An evaluation of three empirical air-to-leaf models for polychlorinated dibenzo-p-dioxins and dibenzofurans

Three empirical air-to-leaf models for estimating grass concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (abbreviated dioxins and furans) from air concentrations of these compounds are described and tested against two field data sets. All are empirical in that they are founded on simplistic bioconcentration and related approaches which rely on field data for their parameterization. One of the models, identified as the EPA Model, partitions the total air concentration into vapor and particle phases, and separately models the impact of both. A second model addresses only the vapor phase; grass concentrations are modeled as a function of vapor deposition. For the third model, it is assumed that the grass plants "scavenge" a fixed volume of air of dioxins, and hence grass concentrations are modeled as a simple product of total air concentration and a constant scavenging coefficient. Field data from two sites, a rural and an industrial site in the United Kingdom, included concurrent measurements of dioxins in air and field grass, and dioxin and furan depositions, for one 6-week sampling period. Principal findings include: (1) the EPA Model underpredicted grass concentrations at the rural field site by a factor of 2, while the Scavenging Model underpredicted grass concentrations by a factor of 3.8, and the Vapor Deposition Model significantly underpredicted grass concentrations (by a factor greater than 10), (2) the presence of high soil concentrations for some of the dioxins and furans at the industrial site appears to have caused higher grass concentrations and confounded the air-to-plant modeling exercise, (3) the Scavenging Model could be calibrated to the data set; however, a key premise of this model that vapor and particle phase dioxins equally impact the plants, is not supported by the field data, (4) measured depositions are highly correlated to but systematically lower than modeled depositions, which could be due to modeling assumptions or a systematic measurement bias.     

A study of polychlorinated dibenzo-p-dioxins and dibenzofurans in the atmosphere of Hong Kong

A total of 27 ambient air samples of were collected from six locations in Hong kong during the period of January-August, 2000 and analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In all sampling locations, higher concentrations of PCDDs/PCDFs, ranging from 0.03 to 0.43 pg I-TEQ/m3 were measured in winter months (January and March) than in the summer months (July and August) of concentrations at 0.018-0.025 pg I-TEQ/m3. These concentrations are similar to annual ranges reported earlier for two Hong Kong urban sites and other urban cities in Asia. Europe, and the United States. Despite significant seasonal variations in ambient air concentrations of PCDD/Fs (expressed in I-TEQ) were observed, the congener profiles of all the samples in this study period were similar, with OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF being the predominant species. However, the homologue profiles for the samples collected at the six locations of this study were found to display significantly different spatial and seasonal trends.     

Characterization of polychlorinated dibenzo-p-dioxins and dibenzofurans in different particle size fractions of marine sediments

The distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was examined according to particle size in marine sediments, with a particular focus on fine particulates. Samples from different coastal sites were fractionated into five size groups (<2, 2-5, 5-10, 10-20, and 20-63 microm diameter) by gravitational split-flow thin fractionation. Despite the different size profiles and PCDD/F contents of the sediments at each site, PCDD/F levels in fractionations tended to increase as the particle size decreased; the PCDD/F levels in the finest particles were up to 16 times higher than in the coarsest particles, which was associated with their organic carbon contents. Log normalization showed high levels of PCDD/Fs in the fine silt particles (2-10 microm), which are consumable by aquatic biota. Because of the different toxicity and bioavailability of PCDD/Fs in different sediment particle sizes, it is important to study particle actions to understand their effects on the aquatic ecosystem.     

Depositional flux of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in an urban setting

Dry and wet deposition fluxes of the PCDD/F substituted congeners were measured at two different sites (Clinton Drive and Lang Road) in Houston, TX between December 2003 and April 2004. Average total dry deposition fluxes of 351 and 125pgm(-2)d(-1) were found at Clinton Drive and Lang Road, respectively. A wet deposition flux of 2.873pgm(-2)d(-1) was measured at the Clinton Drive site. The results indicated that the dry deposition process exhibited spatial variability. In addition, the results also demonstrated that precipitation, although intermittent, is the most important mechanism for the removal of dioxins from atmosphere in the area of study. Combining the contributions of the dry and wet deposition processes at Clinton Drive resulted in a total bulk deposition flux of 527pg m(-2)d(-1). The total dry and wet deposition fluxes were dominated by OCDD followed by 1,2,3,4,6,7,8-HpCDD at both sites. Overall average dry deposition velocities of 0.35 and 0.15cms(-1) were calculated at Clinton Drive and Lang Road sites, respectively. While these velocities were similar to velocities observed in other geographical areas, the contribution of OCDD to the total deposition flux in Houston was significantly higher, probably reflecting the unique nature and character of Houston dioxin sources. The results also showed that lower chlorinated congeners, primarily present in the gas phase, are more likely to be removed from the atmosphere by precipitation. Relationships between the detected congeners in the dry deposition samples and other routinely measured air pollutants/meteorological parameters were found. The results showed that in general, the dry deposition of these congeners was consistently negatively correlated with SO(2) and NO(x) concentrations in the air and positively correlated with relative humidity. However, more research is needed to ascertain those correlations.     

Gas/particle partitioning behaviour of azaarenes in an urban atmosphere

The gas/particle partitioning of azaarenes in the Liverpool urban atmosphere was measured from May 1995 to April 1996. This period included one of the hottest summers and coldest winters recorded in the UK. The changes of the relative proportions of particulate and vapour phases showed a strong seasonal variation in which over 80% of azaarene compounds are associated with the particles in the winter and over 60% of azaarene compounds exist as vapour phase during the summer. The results are fitted into a gas/particle partitioning equation. Calculated vapour pressures, vaporization and desorption enthalpies are also given. Azaarene partitioning behaviour is modelled at a variety of aerosol concentrations and over a temperature range which includes normal ambient temperatures. It is hypothesised that three ring azaarene species are more likely to undergo changes in the relative proportions of particle and vapour phase material than either two or four ring compounds.     

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil samples from Spain

Soil analyses were carried out to evaluate the contamination caused by PCDDs and PCDFs in different soil samples. Monitoring was undertaken at different locations throughout Spain, from 1993 to 1999. A total of 230 samples were analysed. The levels ranged from 0.10 pg I-TEQ/g to 1.08 ng I-TEQ/g. Differences in dioxin levels were observed as a function of the sampling site, with levels at the industrial sites exceeding those at the control sites.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.     

Surface catalyzed formation of polychlorinated dibenzo-p-dioxins/dibenzofurans during municipal waste incineration

A series of reactions was carried out on different surfaces using carbon and CuCl₂, and KCl or HCl as a Cl-source. The PCDD/PCDF congener distribution was seen to vary to a great extent but the isomer distribution remained fairly constant. It is concluded that thermodynamic properties are largely responsible for the PCDD/PCDF isomer distribution. With pentachlorobenzene Cl₂ elimination, assisted by oxygen, appears to be the major pathway for PCDD/PCDF formation.     

Distribution of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and non-ortho coplanar polychlorinated biphenyls in river and offshore sediments

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho chlorine substituted coplanar polychlorinated biphenyl (Co-PCBs, non-ortho Cl CBs) in river and offshore sediment samples were analyzed isomer-specifically using (13)C-labeled their respective internal standards and a selected ion monitoring method of high resolution gas chromatograph-mass spectrometry (GC-MS). These compounds were found in all samples analyzed. The average concentrations of the total PCDDs, PCDFs and Co-PCBs in the 23 sediment samples taken from rivers were 11 000, 1300 and 160 pgg(-1) of dry wt, respectively, those in six offshore sediments were 7600, 980 and 52 pgg(-1), respectively. The concentrations of Co-PCBs were much lower than those of PCDDs and PCDFs in all sediment samples. The magnitude of these concentrations was in the order of lower reach of river > offshore area > upper reach of river. The concentrations of PCDDs and PCDFs in the rural river were higher than those in the urban river, whereas the Co-PCB concentration in an urban river was six times higher than that in a rural river. The Co-PCB concentrations in the urban area and industrial area were higher than that in any other area. These findings suggest that the pollution by PCDDs and PCDFs was derived from some kinds of incinerations and herbicides applied in the past and that Co-PCB pollution was caused by PCB preparation used in the past in urban and industrial areas and by municipal waste incineration in urban areas.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil with vegetable oil

GOAL, SCOPE AND BACKGROUND: This study was carried out to investigate the effect of olive oil on the photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated sawmill soil. Previous studies had shown that the solubility of PCDD/Fs in olive oil is high and a rapid photodegradation of PCDD/Fs takes place in olive oil when irradiated with ultraviolet (blacklight) lamps. The efficiency of this treatment method was evaluated under more practical conditions. These included the use of sunlight irradiation and a lower-grade olive oil, without a preliminary extraction of soil with olive oil. METHODS: A 1-cm layer of contaminated sawmill soil was blended with 20 weight-% of olive oil and exposed to sunlight for four weeks. In another experiment, a new dose of olive oil was added at the middle of the exposure period. The PCDD/F concentrations of the soils were monitored periodically. RESULTS AND DISCUSSION: A reduction in the concentration of 2,3,7,8-chlorinated PCDD/Fs by 59% and in WHO-TEQ in contaminated sawmill soil by 48% was attained after blending the soil with two doses (20 + 20%) of olive oil and exposing the mixture to sunlight for four weeks. Photodegradation with only one dose of olive oil was less efficient. This suggests that periodical additions of olive oil would be needed to maintain a proper degradation rate. After the oil additions, the WHO-TEQ content of the soil declined with first order reaction half-lives of 19.2 to 19.7 d. The overall half-life during the four-week treatment, however, was 30 d. CONCLUSION: A significant reduction in the PCDD/F concentration of aged sawmill soil can be achieved with a relatively simple olive oil-sunlight treatment. RECOMMENDATIONS AND OUTLOOK: Some theoretical and technological questions need to be solved before using the investigated soil decontamination method in larger-scale applications. The functions of vegetable oils in photodegradation processes should be studied in more detail. The amount of oil that is needed for a proper solubilisation and photodegradation of PCDD/Fs should be minimised. Moreover, special care should be taken to prevent mobilisation of PCDD/Fs to the surrounding environment and to avoid leaving bioavailable residuals of PCDD/Fs in soil.     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from various industrial sources

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm3 (N represents normal conditions at 0 degrees C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm3). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 microg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 microg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Release of polychlorinated dibenzo-p-dioxins and dibenzofurans by setting off fireworks.

Selected pyrotechnic articles were set off under laboratory conditions. Residues and vapors of smoke as well as unburnt charges were analyzed for polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and their precursors chlorinated benzenes and phenols. The contamination of the selected products with these organic xenobiotics proved to be very variable. Remains of fireworks contained octachlorinated dioxins and furans up to 142 ng I-TEQ/kg as well as hexachlorobenzene in the range of 0.05 to 1,400 mg/kg. The deflagration of detonating compositions usually resulted in a dispersion of contaminants, whereas continuously burning flare compositions partially led to a thermal decomposition of organic pollutants. A significant rate of formation of polychlorinated dioxins and furans was observed when setting off blue-lightning rockets and fountains. Further investigations revealed that even high temperatures during the deflagration of black powder charges could not suppress the formation of PCDD/F from appropriate precursors.     

Dry deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air

The PCDD/Fs in the ambient air associated with concentration and dry deposition flux of four seasons were characterized in rural area. The mean PCDD/F concentrations were 0.342, 0.221, 0.675, 0.741 pg m(-3) and the mean I-TEQ values were 0.027, 0.016, 0.024, 0.063 pg m(-3) in spring, summer, fall and winter, respectively. Ambient air in winter was higher by a factor of 3.4 and 3.9 for PCDD/F concentration and I-TEQ, respectively, than in summer. The study area is located in a Tropical region. Hence, domestic heating is not found in this area and is not responsible for the elevated winter concentration in comparison to other studies. A smooth plate with a sharp leading edge that is pointed into the wind by a wind vane was used for measuring dry deposition flux of PCDD/Fs. Atmospheric dry deposition fluxes of total PCDD/Fs were 140, 116, 137, and 207 pg m(-2)day(-1) in spring, summer, fall, and winter, respectively, and averaged approximately 150 pg m(-2)day(-1). The total dry deposition flux was found to decrease as the temperature increased. Calculated dry deposition velocities of total PCDD/Fs were 0.45, 0.52, 0.32 and 0.39 cm s(-1) in spring, summer, fall, and winter, respectively, and averaged 0.42 cm s(-1).     

Absorption of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans by breast-fed infants

The absorption of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans was studied in four breast-fed infants. The absorption was measured by comparing the estimated total intake and the excretion in faeces, during 48 hours, at three different time points; 1, 2 and 3 months post parta. The levels of the analysed compounds in the human milk are typical for Sweden, i.e 20 ppt toxic equivalents for the dibenzo-p-dioxins and dibenzofurans and for the polychlorinated biphenyls 16 ppt toxic equivalents. For most of the congeners the absorption is found to be over 95%. Higher excretion is noticed for heptachlorinated and octachlorinated dioxins.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.     

Fate of polychlorinated dibenzo-p-dioxins and dibenzofurans in a fly ash treatment plant

To understand the fate of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a fly ash treatment plant that used the Waelz rotary kiln process (hereafter the Waelz process), the samples of input and output media were collected and analyzed. The most important PCDD/F source in input mass was electric arc furnace (EAF) fly ash, which had a mean PCDD/F content of 18.51 ng/g and contributed more than 99% of PCDD/F input mass, whereas the PCDD/F input mass fractions contributed by the coke, sand, and ambient air were only 0.04%, 0.02%, and 0.000002%, respectively. For the PCDD/F output mass in the Waelz process, the major total PCDD/F contents of 43.73 and 10.78 ng/g were in bag-filter and cyclone ashes, which accounted for approximately 69% and 17%, respectively, whereas those of stack flue gas and slag were 14% and 0.423%, respectively. The Waelz process has a dechlorination mechanism for higher chlorinated congeners, but it is difficult to decompose the aromatic rings of PCDD/Fs. Therefore, this resulted in the accumulation of lower chlorinated congeners. The output/input ratio of total PCDD/F mass and total PCDD/F international toxicity equivalence (I-TEQ) was 0.62 and 1.19, respectively. Thus, the Waelz process for the depletion effect of total PCDD/F mass was positive but minor, whereas the effect for total PCDD/F I-TEQ was adverse overall.     

Exposure of arc-furnace-plant workers to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)

This study aimed to evaluate serum polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) levels in electric-arc-furnace workers according to their corresponding occupational exposure. In addition, the ambient PCDD/Fs of the work environment were measured to provide additional support for the exposure and accumulation inside the electric arc furnace. The ambient PCDD/F concentrations inside the electric arc furnace were 1.557-1.917 pg-TEQ/Nm(3), 5-24 folds higher than those outside (0.080-0.385 pg-TEQ/N m(3)). In addition, higher average serum levels were measured in the workers with high occupational dioxin exposure (24.0 pg WHO-TEQ/g lipid) than in those with lower occupational dioxin exposure (13.8 pg WHO-TEQ/g lipid). Higher PCDFs/PCDDs ratios were found in serum samples from high-exposure groups than in low-exposure groups. The higher ratio of PCDFs/PCDDs was also found in ambient samples consistent with other metallurgical processes reported previously. Our results suggest that PCDD/Fs exposure exits in the smelting process of electric arc furnace, and the occupational hygiene should be taken more seriously concern in that workplace.     

Trend studies of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in human milk

Human milk has been used in studies of long-term changes in the concentrations of organochlorine contaminants in mothers from the Stockholm region. The previously observed decline (1972 to 1985) in the levels of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) seems to have ceased for certain compounds since the levels were about the same in samples collected in 1985 and 1989. Calculating with the proposed toxicity equivalency factors for the different congeners of PCDDs, PCDFs and PCBs it is seen that the congeners of PCBs contribute more to the possible toxicity than those of PCDDs and PCDFs. The mono-ortho substituted congener 2,3′,4,4′,5-pentachlorobiphenyl (IUPAC No. 118) contributes with the largest part.     

Detailed study on the levels of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2,3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.