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Torrefaction constitutes one of the promising technologies for the management of waste biomass and the production of high-carbon products for combustion, gasification, adsorption of pollutants or soil treatment. Unfortunately, waste biomass may be contaminated with toxic persistent organic pollutants, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) and dioxin-like biphenyls (dl-PCB). Literature does not provide consistent measurements on how the low-temperature thermochemical processing, such as torrefaction, affects the toxicity of biomass. This contribution assesses how a torrefaction treatment, conducted at 200 °C, modifies the toxicity due to PCDD/PCDF/dl-PCB in biomass. We deploy the XDS-CALUX biotest on five types of waste biomass (sewage sludge, tree bark, cattle manure, spent coffee ground, common reed), before and after treatment. The content of total dioxin- & biphenyl fraction compounds in the raw biomass, investigated in this study, varies from 0.14 to 3.67 pg BEQ·g−1 d.m. , and in the torrefied biomass between 0.17 and 6.00 pg BEQ·g−1 d.m. ; BEQ stands for bioanalytical equivalent. This increase is statistically insignificant at p = 0.05, taking into account all types of examined biomass. This proves that low-temperature torrefaction cannot detoxify biomass, i.e., chars, produced from biomass characterized by elevated concentration of PCDD/PCDF/dl-PCB, will reflect the contamination of the feedstocks. With respect to heavy metals, we conclude that only the content of Cd in biomass, and, to a lesser extent, the abundance of Cu and Fe, modify the toxicity of this material during its thermochemical treatment at low temperature. [Display omitted] • Torrefaction at 200 °C cannot remove PCDD/PCDF/dl-PCB and metals from biomass. • Toxicity of PCDD/PCDF/dl-PCB is similar before and after treatment. • Cd, Fe, and Cu alter the toxicity of biomass. [ABSTRACT FROM AUTHOR]

Toxic polychlorinated dibenzo- p -dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 45 stack gas samples were measured from 19 medical waste incinerators in South Korea using high-resolution gas chromatography equipped with a high-resolution mass spectrometer. The average concentrations of the sum of 17 toxic PCDD/PCDF congeners emitted from the medical waste incinerators ranged from 0.153 to 101.9 ng/Sm 3 . Based on the World Health Organization toxic equivalency factor, they ranged from 0.007 to 5.437 ng-TEQ/Sm 3 . The congener patterns of PCDDs/PCDFs were described using principal component analysis and presented four patterns. In the evaluation of annual average total TEQ concentrations, outlying stack gas samples were excluded. In this study, the number of chlorine substitutions was evaluated as an important factor in congener patterns. Coefficient of determination values were employed for evaluation of correlation between PCDDs and PCDFs. 1,2,3,4,6,7,8-HpCDF was measured as the most emitted congener, while 2,3,4,7,8-PeCDF was the greatest TEQ contributor. [ABSTRACT FROM AUTHOR]

An earlier demonstration that the relative concentrations of isomers of polychlorinated dibenzofuran do not vary as the flamefront of an iron ore sinter plant progresses through the bed, and profiles are similar for two sinter strands has been widened to include studies of the similarity or otherwise between full scale strand and sinter pot profiles, effect of addition of suppressants and of coke fuel substitution with other combustible materials. For dioxin suppressant addition, a study of the whole of the tetra- penta- and hexaCDF isomer range as separated by the DB5MS chromatography column, indicates no significant change in profile: examination of the ratios of the targeted penta- and hexaCDF isomers suggests the profile is similarly unaffected by coke fuel replacement. Addition of KCl at varied levels has also been shown to have no effect on the ‘fingerprint’ and there is no indication of any effect by the composition of the sinter mix. The recently published full elution sequence for the DB5MS column is applied to the results obtained using this column. It is confirmed that isomers with 1,9-substitution of chlorine atoms are invariably formed in low concentrations. This is consistent with strong interaction between the 1 and 9 substituted chlorine atoms predicted by DFT thermodynamic calculations. Non-1,9-substituted PCDF equilibrium isomer distributions based on DFT-derived thermodynamic data differ considerably from stack gas distributions obtained using SP2331 column separation. A brief preliminary study indicates the same conclusions (apart from the 1,9-interaction effect) hold for the much smaller content of PCDD. [ABSTRACT FROM AUTHOR]

Isomer distribution patterns of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) were investigated in microwave-assisted pyrolysis (MAP) products of woody biomass. The feedstocks included bark and impregnated wood. The results indicated that isomer distributions in MAP are more selective compared to those reported from wood burning and waste incineration. Favored formation of 4-MoCDF and highly selective chlorine substitution at the 2,4-position observed during MAP suggested a preferred formation pathway of PCDFs involving (chloro)phenol precursors followed by subsequent chlorination. The PCDD distribution was dominated by isomers typically formed from chlorophenol condensation at relatively low temperature. The PCN isomer distributions showed a tendency for sequential chlorination from non-substituted naphthalene at successive positions. The presence of isomers such as 1-MoCDD, 4-MoCDF, 1,2,3-TriCN with low thermodynamic stability indicates that kinetic factors may be important in the MAP process. [ABSTRACT FROM AUTHOR]

Fly ash and Air Pollution Control (APC) residues collected from three municipal solid waste incinerators in Denmark and Greenland were treated by electrodialytic remediation at pilot scale for 8–10 h. This work presents for the first time the effect of electrodialytic treatment on polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF), and how these levels impact on the valorization options for fly ash and APC residue. PCDD/PCDF levels in the original residues ranged between 4.85 and 197 ng g −1 , being higher for the electrostatic precipitator fly ash. The toxic equivalent (TEQ) varied ten fold, ranging 0.18–2.0 ng g −1 I-TEQ, with penta and hexa-homologs being most significant for toxicity. After the electrodialytic treatment PCDD/PCDF levels increased in the residues (between 1.4 and 2.0 times). This does not mean PCDD/PCDF were synthesized, but else that soluble materials dissolve, leaving behind the non-water soluble compounds, such as PCDD/PCDF. According to the Basel Convention, PCDD/PCDF levels in these materials is low (<15 μg WHO-TEQ kg −1 ) and the fly ash and APC residue could eventually be valorized, for instance as construction material, provided end-of-waste criteria are set and that a risk assessment of individual options is carried out, including the end-of-life stage when the materials become waste again. [ABSTRACT FROM AUTHOR]

Gas/particle partitioning of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) compounds in the ambient atmosphere were investigated at three different sites (urban-industrial, urban and sub-urban) in İstanbul. Average gas and particle phase concentrations were measured as 133 fg m −3 and 1605 fg m −3 , respectively. Gas phase concentrations of polychlorinated dibenzo-p-dioxin/furan (PCDD/F) compounds were determined to be 128 fg m −3 , 50 fg m −3 , 153 fg m −3 during summer season and 204 fg m −3 , 164 fg m −3 , 154 fg m −3 during winter season for the respective three sampling sites. Particle phase concentrations were determined to be 287 fg m −3 , 176 fg m −3 , 160 fg m −3 during summer and 6586 fg m −3 , 2570 fg m −3 and 1861 fg m −3 during winter season for those three sampling sites. Chlorination level and molecular weight of congeners affected gas/particle partitioning of PCDD/F compounds. Gas phase percentages of 2,3,7,8-TCDD and OCDD concentrations were determined to be 47% and 1% respectively. A relatively high correlation was found between total particle matter (TPM) and particle phase PCDD/F concentration during winter season. [ABSTRACT FROM AUTHOR]

In the marine food-webs, zooplankton is a key element in the transfer of persistent organic pollutants to higher trophic levels. We determined the congener-specific concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in offshore zooplankton (size from 0.2 to 20mm) collected in 2001, 2002 and 2010 in the northern and central Baltic Sea. Of the PCDD/Fs, the concentrations of 2378-TCDF were from 18 to 47 and of 23478-PeCDF from 7.9 to 29pgg−1fat and showed little temporal differences. However, 1234678-HpCDF and OCDF were abundant in 2001-2002 especially in the eastern Gulf of Finland (average concentrations 50 and 89pgg−1fat, respectively). In 2010 the concentrations of these two congeners were lower, 29 and 30pgg−1fat, respectively, but still substantially higher than in the other surveyed areas. The principal components analysis (PCA) supported that area-specific patterns in pollution strongly contributed to the congener profiles particularly in surface sediment and in sediment trap material, but even in zooplankton. The concentrations of the PCBs were highest in the Gulf of Finland and in the Bothnian Bay. The concentrations of most PCBs were somewhat lower in 2010 than in 2001-2002. Of the dioxin-like PCBs, the concentrations of PCB-77 were highest (271-572pgg−1fat) but PCB-126 (32-113pgg−1fat) contributed from 85% to 91% of the total toxicity of PCBs due to its higher toxic potency. Of the PBDEs, the BDE47 and BDE99 were the most abundant (concentrations from 1.2 to 4.6 and from 0.4 to 3.3ngg−1 fat, respectively). The concentrations of most PBDEs were lower in 2010 than in 2001/2002 except in the eastern Gulf of Finland. [ABSTRACT FROM AUTHOR]

Highlights: [•] Case study of remodeled MSWI with PCDD/F emission problems. [•] Analysis of all PCDD/F congeners before and after fabric filters in MSWI plant. [•] PCDD formation within the fabric filters at 220°C was observed. [•] PCDD/F TEQ concentrations and total PCDD/F are independent of each other. [ABSTRACT FROM AUTHOR]

Highlights: [•] The PCDD/Fs and PCBs concentration in people living in Campania. [•] The levels in blood serum were lower than the levels reported in other countries. [•] No difference in blood contamination was found in two areas of the region. [ABSTRACT FROM AUTHOR]

Highlights: [•] Marine fish was analysed as bioindicators of POPs contamination. [•] Levels for PCDD/Fs and PCBs were below the limits established by EU legislation. [•] PCDD/F and DL-PCB concentrations decrease from 2006 to 2012. [Copyright &y& Elsevier]

Abstract: Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) bioaccumulate through the food chain and are therefore of public health concern. Exposure to these compounds was assessed in the second French Total Diet Study (TDS). Food samples (n =583) were collected to be representative of the whole diet of the population, prepared as consumed, and analyzed. Contamination data were combined with national individual food consumption data. Mean exposure (95th percentile) to PCDD/F+DL-PCBs was assessed to be 0.57 (1.29)pgTEQWHO-98 (kgbw)−1 d−1 in the adult population and 0.89 (2.02)pgTEQWHO-98 (kgbw)−1 d−1 in the child and teenager population. Less than 4% of the population exceeded the health-based guidance value for PCDD/F+DL-PCBs. Mean exposure (95th percentile) to the six indicator PCBs (PCB 28, 52, 101, 138, 153, 180) was estimated at 2.71 (7.90)ng(kgbw)−1 d−1 in the adult population and 3.77 (11.7)ng(kgbw)−1 d−1 in the child and teenager population. Only 2.6% of the adults [CI95%: 1.9; 3.3] and 6.5% of the children and teenagers [5.2; 7.8] exceeded the health-based guidance value for total PCBs. These results show that the contamination levels in food and therefore the exposure of the general French population to PCDD/Fs and PCBs have declined (by a factor of 3.2 for PCDD/F+DL-PCBs and about three for total PCBs) since the last evaluation, which was conducted using another methodology in 2005 and 2007, and show the efficiency of the European risk management measures which came into force after these evaluations. [Copyright &y& Elsevier]

Abstract: Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire – “stirring” – promotes better combustion (as evidenced by lower CO/CO2 ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning – while still highly variable – tends to be greater in the later (smoldering) phases of burning when the CO/CO2 ratio increases. [Copyright &y& Elsevier]

Abstract: An extraordinary plan of official control was carried out in 2008 in Campania (Italy) with the aim to monitor polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) levels in buffalo milk and to detect the contaminated farms, most of which are located in Caserta province. For these companies has been ordered seizure and execution of additional analyses has been requested in farms falling in the nearness, within a distance of 3km, for a total of 304 farms examined. Moreover, all non-compliant farms were subjected to a periodic sampling in order to monitor trends in the levels of contamination. In this paper the distribution and the concentrations of 17 PCDD/Fs and 12 dioxin-like PCBs in 460 samples of buffalo milk collected in the province of Caserta (Italy) are presented. The range of WHO-TEQ values for the PCDD/Fs in milk was 0.17pgTEQg−1 fat and 87.0pgTEQg−1 fat with a mean value 3.63pgTEQg−1 fat and medium value 2.25pgTEQg−1 fat. The concentrations of dioxin-like PCBs in the analysed samples ranged from 0.21pgTEQg−1 fat to 15.9pgTEQg−1 fat and the WHO-TEQ values of sum of PCDDs, PCDFs and dl-PCBs ranged from 0.45pgTEQg−1 fat to 103.0pgTEQg−1 fat. The geo-referencing analysis allowed to individuate a restricted area of the region object of the present study where is located the majority of the non-compliant farms. The study of the congeners distribution has finally suggested that the likely cause of contamination is to be attributed to the illegal burning of waste. [Copyright &y& Elsevier]

Abstract: A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO3 in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100°C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116±11% for SRM 1944 and 102±13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10pgg−1 with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup. [Copyright &y& Elsevier]

Abstract: Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (dl-PCBs) are a family of chemically-related lipophilic compounds characterized by similar toxicity. Due to their properties they are universally distributed in the environment and classified as persistent organic pollutants (POPs). From most of studies carried out to evaluate human dietary intake, milk and dairy products result as a major contributors of PCDD/Fs uptake. Of course the main source of milk contamination is animal feeds. Lactating ruminants, cows included, transfer these compounds to the food chain by ingestion of contaminated vegetables or soil. Their resistance to degradation and a high lipophilicity means that PCDD/Fs and dl-PCBs may be accumulated into fat tissues from which they are transferred to milk during lactation period. Seventy-nine cows milk samples, collected in the monitoring plan 2008, were analyzed for PCDD/Fs and dl-PCBs. Eleven milk samples were non-compliant corresponding to five breeding livestock located in Caserta province. The distribution of PCDD/Fs and dl-PCBs congeners in these samples was examined in order to determine the likely sources of dioxins. The results show that the congener profile is characterized by a prevalence of PCDFs in respect of PCDDs, that represents the typical pattern of thermal origin contamination. [Copyright &y& Elsevier]

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were analyzed in freshwater fish (crucian carp) taken from 16 locations in nine rivers and a wetland in Korea, during 2000–2004. Dioxin-like polychlorinated biphenyls (DL-PCBs) were also analyzed in the same samples but over shorter period (2002–2004). Concentrations on a wet weight basis for 3 years (2002–2004) ranged from below the detection limit (DL) to 0.36pg TEQg−1 wet wt. for PCDDs, below the DL to 2.0 for PCDFs, and from 0.02 to 1.9 for DL-PCBs, with a mean of 0.07, 0.33 and 0.83pg TEQg−1 wet wt., respectively. The proportions of PCDDs, PCDFs and DL-PCBs in the total dioxin TEQ for 2002–2004 were 7%, 26% and 67%, respectively. While the temporal trend showed a significant decrease in PCDDs/DFs concentrations over the 5-year study period, DL-PCBs did not show significant change in concentration over the 3-year period. The results suggest that DL-PCBs concentrations should be determined when total dioxin TEQ is analyzed in freshwater fish. [Copyright &y& Elsevier]

High level of PCDD+PCDF contamination in bulk milk (9.7pgWHO-TEg−1 fat) from 1604 Holstein Fresian lactacting cows was observed just four weeks after the beginning of their exposure to a feed supplement contaminated at 10.4ngWHO-TEkg−1 dry matter. In-farm produced hay and silage showed levels not exceeding 0.2ngWHO-TEkg−1 dry matter. After the supplement withdrawal, it was possible to monitor the depletion phase for a following 75-day period in milk, until the levels dropped well below 3.0pgWHO-TEg−1 fat, the EU regulatory Maximum Residue Level for PCDD+PCDF. During this phase, the half-life was calculated as 17±3 days, on WHO-TEQ basis. The full availability of farm data on both cow nutrition and milk production allowed the calculation of the carry-over rate (COR) (PCDD+PCDF milk excretion vs. feed), which was 46% at the end of the exposure. This COR value is justified from the main TE contribution of Penta-CDD and -CDF congeners (63%), and the half-life is among the shortest of all those described in the literature both for experimental and naturally-exposed dairy cows. A fugacity-based model predicts a bulk milk contamination of 5pgWHO-TEg−1 fat, compared to the 10pgWHO-TEg−1 fat level observed. Such findings are discussed in light of the lactation and metabolic status of the herd for which the transition period, characterised by a negative metabolic energy balance and a consequent adipose tissue mobilization, could play a relevant role. [Copyright &y& Elsevier]

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8ngkg−1) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar’s test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r =0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1000ng TEQ kg−1. The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1000ng TEQ kg−1 action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis. [Copyright &y& Elsevier]

Abstract: The aim of this investigation was to evaluate the environmental impact associated to PCDDs/Fs and dioxin-like PCBs in the Ebro River basin. Sediments and fish from several species were sampled at three sites with different historical pollution records, including the Barbastro area with different industrial activities, and the Flix and Monzón sites, associated to heavy organochlorine compound pollution. Seventeen toxic PCDDs/Fs and 12 dioxin-like PCBs were analyzed by GC–MS. The results obtained indicated significant accumulation of dioxin-like PCBs, but not PCDDs/Fs, in sediments and fish at the Flix site compared to the other sites. Concomitantly, cytochrome p450 1A (CYP1A) expression, a known indicator for pollution by dioxins and dioxin-like PCBs, was significantly elevated in barbel (Barbus graellsii) from the Flix site, compared to the population from the Barbastro site. CYP1A expression correlated with the concentration of dioxin-like PCBs in the fish fat, whereas no significant correlation was found with PCDDs/Fs concentrations. Our data suggest a significant biological impact at the Flix site, closely related to the presence of dioxin-like PCBs, whereas the PCDDs/Fs contribution to this impact appears to be non-significant, at least in the studied sites. [Copyright &y& Elsevier]

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) are widespread environmental contaminants. A French national survey was carried out in April 2006 to assess the concentrations of PCDD/Fs and dioxin-like PCBs (DL-PCBs) in raw cow’s milk. A random sampling scheme stratified by region was applied to collect 239 raw milk samples from 93 plants belonging to 17 dairy companies. Compared to a previous survey led in 1998 analyzing half-skimmed drinking milk in France, the PCDD/Fs level was cut by half, with an average concentration of 0.33pg toxic equivalent (TEQ)/g fat in 2006. The mean DL-PCBs concentration was 0.57pg TEQ/g fat and subsequently the sum of PCDD/Fs and DL-PCBs was 0.90pg/g fat, values below the thresholds defined by the European Union regulations. [Copyright &y& Elsevier]

Abstract: Biomonitoring for environmental chemicals presents various challenges due to the expense of measuring some compounds and the fact that in some samples the levels of many compounds may be below the limit of detection (LOD) of the measuring instrument. Even though various statistical methods have been developed to address issues associated with data being censored because results were below the LOD, the expense of measuring many compounds in large numbers of subjects remains a challenge. One solution to these challenges is to use pooled samples. There are many problems associated with the use of pooled samples as compared with individual samples, but using pooled samples can sometimes reduce the number of analytical measurements needed. Also, because pooled samples often have larger sample volumes, using pooled samples can result in lower LODs and thereby decrease the likelihood that results will be censored. However, many data sets obtained from environmental measurements have been shown to have a log-normal distribution, so using pooled samples presents a new problem: The measured value for a pooled sample is comparable to an arithmetic average of log-normal results and thus represents a biased estimate of the central tendency of the samples making up the pool. In this paper, we present a method for correcting the bias associated with using data from pooled samples with a log-normal distribution. We use simulation experiments to demonstrate how well the bias-correction method performs. We also present estimates for levels of PCB 153 and p,p′-DDE using data from pooled samples from the 2001 to 2002 National Health and Nutrition Examination Surveys. [Copyright &y& Elsevier]

Much progress has been made in recent years to address the estimation of summary statistics, using data that are subject to censoring of results that fall below the limit of detection (LOD) for the measuring instrument. Truncated data methods (e.g., Tobit regression) and multiple-imputation are two approaches for analyzing data results that are below the LOD. To apply these methods requires an assumption about the underlying distribution of the data. Because the log-normal distribution has been shown to fit many data sets obtained from environmental measurements, the common practice is to assume that measurements of environmental factors can be described by log-normal distributions. This article describes methods for obtaining estimates of percentiles and their associated confidence intervals when the results are log-normal and a fraction of the results are below the LOD. We present limited simulations to demonstrate the bias of the proposed estimates and the coverage probability of their associated confidence intervals. Estimation methods are used to generate summary statistics for 2,3,7,8-tetrachloro dibenzo-p-dioxin (2,3,7,8-TCDD) using data from a 2001 background exposure study in which PCDDs/PCDFs/cPCBs in human blood serum were measured in a Louisiana population. Because the congener measurements used in this study were subject to variable LODs, we also present simulation results to demonstrate the effect of variable LODs on the multiple-imputation process. [Copyright &y& Elsevier]

This paper reports on an intensive study into releases of polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated furans (PCDF) and polychlorinated biphenyls (PCB) from a diesel engine and the analysis of PCDD/F and PCB in crankcase lubricating oil. Experimental conditions were set and carefully controlled in order to maximize the possible impact of, and our ability to measure the effect of, changes in the levels of chlorine in the lubricant. Emissions to air were measured using modified EPA methods following the principles of the European EN 1948 standards. A series of 40 experimental runs were completed using three reference lubricants formulated to have three levels of chlorine present as a residual component (at levels of 12, 131 and 259mgkg−1 or ppm). The engine was run with and without the diesel oxidation catalyst. All lubricants were realistic oils and the use of unrealistic additives or doping of components – particularly chlorine – in the fuel and lubricant was carefully avoided. Analysis of fuel and lubricant (before and after testing) samples required strenuous attention to achieve acceptable recoveries and showed non-detectable levels of PCB and PCDD/F at a detection limit of around 1.5ng I-TEQ kg−1 (ppt), indistinguishable from the laboratory blank. The testing demonstrated the need for extreme care to be taken in developing measurement methods that are sufficiently sensitive for measuring chlorine content of fluids and PCDD/F in oils, the latter being particularly challenging. Mean emissions of PCDD/F with the diesel oxidation catalyst in place were 23 pg I-TEQ l−1 of fuel and with the diesel oxidation catalyst removed 97 pg I-TEQ l−1 of fuel. The results of this testing showed that the emissions of PCDD/F were greatly reduced by the presence of a diesel oxidation catalyst in the exhaust, a finding that has not been explicitly tested in previous work. They also show that emissions from the engine were not controlled by the level of chlorine in the lubricant and that emissions did not change in response to a much greater step change in the total chlorine entering the combustion chamber due to a change in the level of chlorine in the fuel. Emissions when the engine was configured with a diesel oxidation catalyst showed a consistent pattern that appears to be unique in the experience of the authors. [Copyright &y& Elsevier]

Abstract: 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 302ng/g lipid weight, with BDE 47>100>99∼154>153. For all fish of all species from all sampling areas, the mean PCDD/PCDF International Toxic Equivalent (I-TEQ) was 33.1pg/g lipid. For the three coPCBs (77, 126, 169), the mean I-TEQ for all fish of all species from all sampling areas was 109pg/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. [Copyright &y& Elsevier]

Abstract: We have measured the content of polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (together defined as “dioxins”) in 269 samples of food of animal origin collected through the regional veterinary services, covering the national territory. Quantification of the dioxins was accomplished by isotope dilution method, and toxic equivalents (TEQ) were calculated. The average daily food intake was obtained from two main sources: national data collected by the National Institute of Nutrition, and data from an ongoing cohort study on diet and cancer including 40,000 Italian subjects. The mean value of dioxins measured in food of animal origin was 0.144±0.266pg-TEQ/g (range: 0.003–1.655pg-TEQ/g). Fish was the item with the highest content. The estimated intake of dioxins with main food items of animal origin is presented. The major contribution to dioxins intake with food comes from cow milk and fish consumption. These results are in agreement with what observed in studies conducted in other countries, such as Germany, Finland, Japan, Spain, and are below the limits set by the European legislation. [Copyright &y& Elsevier]

Abstract: Background: Polychlorinated biphenyls (PCBs) and related compounds such as polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-dioxins (PCDDs) alter sexual maturation and endocrine function in animals. In 1978–1979, a mass poisoning occurred in central Taiwan from cooking oil contaminated by heat-degraded PCBs and oxidated compounds PCDFs. We tested the hypothesis that in utero exposed to PCBs/PCDFs alter sexual maturation, endocrine, and reproductive function in the human pubescent females. Methods: In 1997–1999, girls aged 13–19 years, born to mothers exposed to PCBs/PCDFs, was invited to participate in the study. Menstruation characteristic was recorded daily for 84 days and serum levels of estradiol, LH, FSH, and testosterone were measured on the 3rd day of menstruation. Results: A total of 17 exposed girls and controls participated, the exposed girls reported shorter mean duration of bleeding per cycle than 16 unexposed (5.5 vs 6.5 days, P =0.0055). There was a higher rate of irregular menstrual cycle in the exposed girls (40% vs 0%, P =0.018). Serum levels of estradiol (P =0.016) and FSH (P =0.061) were higher in exposed girls as compared to controls. Conclusions: We conclude that prenatal exposure to PCBs/PCDFs resulted in abnormal menstruation and higher estradiol and FSH levels in follicular phase of menstrual cycle in adolescent girls. [Copyright &y& Elsevier]

Abstract: The detoxification of soil and sludge from polychlorinated dibenzo-dioxins (PCDD) and -furans (PCDF) has been achieved by means of the K-PEG technology based on the in situ formation of the complex between polyethylene glycol (PEG) and KOH. Dechlorination of the pollutants was promoted by heating the samples up to 250°C, above the PEG thermal degradation onset (>140°C). As a consequence, a bursting evolution of hydrogen was observed which gave a reductive character to the reaction media and atmosphere. PCDD and PCDF chlorine atoms were progressively eliminated by a hydrodehalogenation reaction. After optimisation of the experimental parameters, the toxicity index was lowered more than 98%. In order to gain insight on the mechanism of the reaction, PEG thermal degradation chemistry was studied in some detail. The analytical results (mainly by mass and IR spectroscopy) suggest that PEG has an essential role on promoting the dehalogenation reaction by acting as a phase transfer agent as well as a source of hydride. [Copyright &y& Elsevier]

Abstract: Air samples were collected simultaneously at three urban sites in São Paulo City, Brazil, in winter, spring, summer and fall (in 2000 and 2001). Andersen PUF samplers were used for gas and particles sequential sampling. Samples were analyzed using HRGC/HRMS according to US EPA Method 8290. The greater metropolitan area of São Paulo is the largest industrialized region of Latin America and has a highly polluted atmosphere. Concentrations of dioxins and furans, which are well-known toxic chemicals, ranged from 1.14pgm−3 to 13.8pgm−3 (0.047pgI-TEQm−3 to 0.751pgI-TEQm−3). Principal component analysis showed that all the variables are highly correlated with one another except the 2,3,7,8-TCDD one. This is consistent with the similar concentration profiles observed for the tetra, penta, hexa, hepta and octa-homologous groups of the three sampling sites studied. At all sites, the most abundant compounds were the hepta and octa congeners. The 2,3,4,7,8-PeCDF accounted for 37–46% of the total toxicity and the 2,3,7,8-TCDD accounted for 7–16%. Highest mass concentrations of PCDD/Fs were found in the site where there is influence of industrial activities and heavy vehicular traffic fueled by gasohol, diesel, and ethanol. [Copyright &y& Elsevier]

Abstract: This work compares two lipid extraction methods for determining 24 polychlorinated biphenyls (PCBs), seven dibenzo-p-dioxins (PCDDs) and ten dibenzofurans (PCDFs) in human blood plasma. The first method was based on conventional liquid–liquid partitioning with chloroform–methanol and the other made use of a sorbent (Chem-Elut) to facilitate the partitioning of lipids into a mixture of hexane and 2-propanol. A multi-layer-silica column including acid- and base-impregnated silica gel was used to reduce the amounts of lipid present in the samples before a basic alumina clean-up step and activated carbon fractionation of planar analytes (PCDD/Fs and non-ortho-PCBs) and non-planar analytes (including ortho-chlorinated PCBs). Gas chromatography coupled to high resolution mass spectrometry was used to identify and quantify the analytes in the two fractions. The wet weight based concentrations obtained by the two methods were in agreement but both methods suffer from large organic solvent consumption. The toxic equivalencies derived for PCBs and PCDD/Fs using the two methods were also in agreement. However, the chloroform–methanol method gave slightly higher lipid recoveries, although with greater variation, than the sorbent-assisted method. Nevertheless, despite giving lower lipid recoveries, the sorbent-assisted method has advantages in ease of use and applicability to whole blood samples. The formation of emulsions was avoided with the Chem-Elut method, which probably explains the lower variability in the lipid determinations. [Copyright &y& Elsevier]

Abstract: Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) were determined in 23 soil samples collected at reference sites of the Swiss national soil monitoring network (NABO). Total PCDD/F and PCB concentrations are well correlated and proportional (R2=0.720). The total PCDD/F levels were between 72 and 703ng/kg corresponding to 1.1–11ng I-TEQ/kg, total PCB concentrations (sum of seven congeners IUPAC no. 28, 52, 101, 118, 138, 153, and 180) were from 1.1 to 12μg/kg. In all samples, the PCDD/F and PCB concentrations were in the range of background levels for these contaminants in Central Europe. Ninteen samples revealed PCDD/F levels below the guide value of 5ng I-TEQ/kg set by the Swiss ordinance relating to impacts on the soil (OIS); concentrations for the remaining four samples were below the trigger value (20ng I-TEQ/kg). All PCB concentrations were below the guide value of 100μg/kg. The elevated PCDD/F and PCB levels in some of the samples originating from forested sites could be attributed to the scavenging effect of forest canopies for semivolatile organic compounds. This interpretation could be substantiated by the observed distortion of the congener and homolog patterns of PCDD/F and PCB which is characteristic for forested sites. [Copyright &y& Elsevier]

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64–2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans. [Copyright &y& Elsevier]

The potential environmental impact of emissions of halogenated aromatics from the steel industry is of growing concern. It has been suggested that electric arc furnaces are the only industrial source with constant or increasing emissions of dioxins to air. Here the results are reported from a pilot plant study on how scrap composition and various treatment alternatives affect the formation and release of chlorinated and brominated aromatics. The experiments were conducted with a statistical mixture design, and it is shown that scrap composition has a significant impact on the outcome. In contrast, the various treatment schemes examined––shredding, disassembly, and briquetting––did not affect the formation and release of halogenated aromatics. Parallel experiments with injection of adsorbents showed that it is possible to reduce emissions without substantial investments, and this option is recommended as a low-cost solution. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined in 30 Swiss cow’s milk samples collected at dairy farms in the vicinity to point sources, in rural/alpine areas distant to known sources, and from tanks in large industrial milk processing plants. The contaminant concentrations in samples collected in 2001 were compared to data from analyses conducted in 1984 and 1990/1991 at the same sites. In 2001, the PCDD/F levels in milk from farms near point sources (0.63 ± 0.26 ng I-TEQ/kg milk fat) are slightly but significantly higher in than milk from remote areas (0.36 ± 0.09 ng I-TEQ/kg milk fat). Consumer milk collected at the processing plants had intermediary levels (0.51 ± 0.19 ng I-TEQ/kg milk fat). However, milk in 2001 was significantly less contaminated than the samples collected in 1990/1991 and 1984. This trend is particularly pronounced near point sources but is also apparent in consumer milk and milk from remote areas. No geographical gradient in the atmospheric input of PCDD/F in Switzerland was found. The reduction in PCDD/F levels in dairy milk is paralleled by and correlated to the remediation of known PCDD/F emitting industries, as enforced by federal authorities. [Copyright &y& Elsevier]

Discharge of WHO toxicity equivalents (TEQs) of PCDF/PCDDs to Frierfjorden, Norway has been reduced from an estimated sum of 50–100 kg in the period 1951–1975 to about 6–7 kg in 1976–1990, and further to about 20 g for 1991–2000. In accordance with this, the yearly monitoring since 1987 has shown considerably decreasing contamination in organisms, first highly significant in all indicator species from 1990 to 1991, then levelling off. Present concentrations thus are still high. Compared with estimated “high background” (reference) concentrations of 10 ng TEQPCDF/PCDD/kg w.w. in liver of cod and in hepatopancreas (“brown meat”) of crabs, Frierfjord samples in 2001 were about 60 and 70 times higher, respectively. With considerable uncertainty due to large fluctuations, the rate of yearly decrease for TEQPCDF/PCDD in cod liver 1991–2001 has been calculated to 10–12%. A hypothetic target value of 50 ng TEQ/kg w.w. will not be reached until 2015–2020, possibly even later. Including contributions from dioxin-like PCBs and PCNs, the weekly maximum tolerable amount of cod liver and crab hepatopancreas from Frierfjorden in 2001 were about 2–3 g. Multivariate analysis of PCDF/PCDD congener profiles in four fish species, mussels and crabs resulted in five distinct groups, separating four of the species and grouping the remaining two together, hence demonstrating examples of species specific accumulation characteristics. [Copyright &y& Elsevier]

Dioxin analyses using a DB5MS chromatography column are presented for samples of dust from an electrostatic precipitator and emissions from the main stack of a UK sinter plant. The analyses have been repeated using the SP2331 column, for which the elution order has been determined for the whole range of tetra to octachlorodibenzo-p-dioxins and dibenzofurans, and which provides a larger degree of separation than the DB5MS column. Polychlorinated dibenzofurans are present in significantly larger amounts in both the dust and stack emissions, and are the main contributors to the I-TEQ. Analysis using the SP2331 column for dioxins show considerable similarity to those of Bacher et al. for soot from a wood-burning fire, but differ markedly from those of Addink et al. for simulation of waste incineration. The similarities to Bacher’s results are less for the dibenzofurans. Comparison of absolute concentrations with reported vapour pressures shows the retention of significant dioxin in the dust to involve mechanisms other than pure condensation. [Copyright &y& Elsevier]

The tissue–blood partition coefficients for a physiologically based pharmacokinetic (PBPK) model were determined, and the concentrations of 17 congeners of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in tissues in Japanese people were estimated using the model. According to the PBPK model established by Lawrence and Gobas [Chemosphere 35 (1997) 427–452], we assumed a steady-state fugacity model for Japanese people in general, and set the route of PCDD/Fs exposure only from food intake. The required partition coefficients for liver, kidney, adipose, muscle, skin, bile, gut and viscera (richly perfused tissue) were calculated using available autopsy data from eight Japanese men and women who were not accidentally exposed to PCDD/Fs. For validation of the partition coefficients, estimated PCDD/F concentrations in liver, kidney, fat, blood and muscle using the model were compared to other two sets of measured concentration data in Japanese tissues. Good agreement was obtained between estimated data and measured data, and most of the measured data were within the simulated concentration range in liver, kidney, blood and muscle. From these results, our model and calculated partition coefficients seem applicable for the estimation of congener-specific concentrations in human tissues. [Copyright &y& Elsevier]