in Finnish human milk were similar to the countries of Central Europe, however, the levels of penta- and heptachlorinated furans were slightly higher than in milk from other countries.     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

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

Both long duration (>6 h) 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 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) 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.     

Thermal degradation of PCDD/F, PCB and HCB in municipal solid waste ash

A thermal degradation procedure for reducing the concentrations of mono- to octa-chlorinated PCDD/Fs, PCBs and hexa-chlorobenzenes (HCB) in filter ash from incinerated municipal solid waste (MSW) is described. Thermal treatment of filter ash samples at 500 degrees C for 60 min in a closed system providing low oxygen conditions resulted in 97% and 99% reductions in the total and I-TEQ concentrations of PCDD/Fs, to 6.8 microg kg(-1) ash and <0.05 microg I-TEQ kg(-1) ash, respectively. Increasing the thermal treatment time to 480 min, at the same temperature, yielded 99% reductions in both total and I-TEQ concentrations of the mono- to octa-chlorinated PCDD/Fs. Similar effects were observed for HCB and PCBs. The data from this study indicate that PCDD/Fs and other toxic organic compounds in ash from incinerated MSW, can be effectively degraded by this procedure, which combines relatively low-temperatures, short treatment times, and low oxygen conditions.     

Suppressing effect of goethite on PCDD/F and HCB emissions from plastic materials incineration

Polyethylene (PE) and polyvinyl chloride (PVC) are the leading plastics in total production in the world. The incineration of plastic-based materials forms many chlorinated compounds, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). In this study the addition of goethite (alpha-FeOOH) was investigated to determine its suppressing effect on the emission of PCDD/Fs and hexachlorobenzene (HCB) during the combustion of wastes containing PE and PVC. Goethite was being considered since it acts as a dioxin-suppressing catalyst during incineration. Results showed that incorporation of goethite greatly reduced the generation of PCDD/Fs and HCB in the exhaust gas and fly ash. The concentration of PCDD/Fs in flue gas decreased by 45% for lab-scale and 52% for small incinerator combustion experiments, where the goethite ratios in feed samples were 0.54% and 0.34%, respectively. Under the same conditions, the concentration of HCB in flue gas decreased by 88% and 62%, respectively. The present study showed a possible mechanism of the suppressing effect of the goethite for PCDD/F formation. It is likely that iron chlorides react with particulate carbon to form organo-chlorine compounds and promote PCDD/F formation in the gas phase. XRD analysis of combustion ash revealed that the goethite was partially dehydrated and converted to alpha-Fe(2)O(3) and Fe(3)O(4) but no iron chlorides formation. Therefore the goethite impregnated plastics can contribute the reduction of PCDD/Fs and HCB in the exhaust gas during incineration of MSW.     

Temporal trends and spatial distribution of PCDD, PCDF, and PCB in pine and spruce shoots

In Germany, there is a lack of consistent and comparable data for the time dependent behaviour and spatial distribution of dioxin-like and indicator PCB in ambient air, deposition and plants. The aim of this study was to improve the data on PCDD/PCDF, dioxin-like PCB and non dioxin-like PCB in spruce and pine shoots from different locations and years by retrospective monitoring. The survey was conducted with archived samples of one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) from the German environmental specimen bank. Two sets of samples from locations in urbanized areas in western and eastern Germany (Warndt and Duebener Heide Mitte, respectively) were investigated as time series. Additionally, spruce shoots from seven different rural locations sampled in the years 2000-2004 were analyzed in order to get an overview about the spatial distribution of PCB and PCDD/PCDF. The analytical results of the samples from the two urbanized areas clearly show that the atmospheric contamination with PCDD and PCDF has declined by about 75% between 1985 and 1997 at Warndt and about 40% between 1991 and 1997 at Duebener Heide. However, concentrations stayed virtually constant at both locations from 1997 to 2004 at a level of about 1 ng WHO-TEQ/kg dry matter (d.m.). Similarly, the investigation of spruce shoots from rural locations from 2000 to 2004 did not reveal a temporal trend at any site. PCDD/PCDF levels were between 0.1 and 1.0 ng WHO-TEQ/kg d.m. At the urbanized location Warndt the six indicator PCB as well as the 12 dioxin-like PCB according to WHO revealed a significant decline by more than 75% between 1985 and 1999. Thereafter, PCB levels stayed virtually constant. At the location Duebener Heide an overall decrease of PCB concentrations in pine shoots of about 60% was detected between 1991 and 2004. Spruce shoots from all locations showed a relevant contribution of dioxin-like PCB to the total WHO toxicity equivalent (PCDD/PCDF+PCB). In most samples, the contribution of dioxin-like PCB was between 21% and 41%. The TEQ contribution of PCB in the samples from three rural sites was higher and similar to the TEQ value of PCDD/PCDF. The investigated pine shoots from the urbanized site Duebener Heide showed a 15-28% contribution of dioxin-like PCB to total TEQ and thus lower than in spruce shoots from different locations. In all samples except one PCB 126 contributed to more than 80% to the PCB-TEQ.     

Formation of artefacts while sampling emissions of PCDD/PCDF from open burning of biomass

Emission factors for PCDD/PCDF determined from open combustion are used to estimate national emission budgets; therefore, it is important to have confidence in their accuracy. It has been suspected that artefacts may form due to the presence of hot metal surfaces of sampling equipment, thus skewing emission factors. In this study, emissions of PCDD/PCDF from open burning of forest biomass over a brick hearth were sampled. Five experiments were carried out using a portable sampler. Experiments were designed where the key variable, sample hood and inlet temperatures were manipulated. Other variables such as fuel origin, type and density were consistent. The measured concentration of PCDD/PCDF in the smoke samples ranged from 0.01 μg TEQ (t fuel)⁻¹ at the lowest maximum hood temperature (185 °C) to 15 μg TEQ (t fuel)⁻¹ at the highest maximum hood temperature (598 °C). when hood inlet temperatures exceeded 400 °C emission factors were significantly elevated and this is attributed to the formation of artefacts that can cause the over estimation of emission factors. The increase in hood temperature also resulted in a change in the PCDD/PCDF congener and homologue profile of the emissions. For example at the lowest temperature (Fire 1) the PCDD/PCDF ratio measured was 50:1, whereas at the highest temperature (Fire 5) this ratio was about 0.53:1. When the sampler hood and inlet temperatures were kept in the normal operating range of <200 °C, emission factors were comparable to those observed in many previous studies in Australia with emissions dominated by PCDD.     

Total TEQ emissions (PCDD/F and PCB) from industrial sources

Flue gas samples from eight different sources (industrial plants and crematories) have been analyzed for PCDD/Fs and PCBs and total Toxicity EQuivalents (TEQ) values have been calculated using the latest WHO toxicity equivalent factors from 1998. A contribution of PCBs to the Total TEQ up to 16% was found, within the 12 WHO-PCBs PCB-126 contributes mostly to the TEQ. Thermodynamic stability of PCBs was calculated semiempirically using the MOPAC program package and differences in the heat of formation (HoF) were compared to the distribution of PCBs in real samples. Partial correspondence between fact and theory could be found.     

Comparison of PCDD/PCDF levels in soil, grass, cow''s milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant

When in the vicinity of a metal reclamation plant in Tyrol, Austria, increased PCDD/PCDF levels were found in soil and spruce needles, the extent of grass contamination as well as the PCDD/PCDF content in milk of cows fed with hay from this area was determined. The milk samples showed a significant increase in PCDD/PCDF levels compared to control samples. In a blood sample of a farmer a significant increase in PCDD/PCDF levels was found. Correlations in PCDD/PCDF levels between soil, spruce needles, grass, cow's milk and human blood will be presented.     

PCDD, PCDF, PCB and PBDE concentrations in breast milk of mothers residing in selected areas of Slovakia

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs) in 33 breast milk samples collected in 2006-2007 from primipara mothers close to four industrial areas of Slovak Republic were determined. The total PCDDs/PCDFs and dl-PCBs expressed as TEQ based on WHO TEFs 1998 in breast milk samples varied from 5.0 to 51.8 pg g⁻¹ fat (median: 13.1 pg g⁻¹ fat; mean: 18.0 pg g⁻¹ fat). The measurements of seven PBDE congeners (IUPAC No. 28, 47, 99, 100, 153, 154, and 183) were performed for the first time in human milk from Slovakia. PBDE levels ranged between 0.22 and 1.62 ng g⁻¹ fat, with median and mean value of 0.43 ng g⁻¹ fat and 0.57 ng g⁻¹ fat respectively. No statistically significant differences were observed between studied areas in total PBDE concentrations.Furthermore, this study presents first results concerning the daily intake (DI) of PCDDs/PCDFs and dioxin-like compounds for the most vulnerable breast-fed infant population in Slovakia. The total PCDD/PCDF and dl-PCB DI for an infant during the first 2 months of life was estimated in a range from 14.4 to 230 pg TEQ kg⁻¹ b.w., with a median value of 58.9 pg TEQ kg⁻¹ b.w.. The DI values substantially exceeded the tolerable daily intake (TDI) 1-4 pg TEQ kg⁻¹ b.w. recommended by WHO. The dietary infant intake concerning PBDEs was estimated to be between 0.69 and 7.1 ng kg⁻¹ b.w. d⁻¹, with median value of 1.7 ng kg⁻¹ b.w. d⁻¹.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

PCDD/PCDF congener profiles in soil and herbage samples collected in the vicinity of a municipal waste incinerator before and after pronounced reductions of PCDD/PCDF emissions from the facility

Congener profiles are the fractional distribution of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) congeners in an environmental release, or in an environmental or biological sample. In 1999, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an old municipal solid waste incinerator (MSWI) from Montcada (Barcelona, Spain). The main goal of the present study was to determine if the environmental PCDD/F levels in the area under direct influence of the facility were mainly due to PCDD/F emissions from the plant. For this purpose, soil and herbage samples were collected near the MSWI before (1998) and after (2000) the technical improvements were performed. PCDD/F congener profiles were determined and compared with those from samples collected in a suburban area of Constantí (Tarragona, Spain) outside of direct emissions from any MSWI. The results of the present study suggest that the MSWI here assessed is not the main responsible for the environmental PCDD/F concentrations in the area under evaluation. Other PCDD/F emission sources in the same area seem also to have a notable impact on the atmospheric levels of these pollutants.     

Effects of combustion and operating conditions on PCDD/PCDF emissions from power boilers burning salt-laden wood waste

This paper discusses the effects of combustion conditions on PCDD/PCDF emissions from pulp and paper power boilers burning salt-laden wood waste. We found no correlation between PCDD/PCDF emissions and carbon monoxide emissions. A good correlation was, however, observed between PCDD/PCDF emissions and the concentration of stack polynuclear aromatic hydrocarbons (PAHs) in the absence of TDF addition. Thus, poor combustion conditions responsible for the formation of products of incomplete combustion (PICs), such as PAHs and PCDD/PCDF precursors, increase PCDD/PCDF emissions. PAH concentrations increased with higher boiler load and/or low oxygen concentrations at the boiler exit, probably because of lower available residence times and insufficient excess air. Our findings are consistent with the current understanding that high ash carbon content generally favours heterogeneous reactions leading to either de novo synthesis of PCDD/PCDFs or their direct formation from precursors. We also found that, in grate-fired boilers, a linear increase in the grate/lower furnace temperature produces an exponential decrease in PCDD/PCDF emissions. Although the extent of this effect appears to be mill-specific, particularly at low temperatures, the results indicate that increasing the combustion temperature may decrease PCDD/PCDF emissions. It must be noted, however, that there are other variables, such as elevated ESP and stack temperatures, a high hog salt content, the presence of large amounts of PICs and a high Cl/S ratio, which contribute to higher PCDD/PCDFs emissions. Therefore, higher combustion temperatures, by themselves, will not necessarily result in low PCDD/PCDFs emissions.     

PCBs fires: Correlation of chlorobenzene isomer and PCB homolog contents of PCB fluids with PCDD and PCDF contents of soot

PCBs, PCDDs, and PCDFs are subject to new regulations promulgated under the Toxic Substances Control Act and the Resource Conservation and Recovery Act. The finding of PCDDs and PCDFs in PCBs could restrict disposal options for PCBs. A review of major fire incidents in the U.S., indicates that PCDDs have been found only in the Binghamton, N.Y., transformer fire incident. Laboratory combustion studies further support PCDFs formation from PCBs and PCDDs from chlorobenzenes. No PCDDs were found in analyses of fluids from transformers involved in transformer fire incidents. PCDFs do not appear to increase in PCBs askarel fluids from normal usage in electrical equipment.     

Formation of PCDF, PCDD, PCB, and PCN in de novo synthesis from PAH: mechanistic aspects and correlation to fluidized bed incinerators

The difference of polychlorinated dibenzofurans (PCDF) isomer patterns between stoker type incinerators and some fluidized bed incinerators (FBI) is a key to understand the formation mechanisms in both types of incinerators. The total yield and the isomer patterns of PCDF, polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), and polychlorinated benzenes (PCBz) formed via de novo synthesis from polycyclic aromatic hydrocarbons (PAH) indicate that chlorinated aromatics in the FBI are formed as a result of PAH breakdown. The detailed analysis of the isomer patterns of PCDF, PCB and PCN gives a first insight into the transformation mechanism of the PAHs and the sequence of degradation, chlorination and oxygen insertion. The major chlorination takes part at the position of the C-C cleavage during degradation of the PAHs. Further chlorination of the hydrogen position of the former PAH takes part preferably in ortho-position to this chlorination or is directed by incorporated oxygen. A perylene structure in soot is proposed as basis for the observed PCDF pattern in the FBI. Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated phenols (PxCP) were formed in lower concentrations from the de novo experiments indicating an additional formation pathway for these compounds in the FBI.     

PAHs, PCDD/Fs, PCBs and HCB in leaves from Brisbane, Australia

The concentrations of SOCs in leaves of an evergreen Australian native tree (Melaleuca leucadendra) and grass collected in Brisbane, Australia were determined. The concentrations of PCDD/Fs and PAHs in the leaf tissue were comparable to those reported for urbanised areas in other industrialised countries. A distinct difference in the compound profiles between the leaves of the two species was observed, with higher concentrations of the lower molecular mass PAHs and PCDD/Fs and lower concentrations of the higher molecular mass PAHs and PCDD/Fs in the Melaleuca leaves relative to the grass leaves. The interspecies differences are explained on the basis of the larger size of the lipophilic compartment (for compounds with low K(OA)) and the lower ratio of surface area to volume in the Melaleuca leaves.