Distribution of PCDD/F in the vicinity of the hazardous waste incinerator at Schwabach

The distribution of PCDD/F and a selection of heavy metals in the surrounding area of the Hazardous Waste Incinerator (HWI) at Schwabach has been determined. The PCDD/F concentrations measured in soil, grass and lettuce samples are compared to modeling studies realized by the TÜV Bayern.     

PCDD/F reduction in incinerator flue gas by adding urea to RDF feedstock

The effect of urea on PCDD/F formation in a pilot incinerator was studied by incinerating urea with refuse-derived fuel (RDF) at three concentrations (0.1%, 0.5% and 1.0%, of the fuel feed). A distinct reduction in both PCDD/F and chlorophenol concentrations could be noticed when urea was introduced into the system. Partial-least-square (PLS) analysis of the data showed the importance of certain chlorophenol isomers as PCDD/F precursors, pointing to the possibility that the impact point of the urea inhibitor could be before the precursor molecules, i.e. chlorophenols, have been formed.     

Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

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.     

Levels of PCDD/F in adipose tissue on non-occupationally exposed subjects living near a hazardous waste incinerator in Catalonia, Spain

The potential adverse effects on human health of hazardous waste incinerators (HWIs) are a subject of concern. The construction of the first and till now only HWI in Spain finished in 1999. In 2007, after approximately 9 years of regular operations in the facility, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined by HRGC/HRMS in samples of adipose tissue of 15 autopsied subjects living in the area under potential impact of the HWI (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/F concentration in adipose tissue was 14.6 pg WHO-TEQ/g of fat (range: 3.3–55.4 pg WHO-TEQ/g of fat). It means significant changes (a reduction of 64% and an increase of 47%) in the mean PCDD/F levels in comparison to those found in 1998 and 2002: 40.1 and 9.9 pg WHO-TEQ/g of fat, respectively. Women showed higher levels of PCDD/F than men (23.8 vs 11.2 pg WHO-TEQ/g of fat). The increase in the last 5 years would not be directly attributable to exposure to PCDD/F emitted by the HWI, as other biological monitors such as human plasma and milk decreased during the same period.     

Dietary exposure to PCDD/PCDFs by individuals living near a hazardous waste incinerator in Catalonia, Spain: temporal trend

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were measured in foodstuffs randomly acquired in July 2006 in various locations of Tarragona County (Catalonia, Spain), which are near a hazardous waste incinerator (HWI). A total of 35 composite samples, belonging to various food groups (vegetables, pulses, cereals, fruits, fish and seafood, meat and meat products, eggs, milk, dairy products, and oils and fats) were analyzed by HRGC/HRMS. The dietary intake of PCDD/PCDFs was subsequently determined and compared with a previous survey performed in 2002. For calculations, recent data on consumption of the selected food items were used. Total dietary intake of PCDD/PCDFs for the general population of Tarragona County was estimated to be 27.81 pg WHO-TEQ/day, value notably lower than that found in the 2002 study, 63.80 pg WHO-TEQ/day. Fish and seafood (28%), oils and fats (22%), eggs (17%), and dairy products (11%) were the most important contributors to this intake, while pulses (1%), milk (2%), vegetables (3%) and fruits (3%) showed the lowest contribution to total WHO-TEQ. The current PCDD/PCDF intake is also considerably lower than the intake estimated in 1998 for the population of the same geographical area, 210.1 pg I-TEQ/day, when a baseline study was carried out during the construction of the HWI. The present intake is also compared with the dietary intakes of PCDD/PCDFs recently (2006-2007) reported for a number of regions and countries.     

Decontamination trends in the aquacultured fish gilthead seabream (Sparus aurata) after feeding long-term a PCDD/F spiked feed

Aquacultured fish gilthead seabream (Sparusaurata), previously exposed to low levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) trough the diet for a 13 months period, were fed on a clean feed for another 22 months. Gilthead seabream is a protandrous hermaphrodite species and this “decontamination” period coincided with the stages of sex differentiation, maturity and reproduction of the fish. PCDD/F levels in the fish tissues (i.e. muscle, liver, perivisceral fat and gonads), expressed in pg WHO-TEQ g⁻¹ fresh weight, showed a general decreasing trend during the “decontamination” period. However, this general trend varied among tissues and was also dependent on sex and lipid contents. Toxicological effects affecting fish behaviour and hepatic marker responses were also evaluated. The results pointed out that exposure to PCDD/Fs did not have an impact on fish development and reproduction, since the proportion of sexes found after the sex reversal process was within the normal range described for this species. In addition, long-term exposure to low PCDD/F levels did not significantly affect the response of most of the biochemical markers considered. On the contrary, some of them (e.g. EROD activity) showed variations in their responses during the sex differentiation process and onwards. Finally, the hepatic AhR mRNA levels increased during dioxin exposure but they returned to values typical for non-exposed fish after the “decontamination” period.     

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.     

Environmental impact of a new hazardous waste incinerator in Catalonia,Spain: PCDD/PCDF levels in herbage samples

In April 1996 and 1998, the concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in 40 herbage samples collected in the neighborhood of a hazardous waste incinerator (HWI) under construction in Constanti (Catalonia, Spain). In April 2000, 20 months after the HWI began operating, herbage samples were again collected at the same sampling points in which samples had been taken in the previous surveys. PCDD/F concentrations ranged between 0.13 and 0.65 ng I-TEQ/kg (dry matter), with a median and mean values of 0.29 and 0.32 ng I-TEQ/kg (dry matter), respectively. The results were compared with those obtained in the 1996 (median, 0.53 ng I-TEQ/kg; mean, 0.61 ng I-TEQ/kg) and the 1998 (median, 0.23 ng I-TEQ/kg; mean, 0.31 ng I-TEQ/kg) surveys. While in the period 1996-1998 a significant decrease (49%, P < 0.001) in the mean PCDD/F levels was noted, in the period 1998-2000 an increase of 3% (P > 0.05) was found in the concentrations of PCDD/Fs. The analysis of the results suggests two potential hypotheses: either the emissions of PCDD/Fs from the HWI are not negligible, or the current PCDD/F emissions from other sources near the HWI remained at similar levels to those reached in 1998. Anyhow, an exhaustive evaluation of the present data shows an absence of notable PCDD/F contamination by the HWI in the area under its direct influence. It seems also probable that the decline in the atmospheric levels of PCDD/Fs due other emission sources of PCDD/Fs in this area is currently stopped.     

Concentrations of PCDD/PCDFs in plasma of subjects living in the vicinity of a hazardous waste incinerator: follow-up and modeling validation

In 2007, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) were determined in plasma of non-occupationally exposed subjects living near the only hazardous waste incinerator (HWI) in Spain (Constantí, Tarragona County, Catalonia). These data were compared with the levels found in two previous surveys performed in 1998 (baseline) and 2002. The current mean PCDD/PCDF concentration in plasma was 9.36pg I-TEQg(-1) of lipid (range: 1.76-23.44pg I-TEQg(-1) of lipid). It means a significant reduction of the mean PCDD/PCDFs levels in plasma in comparison to the concentrations found in 1998 and 2002 (27.01 and 15.70pg I-TEQg(-1) of lipid, respectively). This important decrease agrees well with the notable reduction in the dietary intake of PCDD/PCDFs recently noted for the population of the same area (210.1pg I-TEQd(-1), 63.8pgWHO-TEQd(-1), and 27.8pgWHO-TEQd(-1), in 1998, 2002 and 2007, respectively). The current data were also used to predict theoretical PCDD/PCDF concentrations in plasma by executing a single-compartment empirically-based pharmacokinetic model on the basis of the daily intake of these pollutants by the local population.     

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.     

Assessment of emissions and removal of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) at start-up periods in a hazardous waste incinerator

A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.     

PCDD/Fs atmospheric deposition fluxes and soil contamination close to a municipal solid waste incinerator

Bulk depositions and surface soil were collected in a suburban area, near the Adriatic Sea, in order to assess the contribution of a municipal solid waste incinerator to the area’s total contamination with polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDDs and PCDFs). Samples were collected at two sites, situated in the area most affected by plant emissions (according to the results of the Calpuff air dispersion model), and at an external site, considered as a reference. Results show that the studied area is subject to low contamination, as far as these compounds are concerned. Deposition fluxes range from 14.3 pg m⁻² d⁻¹ to 89.9 pg m⁻² d⁻¹ (0.75 pg-TEQ m⁻² d⁻¹ to 3.73 pg-TEQ m⁻² d⁻¹) and no significant flow differences are observed among the three monitored sites. Total soil concentration amounts to 93.8 ng kg⁻¹ d.w. and 1.35 ng-TEQ kg⁻¹ d.w, on average, and confirms a strong homogeneity in the studied area. Furthermore, from 2006 to 2009, no PCDD/Fs enrichment in the soil was noticed. Comparing the relative congener distributions in environmental samples with those found in stack emissions from the incineration plant, significant differences are observed in the PCDD:PCDF ratio and in the contribution of the most chlorinated congeners. From this study we can conclude that the incineration plant is not the main source of PCDD/Fs in the studied area, which is apparently characterized by a homogeneous and widespread contamination situation, typical of an urban area.     

PCDD/F and PCB in spruce forests of the Alps

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Congener profiles of PCDD/Fs in soil and vegetation samples collected near to a municipal waste incinerator

Recently, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in soil and herbage samples collected in the vicinity of a municipal solid waste incinerator (MSWI) from Tarragona (Catalonia, Spain). Since these concentrations could be increased by the presence of other emission sources of PCDD/Fs in the same area in which the MSWI is placed, the main goal of the present study was to determine the PCDD/F congener profiles in the soil and vegetation samples collected in 1996 and again in 1997 near to the facility and to compare with those from samples collected in a close area outside of direct emissions of the plant. From an accurate inspection of the PCDD/F congener profiles, it was concluded that PCDD/F emissions from the MSWI here examined are neither the only nor the main responsible for the presence of PCDD/Fs in the samples of environmental matrices collected in the area under direct influence of the plant.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Influence of variation in the operating conditions on PCDD/F distribution in a full-scale MSW incinerator

Optimizing the operating parameters to minimize polychlorodibenzo-p-dioxins and polychlorodibenzofurans (PCDD/F) emission is the common interest of the municipal solid waste (MSW) incineration industry. In this study, we investigated the distribution of tetra- to octa-CDD/F along the flue gas line in a full-scale reciprocating grate incinerator and evaluated the effects of temperature control and O(2) level on PCDD/F formation. Six runs were laid out and all performed under sufficient burning conditions, in which the combustion efficiency of MSW was more than 99.9%. The total concentration of tetra- to octa-CDD/F measured at the boiler outlet showed an increasing tendency with the increase of boiler outlet temperature (T(B)) from 214 degrees C to 264 degrees C. When flue gas ran across the semi-dry scrubber and cyclone precipitator, in which the temperature varied from 264 degrees C to 162 degrees C, the concentrations of the lower chlorinated dioxins and furans were significantly raised, especially for the TCDF. Increasing O(2) supply from 6.0% to 10.5% essentially led to a higher yield of tetra- to octa-PCDD/F, suggested that under sufficient burning conditions the lower O(2) level was favorable for reducing PCDD/F formation and emission. The variation of O(2) level did not give rise to a systematical change of PCDD/F homologue pattern. For all measurements, the isomer distributions of tetra- to hepta-PCDD/F were more or less the same, nearly independent of variations in the operating conditions and sampling positions. Only the significant increase of the sum of 1,3,7,8-TCDF and 1,3,7,9-TCDF was found in the zone after the boiler section.     

Levels of PCDD/Fs,PCBs and PBDEs in breast milk of women living in the vicinity of a hazardous waste incinerator: Assessment of the temporal trend

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in previous surveys carried out in the same area in 1998 (baseline study), 2002 and 2007. The current total concentrations of 2,3,7,8-chlorinated PCDD/Fs in breast milk ranged from 18 to 126 pg g⁻¹ fat (1.1–12.3 pg WHO₂₀₀₅-TEQ_PCDD/F), while the total levels of PCBs ranged from 27 to 405 pg g⁻¹ fat (0.7–5.3 pg WHO₂₀₀₅-TEQ_PCB). In turn, PBDE concentrations (sum of 15 congeners) ranged 0.3–5.1 g g⁻¹ fat, with a mean value of 1.3 ng g⁻¹ fat. A general decrease in the concentrations for PCDD/Fs, both planar and total PCBs, and PBDEs in breast milk was observed. The levels of PCDD/Fs, PCBs, and PBDEs in milk of women living in urban zones were higher than those corresponding to industrial zones (41%, 26%, and 8%, respectively). For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants that we have also observed in recent studies carried out in the same area of study.     

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.