PCDDs and PCDFs in sewage sludge, river and lake sediments from south west Germany

Sewage sludges and sediments of rivers and lakes are sinks for “persistent” organic compounds entering the environment. These matrices are therefore useful in the assessment of local and global pollution with certain compounds or classes of compounds. In recent years we have analyzed sediments of the rivers Neckar, Rhine, and Danube, from Lake Constance, and samples of sewage sludge from municipal waste water treatment plants of south-west Germany for PAH, phthalates, organochlorine pesticides, and PCBs. ¹ We have now analyzed a number of these samples for PCDDs and PCDFs. Isomer-specific analyses for 2,3,7,8-subsituted PCDDs/PCDFs were carried out in all cases.

In all samples PCDDs could be detected, and in most cases PCDFs as well. 2,3,7,8-TCDD was never detected at a detection limit of 0.01 ppb. In sediments (14 samples) the total PCDDs ranged from 0.1 to 2.9 ppb and PCDFs from “not detectable” to 1.2 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.06 ppb. In sewage sludges (15 samples) the total PCDDs ranged from 4 to 65 ppb and PCDFs from 1 to 7 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.57 ppb.

Comparison of PCDD/PCDF patterns of congeners and isomers for the sewage sludge and river sediment samples with those of stack gas emissions of waste incinerators and of pentachlorophenol allows the conclusion that the main source of PCDDs and PCDFs found in these samples is pentachlorophenol. Results of the Lake Constance sediment core indicate that here the atmospheric immission from waste incineration might be predominant.     

Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Levels, profile and pattern of PCDDs and PCDFs in samples related to the production and use of chlorine

Analyses of sludge from graphite electrodes used in the chloralkali process show total levels of PCDFs as high as 650000 pg/g sludge. The levels of tetra-, penta-and hexaCDFs were found to be approximately the same. The levels for the corresponding PCDDs were below the detection level. The dominating congeners within each group are the toxic 2,3,7,8-substituted PCDFs at levels of 340000 pg/g, This typical pattern, called the “chloralkali pattern” can also be found in soil samples taken at another chloralkali plant. The typical pattern can also be identified in a solution of ferric chloride. Traces of “chloralkali pattern” are identified in a sludge sample from the drinking water purification plant, the source for PCDFs in the sludge is unknown.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in invertebrate animals from a rural beach in Japan

PCDDs and PCDFs were analyzed by high resolution GC MS in several invertebrate animals collected from a rural beach in Japan. PCDDs and PCDFs were detected in all samples. Total concentration of PCDDs and PCDFs ranged 8.8–120 pg g⁻¹ wet and 3.5–38 pg g⁻¹ wet, respectively. TEQs of invertebrate animals examined ranged from 0.048 pg g⁻¹ wet in sea slug to 0.91 pg g⁻¹ wet in mussel. Isomer profiles in all samples were similar to each other despite of variety of species. Their major sources are estimated to be herbicides such as CNP and PCP, and combustion by using a statistical analysis of isomer profiles.     

Improvements in dioxin abatement strategies at a municipal waste management plant in Barcelona

This study presents the results of a dioxin abatement programme undertaken in the municipal waste incineration plant of Montcada i Reixac (Barcelona, Spain) after the replacement of an obsolete air cleaning device by a new flue gas treatment system. A number of sampling campaigns were conducted with the aim of characterising stack gas emission levels of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and to evaluate initial specifications of dioxin stack gas emission values below 0.1 ng I-TEQ/Nm(3). Preliminary results revealed levels between 44 and 111 ng I-TEQ/Nm(3) when the gas-cleaning system consisted only of an old electrostatic precipitator (ESP). Decreased levels around 15 ng I-TEQ/Nm(3) were observed when the semi-dry scrubber began to operate and the ESP was switched off. Again, remarkable dioxin removal was observed after the installation of the fabric filter and levels around 0.3-0.4 ng I-TEQ/Nm(3) were soon achieved. Nevertheless, the limit of 0.1 ng I-TEQ/Nm(3) was reached by additional injection of activated carbon which helped to lower PCDD/PCDF levels to around 0.036 ng I-TEQ/Nm(3). The results also demonstrated a significant change in the dioxin distribution present in combustion-derived materials (stack gas emission, bottom ash and solid waste from gas treatment). The major dioxin fraction was found in gaseous matrices before the flue gas control system was upgraded. After this step, the major dioxin fraction content was observed in solid waste from gas treatment.     

PCDDs/PCDFs in ambient air (<1 fg m(-3)) - the CTDEP long term sampling (30 d) method

The Connecticut Department of Environmental Protection (CTDEP) commenced monitoring for PCDDs/PCDFs (polychlorinated dibenzodioxins and polychlorinated dibenzofurans) in ambient air in 1987 and adopted the long term (30 d) sampling approach in 1993. The CTDEP method represents the first use of isotopically labeled PCDDs/PCDFs as field surrogates to monitor the behavior of native PCDDs/PCDFs present in actual ambient air samples. This feature first introduced in 1987 was later adopted by US EPA in revisions to sampling methods for PCDDs/PCDFs in ambient air (EPA Method TO9A) as well as development of EPA Reference Method 23 for measurement of PCDDs/PCFDs in stationary source emissions. Results are provided here for a total of twenty-three (23) samples (reported as pairs) representing twelve (12) 30 d sampling events conducted at a site located in metropolitan Hartford CT. Samples were collected in winter months during calendar years 2002-2008. PCDDs/PCDFs concentration data (pg m⁻³) are reported as both congener sums (Cl₄-Cl₈) and 2378-substitued congeners. Total PCDDs/PCDFs concentrations for these twelve (12) sampling events ranged from 0.68 pg m⁻³ (2003) to 4.18 pg m⁻³ (2004) with a mean concentration of 2.04 pg m⁻³.Method performance was monitored through use of collocated samples, in field isotopically labeled compounds, isotopically labeled laboratory applied internal standards and field blank samples. Method performance consistently exceeded goals established in USEPA Method TO9A for these same parameters. Average recoveries of in field labeled PCDDs/PCDFs ranged from 97.5% to 104.2%. Average (mean) recoveries for each of the ten (10) isotopically labeled internal standards ranged from 77.0% (¹³C-OCDF) to 95.5% (¹³C-2,3,7,8-TCDF). Method precision defined as % RPD data for collocated sampler pairs ranged from 8% to 14% for PCDDs and from 5% to 12% for PCDFs. The mean RPD for all PCDDs/PCDFs combined is 9.6%. Field monitoring results demonstrate method sensitivity for all PCDDs/PCDFs congeners and 2378-substituted congeners to be well below concentrations typically found for these compounds in ambient air (all reported data represent measured concentrations). Quantities (pg) found in field blanks represent the major determinant to achieving further enhancements in method sensitivity for selected congeners (OCDD < 42 fg m⁻³; 1,2,3,4,6,7,8-HpCDD < 5.7 fg m⁻³; and 1,2,3,4,6,7,8-HpCDF < 2.1 fg m⁻³). The CTDEP method represents a highly sensitive and reliable technique for monitoring of PCDDs/PCDFs congeners and other persistent organic pollutants (POPs) at ultra trace levels in ambient air (fg m⁻³).     

PCDDs, PCDFs emission control by dry scrubbing system

Presently, in Japan there are no limitations on the emission of PCDDs or PCDFs, but in order to study the feasibility of dry type air pollution control, a pilot plant was constructed in 1988 and the removal efficiencies for PCDDs, acid gas and heavy metals were measured.At the same time PCDDs concentration was compared with that of a previously installed electrostatic precipitator (ESP) plus wet scrubber line.In this paper, the following two items are reported.

1. (1) The difference in the amounts of PCDDs and PCDFs produced due to differences in gas temperature and retention time in ESP and fabric filter (FF).

2. (2) Removal efficiencies of PCDDs and PCDFs of fabric filter.

PCDDs concentration, generally 100–200 ng/Nm³ at the boiler outlet (ESP inlet and/or Quench Reactor (QR) inlet), increased several times at the ESP outlet, but it showed almost no increase at the QR outlet due to a sudden temperature drop. The temperature was 280–310°C, and the gas retention time was 12 sec. during passage through ESP so that it is thought that PCDD was formed under these conditions.On the other hand, a removal efficiency of approx. 90% was obtained with the fabric filter, and the PCDD at the bag outlet was at a sufficiently low level.     

Sampling,occurrence and evaluation of PCDDs and PCDFs from incinerated solid urban waste

The sampling procedure of solid and gaseous pollutants, contained in flue gas emitted into the atmosphere by solid waste incinerating furnaces were investigated. Because of their extraordinary toxicological properties, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are taken into particular consideration. The analytical work is based on the use of high-resolution gas chromatography in combination with low-resolution mass spectrometry. Details of the extensive sample clean-up will follow the GC-MS separation and identification of the isomers detected for each group of PCDDs and PCDFs. Quantitative data of these pollutants distribution levels deriving from different investigated incinerators are also reported.     

Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (<20 − 230 pg/g dw). PCNs appeared at few ng/g (total PCNs) levels. Pulp mills or any other local sources could not be associated with the sedimented PCDDs, PCDFs and PCNs. Coplanar PCB congeners 77 and 105 (IUPAC Nr) were generally found at 20–550 pg/g levels. The most toxic congener 126 was measured (110 pg/g) only at one area near a local PCB leakage. Pulp mill originated aromatic chlorocompounds which coelute with PCDDs and PCDFs in clean up, probably alkyl polychlorobibenzyls (R-PCBBs) appeared at ng/g levels and showed a clear gradient dowstreams from pulp mill effluent points.     

Effects of copper chloride on formation of polychlorinated dibenzo-p-dioxins in model waste incineration

Combustion experiments in a laboratory-scale fluidized-bed reactor were conducted to elucidate the effects of copper chloride as a catalyst on polychlorinated dibenzo-p-dioxins (PCDDs) formation in municipal waste incineration. We used model wastes with and without copper chloride (CuCl₂ · 2H₂O), both of which contained polyvinyl chloride as a chlorine source. Combustion temperature was set to 900 °C, and the amount of air supplied was twice the stoichiometric ratio. The experimental setup was carefully planned to suppress the influences of experimental conditions except the waste composition. Results of these experiments showed that copper chloride in the waste increased the amount of PCDDs formed and made the homologue profile to shift towards the highly chlorinated species. Copper chloride contributes to the PCDDs formation by promoting chlorination, whereby the reaction is important in that organic matter is chlorinated directly by copper compounds. Copper chloride did not exert a great influence on the isomer distribution patterns of PCDDs, while there appeared a significant difference in the case of PCDFs. This points out the difference of the major formation mechanisms between PCDDs and PCDFs. PCDDs are less formed by the catalytic reactions from carbon/polycyclic aromatic hydrocarbons than PCDFs in our experimental conditions.     

Atmospheric concentrations of PCDDs/PCDFs in southern California.

A comprehensive air toxics measurements program designed to establish baseline concentrations of atmospheric polychlorinated dioxins and dibenzofurans (PCDDs/PCDFs) in the South Coast Air Basin has been completed. The program utilized state-of-the-art air sampling and laboratory analysis techniques (HRGC/HRMS) to quantify the fifteen 2,3,7,8-substituted PCDDs/PCDFs congeners of primary toxicological significance. This study, which included nine discrete sampling sessions between December 1987 and March 1989, provides the first systematic assessment of ambient PCDDs/PCDFs concentrations in the state of California. The highest PCDDs/PCDFs concentrations noted during this study occurred in December 1987. This period was dominated by off-shore air flows, suggesting a regional air mass and transport phenomena. Concentrations of the PCDDs/PCDFs were diminished markedly in subsequent sampling sessions where air flow patterns were primarily of on-shore or of coastal origin. Ambient PCDDs/PCDFs concentrations, expressed as toxic equivalents, were highest during the December 1987 sampling period. The El Toro monitoring site, located approximately 40 miles southeast of Los Angeles, consistently showed the lowest measured ambient PCDDs/PCDFs concentrations and toxic equivalents values. In the majority of the sessions and samples examined the PCDDs/PCDFs congener profiles strongly suggest combustion source influences. Typical of combustion source profiles, 1,2,3,4,6,7,8-HpCDD was the predominant 2,3,7,8-substituted species and most prevalent PCDD after OCDD. The congener of highest toxicological significance, 2,3,7,8-TCDD, was reported below the 10-20 fg/m3 detection limit for most of the ambient air samples selected for analysis.     

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.     

Levels of PCDDs and PCDFs in products and effluent from the Swedish pulp and paper industry and chloralkali process

Within the Swedish Dioxin Survey various samples from the pulp and paper industry and the chloralkali process have been analyzed by congener specific analytical methods. In addition to the generally discussed “bleaching pattern” of the tetrachlorinated congeners, these samples also contained higher chlorinated congeners like hexa-CDDs, hepta-CDFs, octa-CDD and octa-CDF. Consequently it is recommended that samples from the pulp industry should be analyzed for all PCDDs and PCDFs (tetra- through octa-). Counted as Nordic Toxic Equivalents (NTEQ), the recycled pulp samples had the highest contamination level followed by TMP, unbleached sulfite and bleached softwood and hardwood. In addition to the bleaching process, various chemicals used in the pulping, bleaching and wastewater treatment can contribute to the contamination.     

PCDDs/PCDFs in ambient air (<1 fg m−3) – The CTDEP long term sampling (30 d) method

The Connecticut Department of Environmental Protection (CTDEP) commenced monitoring for PCDDs/PCDFs (polychlorinated dibenzodioxins and polychlorinated dibenzofurans) in ambient air in 1987 and adopted the long term (30 d) sampling approach in 1993. The CTDEP method represents the first use of isotopically labeled PCDDs/PCDFs as field surrogates to monitor the behavior of native PCDDs/PCDFs present in actual ambient air samples. This feature first introduced in 1987 was later adopted by US EPA in revisions to sampling methods for PCDDs/PCDFs in ambient air (EPA Method TO9A) as well as development of EPA Reference Method 23 for measurement of PCDDs/PCFDs in stationary source emissions. Results are provided here for a total of twenty-three (23) samples (reported as pairs) representing twelve (12) 30 d sampling events conducted at a site located in metropolitan Hartford CT. Samples were collected in winter months during calendar years 2002–2008. PCDDs/PCDFs concentration data (pg m⁻³) are reported as both congener sums (Cl₄–Cl₈) and 2378-substitued congeners. Total PCDDs/PCDFs concentrations for these twelve (12) sampling events ranged from 0.68 pg m⁻³ (2003) to 4.18 pg m⁻³ (2004) with a mean concentration of 2.04 pg m⁻³.Method performance was monitored through use of collocated samples, in field isotopically labeled compounds, isotopically labeled laboratory applied internal standards and field blank samples. Method performance consistently exceeded goals established in USEPA Method TO9A for these same parameters. Average recoveries of in field labeled PCDDs/PCDFs ranged from 97.5% to 104.2%. Average (mean) recoveries for each of the ten (10) isotopically labeled internal standards ranged from 77.0% (¹³C-OCDF) to 95.5% (¹³C-2,3,7,8-TCDF). Method precision defined as % RPD data for collocated sampler pairs ranged from 8% to 14% for PCDDs and from 5% to 12% for PCDFs. The mean RPD for all PCDDs/PCDFs combined is 9.6%. Field monitoring results demonstrate method sensitivity for all PCDDs/PCDFs congeners and 2378-substituted congeners to be well below concentrations typically found for these compounds in ambient air (all reported data represent measured concentrations). Quantities (pg) found in field blanks represent the major determinant to achieving further enhancements in method sensitivity for selected congeners (OCDD < 42 fg m⁻³; 1,2,3,4,6,7,8-HpCDD < 5.7 fg m⁻³; and 1,2,3,4,6,7,8-HpCDF < 2.1 fg m⁻³). The CTDEP method represents a highly sensitive and reliable technique for monitoring of PCDDs/PCDFs congeners and other persistent organic pollutants (POPs) at ultra trace levels in ambient air (fg m⁻³).     

Evaluation of the Spanish hot dip galvanising sector as a source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.     

Relevance of coplanar PCBs for TEQ emission of fluidized bed incineration and impact of emission control devices

Five fluidized bed incinerators combusting municipal solid waste were assessed for the impact of coplanar PCBs on total TEQ emission. In 17 stack measurements, the coplanar PCBs contributed on average less than 3% to total TEQ with a maximum contribution of 7.5% to total TEQ in one measurement. Differences in the design of the flue gas cooling section did not show an effect on the impact of coplanar PCBs on total TEQ. The effect of emission control devices on the impact of coplanar PCBs on the total TEQ was studied in more detail at one incinerator. The relative contribution of PCBs to total TEQ increased along the flue gas line. This was caused by a slightly higher removal efficiency for TEQ relevant PCDDs/PCDFs compared to coplanar PCBs by the bag filters and a higher destruction efficiency for PCDDs/PCDFs compared to PCBs by the SCR catalyst. Additionally, the removal efficiencies of the emission control devices (bag filters and catalyst) for other chlorinated aromatic compounds which have been proposed as TEQ indicator compounds (polychlorinated benzenes and polychlorinated phenols) were compared with those for PCDDs/PCDFs and coplanar PCBs. Removal efficiencies for polychlorinated benzenes or polychlorinated phenols considerably differed from those of PCDD/PCDF and coplanar PCBs. Implications for TEQ assessments using indicator compounds as proposed in the literature are discussed.     

Comparison of variability in dioxin and furan data acquired using single train and simultaneous multiple train stack sampling methods

The variance of polychlorinated dibenzo-p-dioxin (PCDD; dioxin) and polychlorinated dibenzofuran (PCDF; furan) data obtained from single- and simultaneous multiple train methods was compared. Single train triplicate data were used from 4 stack tests obtained from a long dry kiln cement plant and 18 stack tests from a municipal solid waste (MSW) incinerator. Data from the American Society of Mechanical Engineers (ASME) report Reference Method Accuracy and Precision (ReMAP) (Lanier and Hendrix, 2001) were used for the simultaneous multiple samples, which accounted for 27 data points. Nineteen data points were acquired from an ASME research facility, 5 from a MSW incinerator unrelated to the single train MSW incinerator, and 3 from a lightweight aggregate kiln (LWAK). The ReMAP procedure was used to determine the relationship between the standard deviation and the concentration of the single train and simultaneous multiple train data. Results indicated that there was benefit from the use of simultaneous multiple train sampling for concentrations above 129 pg toxic equivalency (TEQ)/m³. There was no indication of benefit from the use of simultaneous multiple train sampling at concentrations below 129 pg TEQ/m³.

Implications:Precision of stack sampling data can be the difference between meeting and failing compliance limits. Generally, three dioxin/furan samples are acquired when stack sampling to meet compliance regulations. A reliable estimation of the data’s true concentration is not possible with this small amount of data. Increasing the precision decreases the chance that the acquired concentration deviates greatly from the true concentration. Facilities that use the appropriate stack sampling method will benefit by either improved data precision or minimal stack sampling expenses. The observations made suggest that facilities that are expected to have dioxin/furan concentrations above 129 pg TEQ/m³ would increase the precision of samples by using simultaneous multiple train sampling.     

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.