HCB,PCB, PCDD and PCDF emissions from ships

Since current estimates of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB), dioxins (PCDD) and furans (PCDF) from ships are based on a relatively limited and old data set, an update of these emission factors has been outlined as a target towards improved Swedish emission inventories. Consequently, a comprehensive study was undertaken focusing on these emissions from three different ships during December 2003 to March 2004. Analyses were performed on 12 exhaust samples, three fuel oil samples and three lubricating oil samples from a representative selection of diesel engine models, fuel types and during different “real-world” operating conditions.The determined emissions corresponded reasonably well with previous measurements. The data suggest however that previous PCDD/PCDF emission factors are somewhat higher than those measured here. As expected the greatest emissions were observed during main engine start-up periods and for engines using heavier fuel oils. Total emissions for 2002, using revised emission factors, have been calculated based on Swedish sold marine fuels and also for geographical areas of national importance. In terms of their toxic equivalence (WHO-TEQ), the PCDD/PCDF emissions from ships using Swedish fuels are small (0.37–0.85 g TEQ) in comparison to recent estimates for the national total (ca. 45 g TEQ). Emissions from other land-based diesel engines (road vehicles, off-road machinery, military vehicles and locomotives) are estimated to contribute a further 0.18–0.42 g TEQ. Similarly, HCB and PCB emissions from these sources are small compared to 1995 national emission inventories.     

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.     

Thermally induced formation of PCDD and PCDF from tri- and tetrachlorobenzene in dielectric fluids

The thermal behavior of dilute (5000-50 ppm) solutions of tri- and tetrachlorobenzene in mineral oil, silicone oil, and tetrachloroethylene (TCE) has been investigated. Although pyrolyses or combustion of neat chlorobenzenes readily forms significant yields of PCDDs/PCDFs, corresponding treatment of dilute solutions was generally non-productive. This result is consistent with the proposition that, under the conditions studied, the rate-limiting step for PCDD/PCDF formation is bimolecular in chlorobenzene. In contrast, earlier studies of PCBs implied a rate-limiting step that was unimolecular in chloroaromatics. Combustion of dilute solutions of chlorobenzenes in tetrachloroethylene did produce detectable concentrations of PCDF; this result reflects combination of chlorobenzene and TCE- or TCE-derived species.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

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.     

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.     

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.     

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/CO₂ 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/CO₂ ratio increases.     

The relative contribution of wood and poly(vinyl chloride) to emissions of PCDD and PCDF from house fires

Emissions of PCDD/F from poly(vinyl chloride) (PVC) burned in house fires has been estimated at <1 g I-TEQ/yr in the US. In the current literature-based study, amounts of wood (21,000 kg) and PVC (180 kg) in a new house of standard construction are calculated and previously published emission factors for wood (0.01–173 μg/t) and PVC (3–6554 μg/t) are reported. Test conditions under which emission factors are generated differ and may not be directly comparable. Typically, PVC is tested at small-scale under relatively poor combustion conditions and wood is tested at large-scale under good combustion conditions. Thus, overall emission from combustion of these two materials of construction in house fires on an as-used basis is estimated to be similar (on the order of 1 g/yr) and a small contributor to the PCDD/F sources inventory. No speculation is made with respect to contents, roofing or other materials of construction.     

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 characteristics of PCDD and PCDF during pyrolysis processes

In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions – industrial light shredder (ILS) and refrigerators (REF) – both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430°C and 470°C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T₄CDF and P₅CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.     

Characteristics of PAHs, PCDD/Fs and PCBs in sediment following forest fires in northern Alberta

Extensive forest fires occurred in northern Alberta, Canada, in 1998. Polynuclear aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were studied following these forest fires in order to explore natural and anthropogenic influences on the affected forest fire area. Specifically, concentrations and profiles of these compounds were determined in sediment samples. A predominance of alkylated PAH derivatives over parent PAHs were observed at the burned and reference sites. Naturally dervied PAHs were abundant at all sites. A high proportion and concentration of retene was observed at the totally burned site and indicates some inputs from forest fires. Very low concentrations of PCDD/Fs and PCBs were observed at all sites, and the profiles were very similar. This likely reflects common atmospheric contributing sources to the study area.     

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.     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.     

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.     

Atmospheric baseline levels of PCDD and PCDF in the region of Oporto

An external monitoring plan (EMP) is being implemented in the region of Oporto, Portugal, to follow the potential effects of a future incinerator of municipal solid waste. Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) were measured during 1998 and the first semester of 1999, prior to the working up of the incineration unit. The baseline levels obtained through this intensive monitoring work are presented and discussed in the present paper.     

A survey of PCDD and PCDF in French long-life half-skimmed drinking milk

A national survey was carried out in order to assess the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in long-life half-skimmed drinking milk produced and consumed in France. 151 Samples were collected from 33 dairy establishments selected for their production amounts following a random sampling scheme. 148 of the 151 results were finally used for statistical assessment. The mean concentration of 2,3,7,8-TCDD toxicity equivalent found is 0.65 pg/g of milk fat. This result is far below the threshold recommended by the European Union.     

Emission and chlorination pattern of PCDD/PCDF predicted from indicator parameters

The emission and chlorination pattern of polychlorinated dioxins and dibenzofurans from waste combustion shows a close covariation with that of chlorinated benzenes and phenols. This covariation can be utilized to predict the emission levels of specific isomers as well as the pattern of congeners.     

Long-term automated sampling of PCDD/PCDF flue gas: current status and critical issues

After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm(3)), compared to average values (4-5 pg I-TEQ/Nm(3)) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15-30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6-8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.     

Analytical procedures to assay environmental samples for PCDD/PCDF, PHA, PCB, chlorobenzenes (CB) and chlorophenols (CP)

Sample extracts from each section of a blank stack sampling train are portioned into two fractions, one to be used for PCDD/PCDF and PCB/CB analysis and the other for PAH/CP. The results of recovery studies for spiked compounds are presented. Developed protocols will be applied to future stack sampling programs and other environmental monitorings.