Emissions of PCDD/Fs,PCBs, and PAHs from legacy on-road heavy-duty diesel engines

Exhaust emissions of seventeen 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin/furan (PCDD/F) congeners, tetra–octa PCDD/F homologues, 12 WHO 2005 polychlorinated biphenyl (PCB) congeners, mono–nona chlorinated biphenyl homologues, and 19 polycyclic aromatic hydrocarbons (PAHs) from three legacy diesel engines were investigated. The three engines tested were a 1985 model year GM 6.2 J-series engine, a 1987 model year Detroit Diesel Corporation 6V92 engine, and a 1993 model year Cummins L10 engine. Results were compared to United States’ mobile source inventory for on-road diesel engines, as well as historic and modern diesel engine emission values. The test fuel contained chlorine at 9.8 ppm which is 1.5 orders of magnitude above what is found in current diesel fuel and 3900 ppm sulfur to simulate fuels that would have been available when these engines were produced. Results indicate PCDD/F emissions of 13.1, 7.1, and 13.6 pg International Toxic Equivalency (I-TEQ) L⁻¹ fuel consumed for the three engines respectively, where non-detects are equal to zero. This compares with a United States’ mobile source on-road diesel engine inventory value of 946 pg I-TEQ L⁻¹ fuel consumed and 1.28 pg I-TEQ L⁻¹ fuel consumed for modern engines equipped with a catalyzed diesel particle filter and urea selective catalytic reduction. PCB emissions are 2 orders of magnitude greater than modern diesel engines. PAH results are representative of engines from this era based on historical values and are 3–4 orders of magnitude greater than modern diesel engines.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.     

Dioxins, PCBs, and HCB in soil and peat profiles from a pristine boreal catchment

The aim of this study was to explore how atmospherically derived soil pollution is affected by environmental processes at two typical boreal catchment landscape type settings: wetlands and forested areas. Measurements of hydrophobic organic compounds (HOCs) in forest soil and peat from an oligotrophic mire at various depths were performed at a remote boreal catchment in northern Sweden. HOCs in peat were evenly distributed throughout the body of the mire while levels of HOCs in the forest soil increased with increased amount of organic matter. Evaluation of HOC composition by principal component analysis (PCA) showed distinct differences between surface soils and deeper soil and peat samples. This was attributed to vertical transport, degradation and/or shifting sources over time. The calculated net vertical transport differed between surface layers (0.3%) and deeper soils (8.0%), suggesting that vertical transport conditions and processes differ in the deeper layers compared to the surface layers.     

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.     

Levels and congener profiles of PCDD/Fs, PCBs and PBDEs in seafood from China

A nationwide investigation into polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in market seafood was conducted for the first time in this study. Total PCDD/F concentrations in fatty fish ranged from 0.13 to 8.64 pg g⁻¹ wet weight (mean 2.05 pg g⁻¹ wet weight), total PCB concentrations ranged from 38.9 to 3514 pg g⁻¹ wet weight (mean 1133 pg g⁻¹ wet weight), and total PBDE concentrations ranged from 42.8 to 913 pg g⁻¹ wet weight (mean 322 pg g⁻¹ wet weight). Corresponding mean toxicity equivalent (TEQ) values for total PCDD/F and dioxin-like PCB were 0.25 pg g⁻¹ wet weight (WHO 98-TEQ) and 0.32 pg g⁻¹ wet weight (WHO 98-TEQ), respectively. OCDD, PCB-138 and PBDE-47 were the dominant compounds according to their respective congeners. WHO 98-TEQ _{PCDD/PCDF/PCB} for fatty fish and shell fish were 0.60 and 0.070 pg g⁻¹ wet weight, respectively, lower than the standard set by the European Commission. The contamination levels and profiles were compared with those documented in previous publications.     

PCDD/F formation from oxy-PAH precursors in waste incinerator flyash

The yield of PCDD/F in relation to the presence of oxygenated PAH in model waste incinerator flyash has been investigated in a fixed bed laboratory scale reactor. Experiments were undertaken by thermal treatment of the model flyash at 250 and 350 °C under a simulated flue gas stream for 2 h. After reaction, the PCDD/F content of the reacted flyash and the PCDD/F released into the exhaust gas, and subsequently trapped by XAD-II resin in a down-stream condensation system were analyzed. The PAHs investigated were, dibenzofuran and benzo[b]naphtho[2,3-d]furan and were spiked onto the model flyash as reactant precursors for PCDD/F formation. The results showed significant formation of furans from both of the PAH investigated, however except from some highly chlorinated dioxin congeners, the formation of dioxins was not so common. Benzonaphthofuran was significantly more reactive than dibenzofuran in PCDD/F formation, in spite of the fact that dibenzofuran is structurally more similar to that of PCDD/F. Thus, there was no clear attribution between the chemical structure of PAH used and the formation of PCDD/F. There were considerable differences between the yields of PCDD/F congeners in the gaseous species and those in the reacted flyash under the same operational conditions. The concentration of PCDD/Fs was reduced at the higher reaction temperature of 350 °C; however, the higher temperature resulted in the majority of the PCDD/F formed on the flyash being released into the gas phase.     

Estimation and characterization of PCDD/Fs and dioxin-like PCBs from Chinese iron foundries

The iron foundry industry is considered to be a potential source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study investigated the emission factors and total emission amounts of PCDD/Fs and dioxin-like polychlorinated biphenyls (DL-PCBs) from iron foundries in China. The concentrations and the World Health Organization toxicity equivalents (WHO-TEQs) are presented and the congener profiles are discussed in this paper.In the present work, 26 fly ash samples were collected and tested to quantify the PCDD/Fs and DL-PCBs generated by 14 plants of different scales, and five stack gas samples were collected from two (named as EFG and LFG) of those plants. The emission levels of PCDD/Fs and DL-PCBs indicated that hot-air cupolas had lower emissions than cold-air cupolas. When iron ore lump and sinter were used as raw material, the emission factors were about 250 ng TEQ t⁻¹ of product. However, if the raw material was scrap, the emission factors varied owing to the different contents of organic materials in the raw materials. It was found that the mean WHO-TEQ values of PCDD/Fs and DL-PCBs were 144 and 34.2 pg Nm⁻³ in stack gas and 20.0 and 1.58 pg g⁻¹ in fly ash. In multiple tests, it was estimated that the mean emission factors of PCDD/Fs and DL-PCBs were 365 and 10.9 ng WHO-TEQ t⁻¹ released to residue and 2719 and 555 ng TEQ t⁻¹ released to air. The total emission amounts of PCDD/Fs and DL-PCBs from Chinese iron foundries with cupola furnaces released to residue and air were 16.8 and 146 g WHO-TEQ in 2008, respectively.     

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m⁻³ (ND ∼ 617) and 1 fg WHO-TEQ m⁻³ (ND ∼ 0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p = 0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.     

PCDD/Fs and dioxin-like PCBs in sediment and biota from the Mondego estuary (Portugal)

The concentrations of 17 polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in sediment and key species as an initial investigation on PCDD/Fs and dl-PCBs contamination in the Mondego estuary (Portugal). The results demonstrated that the values of the total PCDD/Fs (∑PCDD/Fs) concentrations were considerably lower than those of the sum of dl-PCBs (∑dl-PCBs) in all the studied samples. Regarding the contribution of individual congeners, OCDD was the predominant PCDD/F and the mono-ortho PCB 118 and PCB 105 were the dominant PCBs in the majority of the samples. Our results suggest that PCDD/Fs and PCBs behave quite differently along the aquatic food web: ∑PCDD/Fs concentrations were lower in higher trophic-level organisms with fish presenting a distinct PCDD/Fs congeners profile; on the contrary, the higher ∑dl-PCBs values were found in upper-level biota, although not exclusively, and quite similar dl-PCBs congener profiles were observed in nearly all the studied species.     

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.     

Experimental evaluation of PCDD/Fs and PCBs release and mass balance of a WTE plant

The behaviour of waste incineration plants with respect to organic toxic trace contaminants such as PCDDs, PCDFs and, to a minor extent, PCBs, is still a matter of concern for the public opinion and the decision makers. It is therefore very important, first, to evaluate the release of these organic toxic trace contaminants in the environment during waste incineration, not only through the stack gas emission but also with the solid and liquid residues, and then to compare the total release with the input through the treated waste in order to assess the plant behaviour as a “sink” rather than a “source” of organic toxic trace contaminants. The experimental investigation carried out on an Italian full scale incineration plant has shown a total 17 PCDD/Fs and 12 dioxin-like PCBs release of 5.5-27 μg WHO-TEQ per tonne of treated waste and an input flux of 1.6-44 μg WHO-TEQ per tonne of waste, with the difference between the input and the output fluxes rather small and the plant behaviour toward organic trace toxic contaminants in average neutral. Results are compared with similar evaluations conducted in the last decade on a number of waste-to-energy (WTE) plants operating in Italy.     

A probabilistic model for the carry-over of PCDD/Fs from feed to growing pigs

When food producing animals are contaminated with PCDD/F congeners, information on the contaminant’s concentration in the bodies of the animals at time of slaughter is needed for risk management purposes. We have developed a mathematical model for the kinetics of PCDD/Fs in growing pigs in case of contaminated feed fed for a limited duration of time. This model allows the prediction of concentrations in body fat. It considers absorption fractions of PCDD/Fs, clearance by metabolism, dilution by growth and excretion through fecal fat. The model parameters were calibrated by fitting the model to experimental data. On the basis of this toxicokinetic model a probabilistic model has been constructed. The probabilistic model handles the parameters with appropriate probability distributions and Monte-Carlo simulation technique, providing for realistic situations with many animals and a range of contaminations and feeding intervals. We applied the new model to describe the German dioxin incident of winter 2010/2011 and discuss its viability as decision tool. The approach demonstrated here is a showcase how a risk assessment in the case of contaminated feeding can be performed.     

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.     

Formation of PCDD/Fs from oxidation of 2-monochlorophenol over an Fe2O3/silica surface

The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550 °C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe₂O₃ on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ∼2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.     

电子垃圾焚烧排放的二噁英对周围大气环境的影响

为了研究电子垃圾焚烧产生的二噁英对周围环境的影响,同时在E1和E2采样点分别采集9个大气样品.E1周围分布大量的电子垃圾焚烧点,E2则位于E1南9 km处,周围无其他明显的二噁英排放源.所采样品用同位素稀释法进行分析测定,结果表明,E1和E2大气样品中二噁英的平均质量浓度分别为127.37、22.37 pg/m3,平均毒性当量浓度分别为8.777、1.305 pg I-TEQ/m3.八氯代二苯并呋喃(OCDF)、八氯代二苯并二噁英(OCDD)、七氯代二苯并呋喃(1,2,3,4,6,7,8-HpCDF)和七氯代二苯并二噁英(1,2,3,4,6,7,8-HpCDD)对2,3,7,8位氯代的二噁英的总浓度贡献较大,而五氯代二苯并呋喃(2,3,4,7,8-PeCDF)则对总毒性当量浓度贡献最大,其贡献率超过40%.在E1和E2两个采样点,二噁英在气相中的比例均随着氯原子取代数的增加而降低.两采样点相似的二噁英分布模式和气固分配,说明E2大气中二噁英主要来自于E1电子垃圾焚烧产生的二噁英.     

Evaluation of the emission characteristics of PCDD/Fs from electric arc furnaces

Distribution of PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) congeners at two electric arc furnaces (EAFs) in Taiwan is evaluated via intensive stack sampling and analysis. Two kinds of exhaust system in EAFs including stack system and shutter system are selected for measuring dioxin emissions. In addition, dioxin emissions during oxidation and reduction stages at EAF-A were characterized. Results indicate that the PCDD/F concentration of stack gas in EAF-A was 4.39 ng/N m³ while total Toxic Equivalent Quantity (TEQ) concentration was 0.35 ng I-TEQ/N m³. The PCDD/F concentration of stack gas in EAF-B was 2.20 ng/N m³ and the TEQ concentration was 0.14 ng I-TEQ/N m³. 1,2,3,4,6,7,8-H_pCDF, OCDD and OCDF are the major contributors of the dioxin concentrations for two EAFs investigated and the percentage of PCDD/F in particulate phase increases as the chlorination level of the PCDD/F congener increases. The results obtained on gas/particulate partitioning of PCDD/Fs in flue gases prior to the APCD in EAFs indicate that more than 90% exists in particulate phase. In EAF-A, the PCDD/F concentration during oxidation stage is slightly higher than that measured during reduction stage, including the sampling points of CO converter outlet, prior to bag filter and stack. Majority of PCDD/Fs emitted from steel-making processes exists in particulate-phase (about 60–70%) at both EAFs investigated.     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

二(噁)(口英)样品制备与检测技术进展

环境中存在的二噁是一类严重影响食品安全和人类健康的强毒性有机污染物,为了能正确评价这类化合物的来源与环境中分布情况,二噁的分析检测引起了人们强烈的关注。本文介绍了样品检测前处理纯化过程中所用的各种传统的吸附剂(硅酸盐、佛罗里土和活性炭等)和新发展的几种主要吸附剂(2(1芘基)乙基二甲基硅烷化硅胶(PYE)、炭纳米管和多孔石墨炭等)的性能、在样品前处理过程中所起的作用及存在的问题和发展趋势,并在概括样品制备的基础上,阐述了二纯化技术及其检测方法(包括化学分析法和生物分析法)的进展。     

Temporal trends (2005-2009) of PCDD/Fs, PCBs, PBDEs in rice hulls from an e-waste dismantling area after stricter environmental regulations

Primitive e-waste dismantling activities have been of increasing concern due to serious environmental and human health problems, and therefore authorities in China have strengthened the regulations on illegal e-waste recycling activities. In this work, we used rice hull as a passive sampler and investigated temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) in areas near e-waste recycling sites after the stricter regulations. Furthermore, the distribution patterns and composition profiles of these contaminants were also discussed. The average concentrations of the three groups of persistent organic pollutants (POPs) in rice hulls have markedly decreased during the period of 2005-2009. Specifically, from 12.9 (average value in 2005) to 0.37 pg WHO-TEQ/g (dry weight, dw) (in 2009) for PCDD/Fs, 47.6 (2005) to 7.10 ng g⁻¹ dw (2009) for PCBs, and 2.51 (2005) to 0.89 ng g⁻¹, dw (2009) for PBDEs. The significant decrease of combustion markers 2,3,4,7,8-PeCDF, 1,2,3,6,7,8HxCDF and PCB126, and the PCDD/PCDF ratio from 1:9 (2005) to 7:3 (2009) is likely a result of stricter regulations on open combustion activities. This study suggests that stricter control measures, strengthened laws and regulations and more environmental friendly techniques could be effective measures in reducing the release and formation of related POPs in typical e-waste dismantling sites, and these measures could further improve the quality of the environment and health of the local inhabitants.     

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P(L)(0)) and the octanol-air partition coefficient (K(OA)) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K(P)) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O(3) and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol.