Combined approaches to determine the impact of wood fire on PCDD/F and PCB contamination of the environment: a case study

Fires might be the source of persistent organic pollutants (POPs) such as dioxins, furans (PCDD/Fs) and/or polychlorobiphenyls (PCBs) in the environment. In the perspective of defining legal responsibilities a thorough characterization of the impact of such an event should be carried out. However, such characterization is not easy as the environment integrates both local and diffuse sources of such molecules. Thus, a combined approach, which includes gathering field surveys, modeling and laboratory experiments, should be conducted. The objective of this work is to illustrate different approaches to give sufficient insight to determine the actual impact of wood fire on the environment. The work was carried out at the vicinity of a burnt down parcel. The fired material was a mixture of wood and PCB-contaminated soils as the site was a former pyralene-disposal site. Modeling, soil and lichen sampling and experimental combustion were carried out to delineate the contamination for each chemical and to define the area within the fire that was responsible for the environmental contamination. Concentrations of PCDD/F and PCBs were very high on the burnt plot. The combined approach determined that the furans were the predominant compounds in the smoke emitted by the fire. Based on this tracer, it was possible to demonstrate that in terms of environmental contamination of PCDD/F, the impact of the fire was restricted to a 2 km radius from the burnt down plot. For PCBs, no specific tracer was identified. In this case, the delineation of the impact could only be empirical, based on the total concentration of the chemicals.     

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France)

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). summation operator2,3,7,8-PCDD/F and summation operator7ICES PCB air concentrations (0.2-1.4 and 31-57pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476fg L(-1)) and low for PCBs (138-708pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33ng g(-1) d.w., respectively) and mussel (13-21pg g(-1) d.w. and 10-39ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.     

Longitudinal increases in PCDD/F and dl-PCB concentrations in human milk in northern China

There is a dearth of information on the temporal changes in polychlorinated dibenzodioxin/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) contamination, in both environmental and biological specimens, in China. We compared the concentrations of PCDD/Fs and dl-PCBs in human milk collected in Shijiazhuang, Hebei Province, in northern China in 2002 (n=30) and 2007 (n=20). The level of PCDD/Fs and dl-PCBs showed an increasing trend. The mean concentrations of PCDD/Fs plus dl-PCBs were 4.47 TEQ pg g(-1) fat and 6.24 TEQ pg g(-1) fat in human milk from Shijiazhuang in 2002 and in 2007, respectively. Based on statistical analysis of questionnaire data collected by in-person interviews with mothers, we found positive correlations between consumption of sea fish and PCDFs. The PCDDs, PCDFs, PCDD/Fs, and PCDD/Fs plus dl-PCBs levels in individuals consuming greater amounts of sea fish were higher than those consuming less sea fish, both with and without adjustments for potential confounding factors. Among 17 congeners of PCDD/Fs, the 2,3,7,8-TCDF, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF congener concentrations in 2007 increased 134%, 55%, 53%, 57%, 65% and 130% when compared to 2002 levels, respectively. The 2007 dl-PCB congener levels were greater than those of the 2002 samples, with the exception of PCB81 and PCB77. Specifically, PCB105, PCB114, PCB118, PCB123 and PCB156 had increased greater than twofold from 2002 to 2007. Continuous surveillance of PCDD/F and dl-PCB levels in human milk is needed to accurately evaluate both environmental contamination and the human health risk to neonates in China.     

PCDD/F concentrations in milk of nonoccupationally exposed women living in southern Catalonia, Spain

Concentrations of 17 toxic 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) have been determined in pooled samples of breast milk from 15 mothers living in two residential areas (Tarragona downtown and an industrial area) in the vicinity of a new hazardous waste incinerator (HWI), now under construction in Tarragona (southern Catalonia, Spain). PCDD/Fs in human milk samples ranged between 5.9 and 17.1 pg I-TEQ/g fat (162-498 pg I-TEQ/l), with a mean value of 11.8 pg I-TEQ/g fat (310.8 pg I-TEQ/l). The percentages of fat ranged between 1.53 and 3.52. Although PCDD/F levels in milk from mothers living in the industrial area were found to be slightly higher than those observed in women living Tarragona downtown, most differences did not reach the level of statistical significance. In general terms, PCDD/F concentrations in human milk (pooled) samples of mothers living in the area of Tarragona are similar or lower than those previously reported for most industrialized countries.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Relationship of PCDD/Fs congener profiles between beef and raw milk in South Korea

The relationship between profiles of residual PCDD/Fs in beef and raw milk was examined by measuring concentrations and detected frequencies. Unrelated samples of beef and raw milk were collected from nine regions in South Korea. Congener-specific profiles of PCDD/Fs in beef and raw milk were very similar. PCDFs, particularly 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, and 2,3,4,6,7,8-HxCDF, were dominant congeners in both beef and raw milk suggesting that sources of contamination may not significantly differ nationwide. The profiles of PCDD/Fs in domestic beef and raw milk in this study were closer to the profiles of emission from metal industries although Korea imports over 75% of feedingstuffs. The ratios of PCDF/PCDD in TEQ concentration were more than 5 and 15 in beef and raw milk, respectively. The mean concentrations of PCDD/Fs in 60 samples of beef and 60 samples of raw milk were 0.80 pg WHO-TEQ/g fat and 0.65 pg WHO-TEQ/g fat, respectively. The residual profiles of PCDD/Fs in raw milk resembled that in beef although the congener profiles might change throughout the food chain. This indicated that monitoring of dioxins in milk could provide information for contamination of milk itself or other associated food.     

A new enzyme immunoassay for PCDD/F TEQ screening in environmental samples: comparison to micro-EROD assay and to chemical analysis.

A new Enzyme ImmunoAssay (EIA) for PCDD/F TEQ measurement in extracts of environmental samples was described. The bioassay TEQ which derived from EIA and EROD were compared with each other and with results from chemical analysis. For all environmental samples, the EROD-TEQ is higher than the value from chemical analysis. However, the EIA-TEQ is much more identical with the value from chemical analysis. Our results indicate that the EIA assay is a complementary method to the EROD assay and should be useful as a rapid and sensitive screening tool for environmental samples in many situations.     

Evaluation of PCDD/F congener distributions in MWI flue gas treated with SCR catalysts

Partitioning of PCDD/F congeners between gaseous and particulate phases and removal efficiencies of the air pollution control devices (APCDs) for PCDD/Fs at an existing municipal waste incinerator (MWI) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP), wet scrubbers (WS) and selective catalytic reduction system (SCR) as APCDs. The average PCDD/F concentration of stack gas is 1.49 ng/N m³, and the International Toxic Equivalent Quantity (I-TEQ) is 0.043 ng-I-TEQ/N m³. The EP increases PCDD/F concentration by 174.0% while the average removal efficiency of WS + SCR system for PCDD/Fs reaches 99.1%. In addition, the PCDF removal efficiency achieved with WS + SCR system (97.1–99.8%) is higher than that for PCDDs (96.5–99.3%). The results obtained on gas/particulate partitioning in flue gas indicate that the particulate-phase PCDD/Fs accounted for 65% at the inlet of EP, 20% at the outlet of EP and 50% at the stack, respectively, of the total PCDD/F concentrations. This study also indicates that as the chlorination level of PCDD/F congeners increases, the percentage of PCDD/Fs existing in gas phase decreases in all flue gas samples.     

Relationship of PCDD/F and Co-PCB concentrations in breast milk with infant birthweights in Tokyo, Japan

OBJECTIVE: To observe how PCDD/F and Co-PCB concentrations in breast milk relate to infant birthweights in Tokyo, Japan. STUDY DESIGN: Breast milk samples were collected from 240 mothers (aged 25-34years old) residing in Tokyo to measure the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) in the breast milk fat. Individual milk samples (about 50ml) were obtained 30days after delivery, between the months of June and September in 1999 and 2000. The relationship of the infant birthweights with the PCDD/F and Co-PCB concentrations was observed. RESULTS: The birthweights were negatively correlated the concentrations of many of the PCDD/F and Co-PCB congeners, with the mean toxic equivalent quantities (TEQs) of the Co-PCBs, and with the sum of the PCDD, PCDF and Co-PCBs, although their correlation coefficients were less than 0.200. Multiple regression analysis showed octachlorodioxin was statistically significant explanatory variate. CONCLUSIONS: There were slight relationship between the dioxins levels of breast milk and the birthweights of the infants.     

Temporal and local trends of PCDD/F levels in cow's milk in Switzerland

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined in 30 Swiss cow's milk samples collected at dairy farms in the vicinity to point sources, in rural/alpine areas distant to known sources, and from tanks in large industrial milk processing plants. The contaminant concentrations in samples collected in 2001 were compared to data from analyses conducted in 1984 and 1990/1991 at the same sites. In 2001, the PCDD/F levels in milk from farms near point sources (0.63+/-0.26 ng I-TEQ/kg milk fat) are slightly but significantly higher in than milk from remote areas (0.36+/-0.09 ng I-TEQ/kg milk fat). Consumer milk collected at the processing plants had intermediary levels (0.51+/-0.19 ng I-TEQ/kg milk fat). However, milk in 2001 was significantly less contaminated than the samples collected in 1990/1991 and 1984. This trend is particularly pronounced near point sources but is also apparent in consumer milk and milk from remote areas. No geographical gradient in the atmospheric input of PCDD/F in Switzerland was found. The reduction in PCDD/F levels in dairy milk is paralleled by and correlated to the remediation of known PCDD/F emitting industries, as enforced by federal authorities.     

PCDD/F concentrations in soil and vegetation in the vicinity of a municipal waste incinerator after a pronounced decrease in the emissions of PCDD/Fs from the facility

Emission of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by municipal solid waste incinerators (MSWI) is an issue of great concern. In 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an MSWI from Tarragona (Catalonia, Spain). As a result, PCDD/F emissions were significantly reduced. The aim of this study was to determine the current levels of PCDD/Fs in soil and vegetation samples collected near the facility and to compare these levels with those obtained in previous surveys (1996 and 1997). In the period 1997-1999, PCDD/F concentrations in vegetation samples were significantly decreased (60%). By contrast, the levels of PCDD/Fs in soil samples increased slightly (14%, P > 0.05) during the same period. An exhaustive analysis of the present data indicates that other emission sources of PCDD/Fs have also a notable environmental impact on the area under direct influence of the MSWI.     

A design of two simple models to predict PCDD/F concentrations in vegetation and soils

The vegetation and soil levels of the 17 polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) toxic congeners were calculated by means of a vegetation and a soil model, respectively. Both models predicted the levels of the 17 PCDD/F congeners in quite good agreement with the observed results although the soil model was more accurate than the vegetation model. Four different pathways of contribution to the vegetation concentrations were taken into account: vapour-phase absorption, dry particle deposition, wet particle deposition and uptake by root. The most important pathway was the vapour-phase absorption and the less was the uptake by root. In the soils model four pathways were considered: background soil concentration, dry particle deposition, wet particle deposition and uptake by root. After the background concentration, the most important pathway was the wet deposition.     

Effect of urea on fly ash PCDD/F concentrations in different particle sizes

The effect of urea as an inhibitor for reducing polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in flue gases was studied in a pilot scale plant, together with the effect on the particle size distribution of these compounds. Total PCDD/F concentrations decreased by a maximum of 74%, the decrease being greatest for the most highly (octa-) chlorinated isomers. The PCDD/F reduction affected all the particle size classes when an adequate amount of urea was used (1% of the fuel input), which indicates that inhibition, unlike formation, is independent of the fly ash particle size distribution.     

PCDD/F and metal concentrations in soil and herbage samples collected in the vicinity of a cement plant

Juvenoids are biologically active compounds, of relatively low toxicity to humans, that efficiently inhibit the fertility of insects. However, little attention has been paid to the stability and toxicity of products that may be generated by their biodegradation in the ecosystem. This study describes a simple comparison of the toxicity of the active compound and its degradation products generated by aerobic soil microbial isolates. Surprisingly we have found that toxicity of a biologically active carbamate juvenoid N-[2-[4-(2,2-ethylenedioxy-1-cyclohexylmethyl)-phenoxylethyl]carbamate (W328) was comparable with that of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT). The toxic effect was evaluated using the determination of the ATP/ADP content and viability of HeLa S3 cells exposed to various concentrations of the chemicals tested for various durations. DDT was used as a reference compound. Its toxicity was compared with two juvenile hormone analogs. The original compound, W328, was found to be the most toxic. The major product (W329) generated both by yeast isolates and the mixture of moulds lost its activity on reproduction of the tested insect. Its toxicity towards human cells was also decreased. Another two W328 degradation HPLC fractions exhibited significantly reduced toxicity compared to W328.     

Trends of PCDD/F and PCB concentrations and depositions in ambient air in Northwestern Germany

Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations and almost no decrease for the depositions. From the decay rates following first order kinetics, half-lives in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path will continue for another one or two decades in big conurbations.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

PCDD/F and non-ortho PCB concentrations in adipose tissue of individuals living in the vicinity of a hazardous waste incinerator

To assess the influence of a new hazardous waste incinerator (HWI) on public health, a preoperational monitoring program was established during the period of construction. In this study, the levels of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) accumulated in adipose tissue of 15 autopsied subjects living in the area under potential impact of the HWI were determined after approximately 3 years of regular operations in the facility. The non-ortho PCBs 77, 126 and 169 were also determined. PCDD/F concentrations ranged between 1.5 and 41 pg WHO-TEQ/g fat (2.4 and 72 WHO-TEQ/g fat, respectively, including PCBs), with a mean value of 11 pg WHO-TEQ/g fat and a median value of 7.4 pg WHO-TEQ/g fat (22 and 13 WHO-TEQ/g fat, respectively, including PCBs). In the baseline study, the mean level of PCDD/Fs was 36 pg WHO-TEQ/g fat (61 pg WHO-TEQ/g fat, including non-ortho PCBs 77, 126 and 169), which means a reduction of 70% (64% including PCBs). This notable reduction is in accordance with the important decrease observed in recent years in PCDD/F intake through the diet. The current concentrations of PCDD/Fs in human adipose tissue, as well as recent data on PCDD/F levels in plasma and breast milk of subjects living in the vicinity of the same HWI, indicate that there is not any additional significant exposure to PCDD/Fs for this population.     

Textiles as a source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in human skin and sewage sludge

Polychlorinated dibenzo-p-dioxins and dibenzofurans were measured in low- to high-ppb concentrations in several pieces of new clothing from different manufacturers. It was shown that these contaminants are transferred from textiles to human skin during wearing. They were also present in shower water and were washed out of textiles during washing. Extensive evidence was found indicating that contaminated textiles are a major source of chlorinated dioxins and furans in non-industrial sewage sludge, dry cleaning residues and house dust.     

Monitoring PCDD/Fs and other organic substances in workers of a hazardous waste incinerator: a case study

The aim of this study was to measure, 6 years after regular operations, the concentrations of a number of organic substances in blood and urine of 19 workers employed at a hazardous waste incinerator (HWI) in Spain, and to establish the temporal variation with respect to baseline data and previously performed surveys. This facility was the first, and so far the only HWI in that country. The levels of hexachlorobenzene (HCB), polychlorinated biphenyls (PCB 28, 52, 101, 138, 153 and 180) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in six composite plasma samples, while concentrations of di-, tri, and pentachlorophenols, as well those of 1-hydroxypyrene were measured in the urine of these workers. The current mean PCDD/F concentration, 10.4 ng I-TEQ/kg lipid, was significantly lower than that found in the baseline survey, 26.7 ng I-TEQ/kg lipid and similar to that found in the previous (2004) study (7.7 ng I-TEQ/kg lipid). PCDD/F levels in plasma were similar or even lower than those recently reported for various non-exposed populations. For the remaining analyzed substances in plasma and urine, there was not any significant increase in comparison with the levels found in the baseline survey. On the other hand, no marked differences between the concentrations of organic substances in plasma or urine were found according to the respective workplace (plant, laboratory and administration). The results of the present survey indicate that after 6 years of regular operation, the workers at the HWI are not occupationally exposed to PCDD/Fs and other organic substances in their workplaces.     

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.