Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947 ng kg⁻¹ dw (0.02-49.9 ng WHO-TEQ kg⁻¹ dw) for 17 PCDD/Fs, 17.5-66 761 μg kg⁻¹ dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29 604 μg kg⁻¹ dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618 μg kg⁻¹ dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.     

Emission characterization of unintentionally produced persistent organic pollutants from iron ore sintering process in China

Emission of unintentionally produced persistent organic pollutants (Unintentional POPs), including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychorinated biphenyls (PCBs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz), were investigated in four typical iron ore sintering plants in China. The emission factors and annual mass releases of the Unintentional POPs were calculated. The results indicated that PCDFs contributed more than 60% to the overall toxic equivalent quantity (TEQ) values, while the contribution of the dl-PCBs is relatively low, and only in the range of 8-9%. The dominant congeners of PCDD/Fs and dl-PCBs contributing most to the total TEQ were 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126. With regard to the TEQ contributions, the most abundant homologues were PeCDFs and HxCDD/Fs, followed by PeCDDs and non-ortho dl-PCB, whereas HpCDD/Fs, OCDD/Fs and mono-ortho dl-PCBs almost made no contributions. Due to the massive use of recycled waste in the feeding materials, the average emission factor of PCDD/Fs and dl-PCBs of the four plants was 3.95 μg WHO-TEQ ton⁻¹. Based on the results, the annual release of PCDD/Fs and dl-PCBs in 2007-2009 were estimated to be 2070 g, 2212 g, and 2307 g WHO-TEQ, respectively.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Effect of land use change from paddy to vegetable field on the residues of organochlorine pesticides in soils

The effect of land use change from paddy to vegetable field on the residues of organochlorine pesticides (OCPs) was investigated. Soil residues of OCPs were analyzed in vegetable fields which had been converted from paddy fields for 0, 5, 10, 15, 20, 30, 50 year in Yixing, China in 2003. The mean concentrations of OCPs followed a sequence of: ∑DDTs (13.7 μg kg⁻¹) > ∑HCHs (8.6 μg kg⁻¹) > > HCB (2.09 μg kg⁻¹) > α-endosulfan (1.30 μg kg⁻¹) > endrin (1.08 μg kg⁻¹) > PCNB (0.76 μg kg⁻¹) > dieldrin (0.58 μg kg⁻¹). The mean residues of OCPs especially DDTs increased significantly with vegetable planting time after land use change in the first 15 years, then decreased from 20 to 30 years and increased a little afterward. The time under anaerobic and aerobic conditions was suggested to control mainly the change of the residues of OCPs.     

Contamination and emission factors of PCDD/Fs, unintentional PCBs, HxCBz, PeCBz and polychlorophenols in chloranil in China

The production of chloranil is regarded as a potentially significant source of unintentional POPs. This research aimed to identify the contamination levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HxCBz), pentachlorobenzene (PeCBz) and polychlorophenols in chloranil samples and identify the formation pathways. The toxicity equivalent (TEQ) values for PCDD/Fs in the chloranil samples ranged from 163 to 1 540 200 pg I-TEQ g⁻¹, while the PCB TEQ values ranged from 1.9 to 3.3 pg WHO-TEQ g⁻¹. High levels of HxCBz, PeCBz and polychlorophenols were also detected in the chloranil samples. The average emission factors were 522.2 mg I-TEQ t⁻¹ (PCDD/Fs), 0.0026 mg WHO-TEQ t⁻¹ (PCBs), 32.6 mg t⁻¹ (HxCBz), and 136.6 mg t⁻¹ (PeCBz). The PCDD/Fs and PCBs are thought to be formed from the polychlorophenols and polychlorobenzenes generated during the chloranil production process. Purification of the chloranil products can reduce the unintentional POPs releases and protect the environment.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.     

Estimation and characterization of PCDD/Fs, dl-PCBs, PCNs, HxCBz and PeCBz emissions from magnesium metallurgy facilities in China

Magnesium production is considered to be one potential source of unintentional persistent organic pollutants (unintentional POPs). However, studies on the emissions of unintentional POPs from magnesium metallurgy are still lacking. Emissions of unintentional POPs, such as polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), polychlorinated naphthalenes (PCNs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz) are covered under the Stockholm Convention. In this study, these emissions were investigated through a magnesium smelting process. Stack gas and fly ash samples from a typical magnesium plant in China were collected and analyzed to estimate the emissions of unintentional POPs from magnesium metallurgy. Emissions factors of 412 ng TEQ t⁻¹ for PCDD/Fs, 18.6 ng TEQ t⁻¹ for dl-PCBs, 3329 μg t⁻¹ for PCNs, 820 μg t⁻¹ for HxCBz, and 1326 μg t⁻¹ for PeCBz were obtained in 2009. Annual emissions from magnesium metallurgy in China were estimated to be 0.46 g WHO-TEQ for PCDD/Fs and dl-PCBs, 1651 g for PCNs, 403 g for HxCBz and 653 g for PeCBz, respectively.     

A national inventory to estimate release of polychlorinated dibenzo-p-dioxins and dibenzofurans in Portugal

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2-217.9 g TEQ year⁻¹, with the most likely value of 95.2 g TEQ year⁻¹ achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Risk ranking of multiple-POPs in detritivorous fish from the Río de la Plata

To evaluate the bioaccumulation and the risk associated to consumption of lipid-rich detritivorous fish, a comprehensive set of organic pollutants (n = 213) including polychlorinated biphenyls (PCBs), dioxin like PCBs (dlPCBs), chlorinated pesticides (CHLPs), chlorobenzenes (CBzs), polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo dioxins and furans (PCDD/F), resolved (ALI) and unresolved aliphatic hydrocarbons (UCM) and linear alkyl benzenes (LABs) were analyzed in Sábalo fish (Prochilodus lineatus) collected in the polluted Metropolitan Buenos Aires coast and in migrating specimens. Fatty fish muscles (lipids: 74 ± 9.3% dry weight) contained homogeneous (24-51% variability) and very high-concentrations of organic pollutants ranging from 60 to 1300 μg g⁻¹ fresh weight (fw) ALI + UCM; 10-40 μg g⁻¹ fw LABs and PCBs; 0.1-1 μg g⁻¹ fw dlPCBs, DDTs, chlordanes, CBzs and PBDEs; 0.01-0.1 μg g⁻¹ fw mirex, endosulfans, aldrin, dieldrin, endrin and 0.07-0.2 ng g⁻¹ PCDD/F. Total toxicity equivalents (TEQs) ranged from 60 to 395 pg g⁻¹ fw (34 ± 17 and 213 ± 124 pg g⁻¹ TEQs for PCDD/F and dlPCBs respectively). These are among the highest concentrations reported for fish and point out the remarkable ability of Sábalo to feed on anthropogenic organic-enriched particles and tolerate a high pollutant load. Contaminant signatures show partial alteration with still abundant lower molecular weight components indicating that fish feeds directly in the outfalls. Consumption limits based on reference doses ranged from 0.1 (PCBs) to >12 000 g d⁻¹ (endosulfan) allowing a comprehensive risk-based ranking of contaminants in this long-range migrating, detritivorous fish.     

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.     

Monitoring of environmental contaminants in raw bovine milk and estimates of dietary intakes of children in South Korea

Persistent organic pollutants (POPs) are ubiquitous residual contaminants in the environment and in the food chain. Milk is an important matrix for monitoring POP contamination. This study determined the concentrations of POPs including polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (DL-PCBs) in raw bovine milk, and the data was used to estimate dietary intakes in South Korea. The average concentrations of PBDEs, HCB, PCDD/Fs, and DL-PCBs in raw milk were 0.29 ng g⁻¹ fat, 0.50 ng g⁻¹ fat, 0.27 pg TEQ g⁻¹ fat, and 0.33 pg TEQ g⁻¹ fat, respectively. No significant relationship was found between the concentrations of analytes and the regions sampled. The dietary intakes of PBDEs from the consumption of milk was calculated to be 0.26, 0.10, and 0.05 ng kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. The dietary intakes of HCB was calculated to be 0.44, 0.16, and 0.09 ng kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. The dietary intakes of PCDD/Fs and DL-PCBs was calculated to be 0.78, 0.29, and 0.16 pg TEQ kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. These results indicated that the residual levels of PBDEs, HCB, PCDD/Fs, and DL-PCBs in raw bovine milk were within safe levels.     

Determination of dioxin concentrations in fish and seafood samples using a highly sensitive reporter cell line, DR-EcoScreen cells

There is a strong need for the development of relatively rapid and low-cost bioassays for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in environmental and food samples. In this study, we applied a reporter gene assay using DR-EcoScreen cells (DR-cell assay), which is highly sensitive to dioxins, to the determination of PCDD/Fs and dl-PCBs in fish and seafood samples. The PCDD/Fs and dl-PCBs were extracted from homogenated samples (10 g) of 30 fish and shellfish, purified by clean-up procedure using a multilayered silica gel column and an alumina column, and applied to DR-cell assay. Interestingly, the bioanalytical equivalent (BEQ) values obtained from the DR-cell assay [<0.1 ∼ 5.4 pg BEQ g⁻¹ wet weight (ww)] were closely correlated with the toxicity equivalent (TEQ) values from conventional high-resolution gas chromatography/high-resolution mass spectrometry (HRGC-HRMS) analysis (r² = 0.912), and the slope of regression line was 0.913. Therefore, we multiplied the BEQ values from the DR-cell assay by a conversion coefficient (1.095, the reciprocal of 0.913) to approximate the TEQ values from the HRGC-HRMS analysis. Furthermore, we used this DR-cell assay to perform a prescreening test of PCDD/Fs and dl-PCBs in 16 fish and seafood samples purchased from a supermarket, revealing that a sample from the fatty flesh of a bluefin tuna exceeded 8 pg TEQ g⁻¹ ww (the European Union-tolerance limit). Taken together, these results suggest that the DR-cell assay might be applicable as a rapid and low-cost prescreening method to determine dioxin levels in fish and seafood samples.     

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.     

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.     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

Environmental release of dioxins from reservoir sources during beach nourishment programs

In late 1990s, USEPA/FDA made an important connection regarding the presence of elevated levels of dioxins (e.g., 1500 ng kg⁻¹ TEQ) in ball clays mined in Mississippi (USA) from a geological deposit dated to ∼40 million years (Mississippi Embayment) that stretches over several states (northern part of Mississippi to Kentucky) and levels of dioxins in selected animal food sources. Following a recent beach nourishment program along the mid-Atlantic coast of the US, a number of dark gray, blue tinted nuggets of varying sizes were found on beach strands and near the shoreline. Using the presence of these balls of clay (shape, color, and knowledge regarding their use in pottery) on the beach, together with our direct experience analyzing ball clays for dioxins, we made a possible association between these clays and elevated dioxins. Concerns regarding the potential of nourishment programs to cause severe damage to our beaches drove us to test the dioxin content of nourishment exposed clays. A number of the nuggets, along with freshly dredged and deposited sand (collected the morning after nourishment) with the same coloration, and others (sun-bleached), collected approximately 2 weeks after the completion of the nourishment efforts, were analyzed for the presence of PCDD/Fs, PCBs, and selected semi-volatile chlorinated organics. The clay PCDD/F WHO2005-TEQs (dry weight; ND = DL; EMPC = EMPC) ranged from 0.41 to 5.78 ng kg⁻¹ with an average of 2.64 ng kg⁻¹, whereas the sand sample’s TEQs ranged from 0.18 to 0.31 ng kg⁻¹ PCDD/F WHO-2005, with an average of 0.22 ng kg⁻¹. The average total tetra- through octachlorinated dibenzo-p-dioxin concentration was 2700 ng kg⁻¹ (with a maximum of 5800 ng kg⁻¹) for the clays and 8.5 ng kg⁻¹ (with a maximum of 16.8 ng kg⁻¹) for the sand samples. The congener 2,3,7,8-TCDD (TEF = 1) was detected in half of the clay samples (0.11-0.77 ng kg⁻¹). All of the clay and sand samples displayed an unambiguous and dominating 1,4,6,9-chlorination pattern across homolog groups. No other chlorinated aromatics were detected above background levels. The observations, along with the absence or an extremely low level of polychlorinated dibenzofurans, together with the mineralogical analysis, supports the conclusion that off-shore dredging activities are reaching reservoir sources containing dioxin-tainted, smectic/kaolinite clay minerals. Subsequent beach erosion provides additional environmental releases over time, as buried balls of clay from previous nourishment efforts become exposed.     

Organochlorine pesticide residues in sediments from the Uganda side of Lake Victoria

Organochlorine (OC) residues were analysed in 117 sediment samples collected from four bays of the Uganda side of Lake Victoria. The sediments were collected with a corer at a depth of 0-20 cm, and extracted for OC residues using a solid dispersion method. The extracts were cleaned using gel permeation chromatography and analysed for pesticide residues using a gas chromatograph (GC) equipped with an electron capture detector. The results were confirmed using a GC equipped with a mass spectrometer (MS). A total of 16 OC residues, most of them persistent organic pollutants (POPs) were identified and quantified. The OC residue levels were expressed on an oven dry weight (d.w.) basis. Endosulphan sulphate, in the range of 0.82-5.62 μg kg⁻¹d.w., was the most frequently detected residue. Aldrin and dieldrin were in the ranges of 0.22-15.96 and 0.94-7.18 μg kg⁻¹d.w., respectively. DDT and its metabolites lay between 0.11-3.59 for p,p′-DDE, 0.38-4.02 for p,p′-DDD, 0.04-1.46 for p,p′-DDT, 0.07-2.72 for o,p′-DDE and 0.01-1.63 μg kg⁻¹d.w. for o,p′-DDT. The levels of γ-HCH varied from 0.05 to 5.48 μg kg⁻¹d.w. Heptachlor was detected only once at a level of 0.81 μg kg⁻¹d.w., while its photo-oxidation product, heptachlor epoxide, ranged between non-detectable (ND) to 3.19 μg kg⁻¹d.w. Chlordane ranged from ND to 0.76 μg kg⁻¹d.w. Based on the threshold effect concentration (TEC) for fresh water ecosystems, aldrin and dieldrin were the only OCs that seemed to be a threat to the lake environment.     

Formation of artefacts while sampling emissions of PCDD/PCDF from open burning of biomass

Emission factors for PCDD/PCDF determined from open combustion are used to estimate national emission budgets; therefore, it is important to have confidence in their accuracy. It has been suspected that artefacts may form due to the presence of hot metal surfaces of sampling equipment, thus skewing emission factors. In this study, emissions of PCDD/PCDF from open burning of forest biomass over a brick hearth were sampled. Five experiments were carried out using a portable sampler. Experiments were designed where the key variable, sample hood and inlet temperatures were manipulated. Other variables such as fuel origin, type and density were consistent. The measured concentration of PCDD/PCDF in the smoke samples ranged from 0.01 μg TEQ (t fuel)⁻¹ at the lowest maximum hood temperature (185 °C) to 15 μg TEQ (t fuel)⁻¹ at the highest maximum hood temperature (598 °C). when hood inlet temperatures exceeded 400 °C emission factors were significantly elevated and this is attributed to the formation of artefacts that can cause the over estimation of emission factors. The increase in hood temperature also resulted in a change in the PCDD/PCDF congener and homologue profile of the emissions. For example at the lowest temperature (Fire 1) the PCDD/PCDF ratio measured was 50:1, whereas at the highest temperature (Fire 5) this ratio was about 0.53:1. When the sampler hood and inlet temperatures were kept in the normal operating range of <200 °C, emission factors were comparable to those observed in many previous studies in Australia with emissions dominated by PCDD.