Levels of PCDDs and PCDFs in Korean river sediments and their detection by biomarkers

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of toxic halogenated aryl hydrocarbons inducing various physiological disorders against biological organisms. Here, we investigated their levels in sediment samples taken from 12 different rivers in Korea. The levels of PCDD/PCDFs in sediment samples were expressed as concentrations and international TEQ values. Among 17 PCDD/PCDFs selected as target compounds in this study, the 1,2,3,4,7,8-HxCDD and OCDD were found in all river sediments with significant variation in various congener profiles of PCDD/PCDFs in sediments. PCDD/PCDFs could be monitored by sensitive biomarkers using insect immune system. Out of 12 river sediment samples, the biomarkers reported four spots (up, middle, and down Singil sites and Ansan) as putative contamination areas. When comparing both chemical and biological monitoring results, two methods agreed three spots of Singil as contamination areas (above 10ppt levels) as well as six river sediment samples as relatively less-contaminated areas, but differed in the results in Ansan and Miho, probably due to relative non-specificity of biomarkers. Despite some disparity between bio- and chemical monitoring results, the biomarkers can be recommended as a device warning the contamination of dioxins in the environment because of a fast and inexpensive detection method.     

PCDDs and PCDFs in sewage sludges from two wastewater treatment plants in Beijing, China

The levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were analyzed by an isotope-dilution high-resolution mass spectrometric in 16 sewage sludges, sampled from 2004 to 2009, from two municipal wastewater treatment plants (WWTPs) in Beijing. Total toxicity equivalent (TEQ) values were evaluated using the toxicity equivalent factors proposed by International for PCDD/Fs. The I-TEQs for these sewage sludges were from 0.97 to 15.0 pg g⁻¹ dry weight (dw) with a mean value 4.43 pg g⁻¹ dw, indicating that all I-TEQs were below Chinese legislation limit value regulated for agricultural use in soils.The results from limited samples (16 samples) showed that the levels of PCDD/Fs might be correlated with the sludge age. Meanwhile, the temporal trends of PCD/Fs suggested that the I-TEQs may correlate with rainfall in the present study.     

PCDDs, PCDFs, PCBs and HCB in marine and estuarine sediments from Queensland, Australia.

Concentrations of 2,3,7,8-chlorine substituted PCDDs, PCDFs, selected PCB congeners and HCB were determined in sediment samples collected from sites along the east coast of Queensland in northern Australia. PCDDs were detectable in all sediment samples while PCDFs, PCBs and HCB were mainly found in sediment samples collected from sites in the Brisbane metropolitan area. The results provide evidence that an unidentified source for higher chlorinated PCDDs exists along the Queensland coast.     

A comparison of TEQ contributions from PCDDs,PCDFs and dioxin-like PCBs in sewage sludges from Catalonia,Spain

Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ(PCDD/F) values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ(PCB) levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ(PCB) contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.     

Spatial variations and correlations in the distribution of PCDDs, PCDFs and related compounds in sediments from the river Rhine — Western Europe

PCDDs, PCDFs and some related aromatic compounds were determined isomer specifically in sediments from the river Rhine and its tributaries, in order to study sources and environmental fate of these compounds. Additionally, waste water effluents from industries that unintentionally might coproduce PCDDs or PCDFs were analyzed. In all sediments and in some waste water effluents these compounds could be detected. Variations of the isomeric patterns of the PCDFs enabled a distinct industrial area, that was associated with PCB contamination to be identified. The contamination of sediments and organisms from the Dutch river Rhine delta with these compounds mainly could be attributed to the transboundary pollution of the river Rhine.     

An assessment of the risks associated with PCDDs and PCDFs following the application of sewage sludge to agricultural land in the UK

A model has been developed to describe the transfer of PCDDs and PCDFs from sludge-amended soils to the human foodchain. The model is conservative and assumes that all foods consumed by an individual are derived from sludge-amended soils. Predicted concentrations of PCDDs and PCDFs in potatoes, cereals, root vegetables and leafy vegetables were in close agreement with mean concentrations reported in the food survey conducted by MAFF in the UK. Predicted concentrations in milk were well below the Maximum Tolerable Concentration adopted by MAFF. Assuming a half-life of ten years in sludge-amended soils, the maximum estimated incremental daily intake (IDI) predicted by the model following ten applications of sludge to agricultural land was 0.80 pg I-TEQ kg⁻¹ day⁻¹, representing an increase of approximately 45% on current levels of background exposure. For an individual whose diet is solely derived from sludge-amended soils, the total exposure is predicted to be approximately 181 pg I-TEQ day⁻¹ or 2.6 pg I-TEQ kg⁻¹ day⁻¹. This compares with an average background exposure of approximately 2 pg I-TEQ kg⁻¹ day⁻¹, well within the TDI of 10 pg I-TEQ kg⁻¹ day⁻¹ and indicates that the application of sewage sludge to agricultural land under the conditions assumed would not appear to present a significant health risk under the conservative scenarios considered in this assessment.     

The influence of sewage sludge applications to agricultural land on human exposure to polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs)

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) are organic chemicals of suspected extreme toxicity. PCDD/Fs are ubiquitous in the environment and relatively enriched in sewage sludges. The deliberate application of sewage sludge to agricultural land can therefore potentially increase exposure of the human population to these compounds via transfers through the foodchain. This paper presents a protocol for assessing the background human exposure to all seventeen 2,3,7,8-substituted PCDD/Fs for which toxic equivalent factors (TEFs) are available. Background daily human exposure in the UK to 2,3,7,8-T(4)CDD and I-TEQ are calculated to be 0.0239 ng and 0.203 ng, respectively. The potential increases in crop plant and livestock tissue PCDD/F concentrations, and hence in human exposure, following applications of sewage sludge to agricultural land are quantified for different sludge application scenarios. The key role of PCDD/F transfer into livestock via ingestion of sludge adhered to vegetation in determining increases in human exposure is demonstrated.     

PCDDs, PCDFs, PCBs and DDE in edible marine species from the Adriatic Sea

Edible marine species from several areas of the Adriatic sea were analyzed for their content in persistent organic pollutants (POPs), such as polychlorinated dibenzodioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and pp'-DDE (dichlorodiphenyldichloroethylene), a metabolite of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT). On the whole, PCDD/F contamination levels were low. In general, I-TEQ findings were greater for those species at higher levels in the trophic web (mackerel > red mullet > anchovy). Contamination levels were within 0.23 and 1.07 pg TEQ/g fw (fresh weight) in the aforesaid species, while all remaining species exhibited contamination levels ranging from approximately 0.07 to 0.25 pg TEQ/g fw. Besides, TEQ cumulative findings in species from the northern area were in general greater than those from the central and southern areas. PCB cumulative findings in the samples also revealed a detectable difference in contamination levels in species obtained from the northern, central, and southern sampling sites, between 7.6 and 177, 2.3 and 157, and 4.5 and 94 ng/g fw, respectively. The greatest PCB concentrations were found in mackerel (94-177 ng/g fw). Finally, DDE concentration levels varied from 0.7 to 32.4 ng/g fw. The highest levels of contamination were found in mackerel, red mullet and anchovy (17.7-32.4 ng/g fw, 8.1-9.8 ng/g fw, and 6.4-11.9 ng/g fw, respectively).     

Polybrominated diphenyl ether in sewage sludge in Germany

Sewage sludge samples from 11 municipal waste water treatment plants in Germany were collected from March 2002 to June 2003. Total Tri- to HpBDE concentrations (sum of significant congeners BDE 28, 47, 99, 153, 154 and 183) ranged from 12.5 to 288 (median 108) and DeBDE (BDE 209) concentrations from 97.1 to 2217 (median 256) ng/gd.m. BDE 209 dominated the congener profile. A significant change of the Tri- to HpBDE congener profile (% of total BDE 28, 47, 99, 153, 154, 183 without 209) in sludge from different stages of the waste water treatment process (primary sludge, secondary excess sludge and (dewatered) digested sludge), indicating a degradation of DeBDE to these congeners, was not observed.     

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.     

Update of daily intake of PCDDs, PCDFs, and dioxin-like PCBs from food in Japan

Total diet study (TDS) samples of 14 food groups from 16 locations in Japan, collected in 1999 and 2000, were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) to estimate the update of daily intake of these contaminants from food. The mean daily intake of toxic equivalency (TEQ) for an adult weighing 50 kg, calculated at non-detected isomer concentrations equal to zero (ND=0), was estimated to be 2.25 pg TEQ/kg b.w./day. When non-detected isomer concentrations are assumed to be equal to half of the limits of detection (ND=1/2 LOD), the mean daily intake was estimated to be 3.22 pg TEQ/kg b.w./day. These values were below the tolerable daily intake (TDI) of 4 pg TEQ/kg b.w. for PCDD/Fs and dioxin-like PCBs set in Japan. In both the estimates, the mean daily intakes were highest from fish and shellfish (76.9% at ND=0 and 53.9% at ND=1/2 LOD of the total TEQs), followed by those from meat and eggs (15.5% at ND=0 and 11.7% at ND=1/2 LOD of the total TEQs). Congener specific data revealed that these total TEQ levels were dominated by 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in each case (71.7% at ND=0 and 63.1% at ND=1/2 LOD of the total TEQs). The dioxin-like PCBs (non-ortho and mono-ortho PCBs) accounted for about 50% of these total TEQs. These data will be very useful in the risk assessment of PCDD/Fs and dioxin-like PCBs from food in Japan.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

PCDDs and PCDFs in vehicle exhaust particles in Japan.

Vehicle exhaust particles from gasoline and diesel engine cars were analyzed for PCDDs and PCDFs. The congener patterns of PCDDs and PCDFs in exhaust particles were different between gasoline and diesel engine cars. Suspended particulate matter from electrostatic precipitator connected to a highway tunnel was also analyzed for PCDDs and PCDFs. The congener pattern of suspended particular matter was different from both of gasoline and diesel engine cars. Total amounts of PCDDs/PCDFs sum concentrations in gasoline, diesel and suspended particulate matter were 0.21, 0.87 and 26.0 ng/g, respectively. The I-TEQs levels in gasoline, diesel and suspended particulate matter were 4.2, 11 and 242 pg/g, respectively.     

The presence of PCDDs and PCDFs in human breast milk from the Netherlands

Sixteen individual and two pooled human milk samples were analyzed for PCDDs and PCDFs. All detected PCDD and PCDF congeners had a 2,3,7,8-chlorine substitution pattern.The PCDDs and PCDFs were associated with the lipid fraction of the milk. Major components were 2,3,4,7,8-PnCDF (0.2 – 2.6 ppt), 1,2,3,6,7,8-HxCDD (0.2 – 5.7 ppt), 1,2,3,4,6,7,8-HpCDD (1.3 – 19.1) and OCDD (1.7 – 37.8 ppt), with concentrations on total milk basis.Minor components were 1,2,3,7,8-PnCDD, 1,2,3,7,8,9- and 1,2,3,4,7,8- HxCDD (⩽ 1 ppt). Qualitatively and quantitatively the milk samples from the Netherlands strongly resemble those from Sweden and West-Germany. A linear relationship was found between some congeners. This correlation was highest for congeners having an equal number of chlorine atoms or those with a difference of one chlorine atom.By using a one compartment open model for multiple doses, a maximum liver concentration of approximately 200 ppt 2,3,4,7,8-PnCDF in the neonate was calculated after six months.     

Levels of PBDEs, PCDDs, PCDFs, and coplanar PCBs in edible fish from California coastal waters

The levels of polychlorinated dibenzo-dioxins (PCDDs), polychlorinated dibenzo-furans (PCDFs), coplanar polychlorinated biphenyls (coPCBs), and polybrominated diphenyl ethers (PBDEs) were measured in fish collected from San Francisco Bay in 2000 and from the California coast in 2001. The samples were composites of only the edible portions of the fish (skin on, skin off, or whole body minus head and guts) of comparable size and from distinct geographical areas. Sixty-five composite samples were analyzed for PCDD/PCDF/coPCBs, and 43 composite samples were analyzed for PBDEs. For all fish of all species from all sampling areas, the mean concentration of the sum of BDEs 47, 99, 100, 153, and 154 was 302 ng/g lipid weight, with BDE 47>100>99 approximately 154>153. For all fish of all species from all sampling areas, the mean PCDD/PCDF International Toxic Equivalent (I-TEQ) was 33.1 pg/g lipid. For the three coPCBs (77, 126, 169), the mean I-TEQ for all fish of all species from all sampling areas was 109 pg/g lipid. The highest concentrations of both PCDD/PCDF/coPCBs and PBDEs were found in the highly populated areas of San Francisco Bay, the Los Angeles area, and San Diego Bay.     

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficient for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (1-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.     

Determination of PCDDs and PCDFs in PCB oil from a hazardous waste site

This paper describes the analysis of hazardous waste oil samples with procedures that were developed primarily to clean up and analyze biological samples. Details of the cleanup procedure and the results from the analysis of several waste PCB oil samples are presented.