Temporal trends and spatial distribution of PCDD, PCDF, and PCB in pine and spruce shoots

In Germany, there is a lack of consistent and comparable data for the time dependent behaviour and spatial distribution of dioxin-like and indicator PCB in ambient air, deposition and plants. The aim of this study was to improve the data on PCDD/PCDF, dioxin-like PCB and non dioxin-like PCB in spruce and pine shoots from different locations and years by retrospective monitoring. The survey was conducted with archived samples of one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) from the German environmental specimen bank. Two sets of samples from locations in urbanized areas in western and eastern Germany (Warndt and Duebener Heide Mitte, respectively) were investigated as time series. Additionally, spruce shoots from seven different rural locations sampled in the years 2000-2004 were analyzed in order to get an overview about the spatial distribution of PCB and PCDD/PCDF. The analytical results of the samples from the two urbanized areas clearly show that the atmospheric contamination with PCDD and PCDF has declined by about 75% between 1985 and 1997 at Warndt and about 40% between 1991 and 1997 at Duebener Heide. However, concentrations stayed virtually constant at both locations from 1997 to 2004 at a level of about 1 ng WHO-TEQ/kg dry matter (d.m.). Similarly, the investigation of spruce shoots from rural locations from 2000 to 2004 did not reveal a temporal trend at any site. PCDD/PCDF levels were between 0.1 and 1.0 ng WHO-TEQ/kg d.m. At the urbanized location Warndt the six indicator PCB as well as the 12 dioxin-like PCB according to WHO revealed a significant decline by more than 75% between 1985 and 1999. Thereafter, PCB levels stayed virtually constant. At the location Duebener Heide an overall decrease of PCB concentrations in pine shoots of about 60% was detected between 1991 and 2004. Spruce shoots from all locations showed a relevant contribution of dioxin-like PCB to the total WHO toxicity equivalent (PCDD/PCDF+PCB). In most samples, the contribution of dioxin-like PCB was between 21% and 41%. The TEQ contribution of PCB in the samples from three rural sites was higher and similar to the TEQ value of PCDD/PCDF. The investigated pine shoots from the urbanized site Duebener Heide showed a 15-28% contribution of dioxin-like PCB to total TEQ and thus lower than in spruce shoots from different locations. In all samples except one PCB 126 contributed to more than 80% to the PCB-TEQ.     

PCDD/PCDF,chlorinated pesticides and PAH in Chinese teas

Four samples of Chinese tea (two green teas, and two brick teas) were analyzed for their concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF), chlorinated pesticides and PAH. The infusions prepared from these teas were also analyzed for PCDD/PCDF. The levels of DDT and its metabolites in tea leaves were within the safety limit of 0.2 mg/kg. Rather high levels of total PAH were obtained in brick tea (1048–1162 mg/kg), when compared with green tea (497–517 mg/kg). In terms of PCDD/PCDF, the concentrations of green tea and brick tea differed by a factor of 16, while the concentrations of all infusions were within a factor of 2. The dioxin concentrations in green tea leaves can be explained through uptake of atmospheric PCDD/PCDF. The higher concentrations in the brick tea leaves are due the longer exposure time, and to certain extent, the use of old leaves, branches and roots when making the tea, and additional components such as soil particulates through contamination. Certain Chinese populations drinking a large amount of brick tea (>3 l per day) indicated that individuals of these populations consume more tea than Europeans or North Americans result in a comparably higher intake of PCDD/PCDF. Tea consumption can attribute to up to 10% of the TDI recommended by WHO (only PCDD/PCDF considered, no PCB analyzed).     

Environmental prospection for PCDD/PCDF, PAH, PCB and heavy metals around the incinerator power plant of Reggio Emilia town (Northern Italy) and surrounding main roads

Samples of soil, sediment and pine needles from the Reggio Emilia area were analysed in order to estimate the environmental pollution caused by an MSWI. PCDD/PCDF, PCB, PAH and metals were analysed in the collected samples. The data obtained showed relatively low pollution levels. Indeed, the PCDD/PCDF and PCB data were comparable to the values usually found in the grazing areas of the European Union countries. Metal concentrations in soils and sediments may be related to local geological occurrences and to agricultural activities. PAH values are significantly lower than the limit values set by the Italian law.     

Sources and fate of PCDD and PCDF

PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.     

Correlation of PCDD/PCDF and CO values in a MSW incinerator--indication of memory effects in the high temperature/cooling section

The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.     

PCDD/PCDF emissions from small firing systems in households

This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.     

Human PCDD/PCDF levels near a pentachlorophenol contamination site in Tainan, Taiwan

A pentachlorophenol (PCP) manufacturing plant in southern Taiwan discontinued production in 1989. The site of the abandoned plant was heavily contaminated by PCDD/PCDFs, impurities formed in the PCP production process. Serum samples collected from 27 residents living near the deserted plant were evaluated to determine whether this contamination had associated serum levels of PCDD/PCDFs in local residents. The average level of 17 tested congeners ranged from 556 to 5240 pg/g lipid (mean, 1670 pg/g lipid). The corresponding 2,3,7,8-TCDD toxicity equivalent quotient values calculated by international toxicity equivalent factors (I-TEFs) and those recommended by WHO (WHO-TEFs) were 47.2 pg I-TEQ/g lipid and 53.4 pg WHO-TEQ/g lipid, respectively. Levels in other parts of Taiwan typically range from 15 to 20 pg WHO-TEQ/g lipid; therefore, it is likely that the heavily contaminated plant site caused these unusually high serum levels. The average PCDD/PCDF levels of 29 fish-tissue and nine soil samples collected from the sea reservoir surrounding the abandoned PCP plant were also abnormally high: 8630 pg/g lipid (985 pg WHO-TEQ/g lipid) and 606000 pg/g-sample (922 pg WHO-TEQ/g-sample), respectively. Factor analysis indicated that the congener pattern of human serum samples collected from residents living near the abandoned PCP plant different from samples collected from other areas in Taiwan without known PCDD/PCDF pollution. Similar results were observed for the fish tissue and soil samples. The current study may have discovered a "hot spot" for elevated dioxin human exposure in Taiwan. The preliminary finding has raised a public health concern in the inspected area and requires further investigations to clarify the nature of the contamination and potential impact on the local environment and human health.     

Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

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.     

Influence of temperature on PCDD/PCDF desorption from waste incineration flyash under nitrogen

A municipal solid waste incinerator flyash was heated to between 200 and 400 degrees C under nitrogen in a bench-scale, static bed reactor for 4 days soak time. The influence of temperature on the levels of PCDD and PCDF remaining in and desorbed from the ash were investigated using GC-MS/MS. PCDD and especially PCDF formation was seen on the flyash between 225 and 300 degrees C. Large increases in the I-TEQ of the treated ash relative to the increase in its overall PCDD/PCDF content indicated that the formation of 2378-substituted congeners was favoured over that of other substitution patterns. In the absence of a source of gaseous oxygen, formation was mainly attributed to de novo reactions involving solid phase oxygen. Dechlorination of the PCDD/PCDF in flyash became increasingly important above 275 degrees C. Maximum desorption was seen at 325 degrees C, with the equivalent of 35 wt% of the PCDD/F in the original flyash being recovered from the exhaust traps at this temperature. The desorbed species were mainly M(1)CDD/CDDF-T(3)CDD/CDDF resulting from dechlorination of higher chlorinated PCDD/PCDF, with consequently low I-TEQ values.     

Photodegradation of PCDD/Fs adsorbed on spruce (Picea abies (L.) Karst.) needles under sunlight irradiation

Spruce (Picea abies (L.) Karst.) needles were exposed to exhaust gas containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) generated by combustion of polyvinyl chloride, wood, high-density polyethylene, and styrene. Photodegradation of PCDD/Fs adsorbed on spruce needles under sunlight irradiation was studied. The photodegradation of PCDD/Fs follows pseudo-first-order reaction kinetics, with photolysis half-lives ranging between 40 and 100 h. The photolysis rates of PCDF congeners are higher than PCDD congeners with the same chlorinated substitutions. Higher chlorinated PCDD/Fs tend to photolyze slowly. The wax components in spruce needles may act as proton donors and accelerate the photolysis rate. C-Cl cleavage through the addition of protons to PCDD/F molecules may be an important route for PCDD/Fs photodegradation.     

Effects of combustion and operating conditions on PCDD/PCDF emissions from power boilers burning salt-laden wood waste

This paper discusses the effects of combustion conditions on PCDD/PCDF emissions from pulp and paper power boilers burning salt-laden wood waste. We found no correlation between PCDD/PCDF emissions and carbon monoxide emissions. A good correlation was, however, observed between PCDD/PCDF emissions and the concentration of stack polynuclear aromatic hydrocarbons (PAHs) in the absence of TDF addition. Thus, poor combustion conditions responsible for the formation of products of incomplete combustion (PICs), such as PAHs and PCDD/PCDF precursors, increase PCDD/PCDF emissions. PAH concentrations increased with higher boiler load and/or low oxygen concentrations at the boiler exit, probably because of lower available residence times and insufficient excess air. Our findings are consistent with the current understanding that high ash carbon content generally favours heterogeneous reactions leading to either de novo synthesis of PCDD/PCDFs or their direct formation from precursors. We also found that, in grate-fired boilers, a linear increase in the grate/lower furnace temperature produces an exponential decrease in PCDD/PCDF emissions. Although the extent of this effect appears to be mill-specific, particularly at low temperatures, the results indicate that increasing the combustion temperature may decrease PCDD/PCDF emissions. It must be noted, however, that there are other variables, such as elevated ESP and stack temperatures, a high hog salt content, the presence of large amounts of PICs and a high Cl/S ratio, which contribute to higher PCDD/PCDFs emissions. Therefore, higher combustion temperatures, by themselves, will not necessarily result in low PCDD/PCDFs emissions.     

Comparison of PCDD and PCDF in flyash collected from muncipal incinerators of different countries

Flyash samples were collected from the electrostatic precipitators of seven municipal refuse incinerators of four different countries. Analytical results of PCDD and PCDF in these samples shows a very similar iosmer distribution pattern for all PCDD/PCDF although concentrations of PCDD and PCDF vary. These results imply that PCDD/PCDF were formed through the same mechanism in those incinerators regardless of garbage composition or incinerator design.     

Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators

The effect of thermal treatment of fly ash on the behaviour of PCDD/PCDF was studied in the range between 120 and 600° C. Annealing at 300° C (2 hrs) resulted in an increase of PCDD/PCDF concentration by a factor of 10 to 15. At 600° C degradation to concentrations below 0.1 ng/g is observed.     

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.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

PCDD/PCDF reduction by the co-combustion process

A novel process, termed the co-combustion process, has been developed and designed to utilise the thermal treatment of municipal solid waste (MSW) in cement clinker production and reduce PCDD/PCDF emissions. To test the conceptual design; detailed engineering design of the process and equipment was performed and a pilot plant was constructed to treat up to 40 tonnes MSW per day. The novel process features included several units external to the main traditional cement rotary kiln: an external calcinations unit in which the hot gas calcined the limestone thus making significant energy savings for this chemical reaction; the lime generated was used in a second chamber to act as a giant acid gas scrubber to remove SOx and particularly HCl (a source of chloride); an external rotary kiln and secondary combustion unit capable of producing a hot gas at 1200 degrees C; a gas cooler to simulate a boiler turbogenerator set for electricity generation; the incorporation of some of the bottom ash, calcined lime and dust collector solids into the cement clinker. A PCDD/PCDF inventory has been completed for the entire process and measured PCDD/PCDF emissions were 0.001 ng I-TEQ/Nm(3) on average which is 1% of the best practical means [Hong Kong Environmental Protection Department, 2001. A guidance note on the best practicable means for incinerators (municipal waste incineration), BPM12/1] MSW incineration emission limit values.     

Long-term automated sampling of PCDD/PCDF flue gas: current status and critical issues

After entry into force of the Stockholm Convention and Aarhus Protocol and in order to implement the upcoming European legal background, the European countries are asked to apply control measures to reduce the release of persistent organic pollutants (POPs) such as dioxins and furans (PCDD/PCDF) and polychlorinated biphenyls as well as to establish POPs release inventories. In this perspective, development of measuring techniques of emissions is a focal issue in acquiring useful information. In this paper, results of various measurement campaigns at different municipal waste incineration (MWI) plants using long-term automated sampling of PCDD/PCDF are presented. The samples collected from both manual and automated campaigns were analyzed following the European Standard EN-1948:2006 by high-resolution gas chromatograph/high-resolution mass spectrometer. Performances of two different commercial systems have been investigated. Anomalous values occurred during one long-term campaign (22.16 pg I-toxic equivalent (TEQ)/Nm(3)), compared to average values (4-5 pg I-TEQ/Nm(3)) of the MWI. At this maximum value, a main occurrence of abnormal and instable operating conditions has been found. Sampling based on long-term basis was found to be more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Nevertheless, the results of long-term campaigns demonstrate that emission levels detected in 15-30 days campaigns, when unsteady operating conditions can occur, as start-up and shut down, are not immediately comparable to the typical levels in a 6-8 h, when operating conditions are generally stable. Moreover, there are often differences observed in the congener profiles between short- and long-term campaigns.     

Simultaneous monitoring of PCDD/Fs and PCBs in contaminated air with semipermeable membrane devices and fresh spruce needles

The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.     

Kinetics of carbon degradation and PCDD/PCDF formation on MSWI fly ash

The native carbon oxidation and PolyChloroDibenzo-p-Dioxins and PolyChloroDibenzoFurans, PCDD/F, formation were simultaneously studied at different temperatures (230-350 degrees C) and times (0-1440 min) in order to establish a direct correlation between the disappearance of the reagent and the formation of the products. The kinetic runs were conducted in an experimental set up where conditions were chosen to gain information on the role of fly ash deposits in cold zones of municipal solid waste incinerators in PCDD/F formation reaction. The carbon oxidation measured as the decrease of total organic carbon of fly ash was in agreement with the carbon evolved as sum of CO and CO(2). The carbon mass balance indicated an increase in the efficiency of carbon conversion in CO and CO(2) with temperature. The CO and CO(2) formation was the result of two parallel pseudo first order reactions thus giving significant information about the reaction mechanism. PCDD/F formation as a function of temperature showed that the maximum formation was achieved in a narrow range around 280 degrees C; the time effect at 280 degrees C was a progressive formation increase at least up to 900 min. The PCDF:PCDD molar ratio increased with temperature and time, and the most abundant homologues were HxCDD, HpCDD, OCDD for PCDD, and HxCDF, HpCDF within PCDF. These experimental results supported the hypothesis that the formation mechanism was the de novo synthesis.