Predictions for isomer distributions of toxic dioxins and furans in selected industrial combustion processes

Three thermodynamic databases of polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) have been used to simulate the PCDD/F isomer distribution in industrial combustion processes. The three databases had been derived using the Group Additivity approach and two computational molecular modelling methods, Modified Neglect of Diatomic Overlap (MNDO) and Parametrized Model 3 (PM3), respectively. The predictions of the toxic PCDD/F isomer distributions using the three different databases have been compared with measured values from industrial processes. An excellent agreement between the predictions using the MNDO method and the measured data has been obtained. It is concluded that the PCDD/F isomer distributions within each group observed in these combustion processes may be thermodynamically controlled.     

Variation of dioxins and furans in human tissues

A number of chlorinated dibenzo-p-dioxins (PCDDs) and chlorinated dibenzofurans (PCDFs) occur in human adipose tissue at levels from 5 pg/g for 2, 3, 7, 8-TCDD to approximately 1000 pg/g for octachlorodibenzo-p-dioxin (OCDD). The variation of these compounds in tissues has been studied with respect to age, sex, tissue type, and country. A sampling of 46 adipose tissues from Canada in 1976 has shown a positive correlation of 2,3,7,8-TCDD level of detectable samples with age but not sex. This relationship is supported by the analysis for the first time of tissue from a 6 month old infant and the demonstration of little or no measurable levels of PCDDs/PCDFs. Three additional tissue types, pancreas, brain, and testis, from two autopsies were assayed for PCDDs/PCDFs for the first time but little or none were found even though the first two tissues had up to 10% lipid. A small sampling of adipose tissue from the general population in Japan in 1984 contained generally the same types and concentrations of PCDDs/PCDFs as are found in tissues from other industrialized countries.     

Portuguese inventory of dioxins and furans atmospheric emissions

This article presents the results of the most recent estimation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) atmospheric emissions in Portugal, which has covered the period 2004–2009 and includes 27 emission sources types. The results are compared with previous emissions inventories published for Portugal. The main objective of this work is to provide relevant information about the amounts of the compounds that are released into the atmosphere in Portugal, and identify their major sources and trends.     

Thermal properties of dioxins, furans and related compounds

Vapor pressures are important parameters for modeling of environmental fate and incineration behaviour of chloro-dibenzodioxins and -dibenzofurans. Vapor pressures, enthalpies and entropies of sublimation were measured for four dibenzofurans and were compared to corresponding data on chlorodioxins. A vapor pressure correlation method, which uses the liquid phases as reference states was introduced. Boiling points, enthalpies and entropies of fusion could be calculated from the vapor pressure data by this method. The determined parameters were correlated with the degree of chlorine substitution and the correlations permit the estimation of boiling points, enthalpies of fusion and of sublimation pressures of n-chlorodioxins and -furans of known melting points. The predicted vapor pressures of 2,3,7,8-TCDD were found to be in good agreement with literature reportings.     

Levels of dioxins and furans in urban surface soil in Trondheim, Norway

A study was conducted on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in surface soil in order to determine the concentration levels and possibly distinguishing between known and potential sources. The concentration levels are low (0.16-14 ng I-TEQ kg(-1)). The results show a clear pattern where the highest concentration levels were found in the oldest parts of the city. A number of sources were recognised in the soil samples through congener profiles, not all of them active, although similar congener profiles make it extremely difficult to distinguish between different sources. Estimations show that the municipal solid waste incinerator (MSWI) and domestic wood burning are the largest PCDD/F pollution sources within the area.     

Comparison of emission of dioxins and furans from gasohol- and ethanol-powered vehicles

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (www.epa.gov/ttn/ emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/ hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the.gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km(-1) (average of 0.0294 pg I-TEQ km(-1)), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km(-1) (average of 0.031 pg I-TEQ km(-1)). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.     

A survey of drinking water supplies in the Province of Ontario for dioxins and furans

A survey of drinking water supplies in the Province of Ontario was initiated in 1983 to determine the extent of their contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). This drinking water survey arose from concerns regarding the discovery of PCDDs and PCDFs in sport fish from western Lake Ontario in the early 1980's.A total of 49 water supplies throughout all Regions of Ontario have been examined to date. Water supplies in the vicinity of chemical industries and pulp and paper mills were sampled more frequently; as many as 20 times. Detection limits were in the low parts per quadrillion (ppq) range for all tetra- to octachlorinated PCDDs and PCDFs.As of February 1989, 4, 347 results were received for 399 raw and treated water samples. Only 37 positive results were reported, constituting less than 1 percent of the total number of results. The O₈CDD congener accounted for 36 of the 37 positive results. The 2,3,7,8- TCDD isomer was not detected in any sample.     

Destruction of dioxins and furans adsorbed on flyash in a rotary kiln furnace

The paper deals with the use of a rotary kiln furnace for thermal destruction of dioxin combined with a baghouse filter for the recycling of entrained flyash and an activated carbon filter for adsorbtion of dioxin traces transported by gas phase.Measurements performed at a pilot plant with a throughput of 200 kg flyash/hr revealed 99.5 % destruction of dioxins and furans. Furthermore, the destruction of all organics, 95 % desorbtion of mercury and quantitative elimination of peripheral (located at the surface) Chromium (CrVI) were achieved.An activated carbon filter placed in the fluegas stream of an municipal waste incinerator was started up to investigate the influence of interfering constituants like SO₂, HCl etc. on the filter performance. Loading data, removal efficiency and make up performance were collected.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

An updated assessment of the exposure of Canadians to dioxins and furans

Dioxins and furans substituted in the 2,3,7, and 8 positions are highly toxic substances. The governments of Canada and Ontario have recently concluded that human exposure should not exceed 10 pg TEQ/kg bw/d. Updated estimates of average lifetime intakes by Canadian adults of dioxins and furans from all sources are under 10 pg TEQ/kg bw/d. The estimation of exposure calculated from current tissue concentrations in Canadian adults supports this finding. Excessive consumption of some highly contaminated fish and wildlife species may lead to intakes of dioxins and furans that approach or exceed the 10 pg TEQ/kg bw/d value and constitutes a danger to health.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Urine concentrations of selected trace metals in a cohort of Irish adults

Environmental Science and Pollution Research - Human biomonitoring studies are of increasing importance in regulatory toxicology; however, there is a paucity of human biomonitoring data for the...     

Levels of dioxins, furans and PCBs in human serum and milk of people living in Greece

In an attempt to evaluate the background levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho, mono-ortho and indicator polychlorinated biphenyls (PCBs) in people living in an urban (Athens) and a rural (Kozani) area of Greece, blood serum and mother milk samples were analyzed. Analytical results are reported in this study. Statistically significantly differences were observed between regions, sexes and ages. Contamination levels in blood and human milk from Greece reported here are low compared to the previously reported dioxin data from other European countries and give no indication of particular health risk.     

A screening study of the treatability of dioxins and furans in bleach plant filtrates and mill wastewaters

Findings are presented of a study to provide the pulp and paper industry with basic data regarding the feasibility for treatment of bleach plant filtrates or combined treated mill effluents for 2,3,7,8-TCDD and 2,3,7,8-TCDF reduction.     

Determinants of dioxins and furans in blood of non-occupationally exposed populations living near Portuguese solid waste incinerators

Biomonitoring of dioxin body burden, as evaluated by PCDD/F levels in blood, has been carried out in a total of 138 adults from general population living in the vicinity of solid waste incinerators in Portugal. Measurements were performed included in cross-sectional surveys within two Environmental Health Surveillance Programs launched in response to ecotoxicological concern in relation to solid waste incinerators near Lisbon and in Madeira Island. Overall conclusion from first published results is indicative that dioxin exposure of global populations cannot be related to the emissions of these facilities, meaning that dioxin sources control seems to be effective in relation to both incinerators. Main objective of present work was to investigate potential determinants of dioxin levels in the studied populations. Findings from this investigation also suggest that incineration does not impact on dioxin blood levels of nearby residents. Follow-up of a small group of individuals (22) from Lisbon gives preliminary indication on temporal control effectiveness of the Lisbon facility. Regarding comparison between PCDD/F levels from Lisbon and Madeira communities, individuals from Lisbon show higher median PCDD/F levels, likely to be better explained by more highly polluted areas in Lisbon than by eventual differences in dietary habits of the studied groups. In fact, analysis performed on the diet of both groups (not detailed in the present study) does not show a statistically significant difference in relation to any of the most relevant foodstuffs in the context of dioxin exposure. Comparison between Lisbon and Madeira in relation to pattern of the single congeners for PCDD/Fs shows a very similar profile. The highest contributions to the PCDD/Fs toxicity came from 12378-PCDD, 23478-PCDF, Hexa-CDD, 2378-TCDD and Hexa-CDF.     

Rapid formation of polychlorinated dioxins/furans in the post combustion region during heterogeneous combustion

The formation of chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) downstream from the combustion zone of a heterogeneous combustor occurred within seconds in the temperature range of 430-380°C, but not at substantially lower temperatures. A spouted bed reactor was used with sand as the heterogeneous medium and a fuel mixture of 1,2-dichlorobenzene/heptane. Total PCDD/F-concentrations were in the range of 100 ng m⁻³; chlorobenzenes other than the starting compound and chlorophenols were formed. The formation of PCDD/F may be mediated by high surface area particles originating from the bed due to attrition. Homogeneous gas phase mechanisms cannot account readily for the levels observed.     

Monitoring dioxins and furans in a population living near a hazardous waste incinerator: levels in breast milk

In this study, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) in breast milk from mothers living in the vicinity of a new hazardous waste incinerator (HWI) were determined. Monitoring was performed after three years of regular operations in the facility and the present results were compared with baseline concentrations obtained in a pre-operational program. PCDD/PCDF levels were determined by HRGC/HRMS in 15 samples. In the present study, PCDD/PCDF concentrations ranged from 4.9 to 39.9 pg I-TEQ/g fat (5.1-46.8 pg WHO-TEQ/g fat), with a median value of 7.7 pg I-TEQ/g fat (9.1 pg WHO-TEQ/g fat). In the baseline survey, PCDD/PCDF concentrations ranged between 5.9 and 17.1 pg I-TEQ/g fat, with a median value of 11.7 pg I-TEQ/g fat. In relation to this, a percentage of reduction of 34.2% was noted. This decrease is in agreement with the relevant reduction found in the dietary intake of PCDD/PCDFs between both surveys. The results of the present study, as well as other recent environmental and biological data, indicate that living in the vicinity of this HWI should not mean additional health risks due to PCDD/PCDFs for the general population.