The effect of inorganic and organic chlorine on formation of highly chlorinated organic compounds during incineration: Laboratory pilot study

Aliphatic liquid as a basic fuel was incinerated in a laboratory scale pilot plant. Inorganic chlorine and organic chlorine mixed with basic fuel were used as additive chemicals. Sodium chloride (NaCl) and tetrachloroethylene (C₂Cl₄) were used as the sources of inorganic and organic chlorine. Combustion parameters were adjusted for optimum combustion and, consequently, the amount of particles in flue gases was low. The concentrations of chlorine in flue gases were high enough for possible formation reactions of organic chlorinated compounds in all of the chlorine input tests. An increase in chlorine input did not significantly increase the amounts of highly chlorinated organic compounds, like PCDD/Fs. The main result was that chlorophenol concentrations increased in parallel with organic chlorine input. Comparing organic chlorine to inorganic chlorine tests showed that more highly substituted PCDD/F congeners were formed when organic chlorine was the additive chlorine source. The formation of highly chlorinated organic compounds such as PCDD/Fs requires not only chlorine and aliphatic fuel to be formed, but some catalysts are also needed.     

PCDD/F in waste water discharges from flue gas scrubbers of waste incinerators and coal operated power plants

Scrubber water samples from different combustion plants and gypsum samples as obtained in the flue gas washing with lime water were analyzed for PCDD/F. Three of the investigated nine scrubber water samples showed PCDD/F contents between 0,4 and 11,5 ng I-TEq/1 where as in the 17 gypsum samples examined only in a few cases very low levels of HpCDD and OCDD could be detected.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.     

氯代二恶英微生物降解性的初步探讨

本研究通过分离和筛选，从氯苯生产车间附近土壤和施用五氯酚除草剂的湖泊底泥中选出八支菌株，均能降解一氯代二恶英，３周内最多可降解４５％，但随氯取代数的增加而降解能力减弱，多数菌株不能降解三氯代二恶英，选择邻二氯苯为共代谢物的初级营养物，４１号株３周内可降解３３％三氯代苯基二恶英，说明选择适当的共代谢物，可改善微生物对高氯代二恶英的降解性。     

Brominated flame retardants and polychlorinated biphenyls in fish from the river Scheldt, Belgium

Levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and polychlorinated biphenyls (PCBs) were measured in several fish species originating from the river Scheldt (Belgium). Five sampling locations were chosen in a highly industrialized area along the river, while two ponds in the vicinity of the river served as reference sites. The present study is a follow-up of a survey performed in 2000 which reported extremely high levels of PBDEs and HBCDs in eel (Anguilla anguilla) collected from the same region (Oudenaarde, Flanders). The sum of tri- to hepta-BDE congeners (2270+/-2260 ng/g lipid weight (lw), range 660-11500 ng/g lw) and total HBCDs (4500+/-3000 ng/g lw, range 390-12100 ng/g lw) were one order of magnitude higher than levels usually reported from freshwater systems, indicating the presence of point sources. In most samples, levels of total HBCDs were higher than those of PBDEs, probably due to the high density of factories using HBCD as an additive brominated flame retardant (BFR). The high values of HBCDs were confirmed by both gas- and liquid-chromatography-mass spectrometry. Although BFR levels were between the highest ever reported in freshwater ecosystems, PCBs could be detected at even higher concentrations (16000+/-14300 ng/g lw, range 3900-66600 ng/g lw), being among the highest levels recorded in Belgium. The inter-sampling site variation of PBDEs, HBCDs and PCBs was comparable. All locations presented similar PBDE congener profiles, with BDE 47 being the dominant congener, followed by BDE 100, BDE 99 and BDE 49, probably originating from the former use of the penta-BDE technical mixture. In order to estimate the impact of these point sources on human exposure, we further focussed on eels which showed a considerable decrease in the PBDE and HBCD levels between 2000 and 2006. Due to the wide span in concentrations between the different sampling locations, a variable contribution to the total human exposure through local eel consumption was estimated. The calculated daily intake ranged from 3 ng to 330 ng PBDEs/day for normal eel consumers, but was as high as 9800 ng PBDEs/day for anglers, which may be considered at risk.     

Fish consumption reduces transfer of BDE47 from dam to murine offspring

Fish and seafood are important contributions to a healthy diet, but also contain persistent organic pollutants (POPs) like polybrominated diphenylethers (PBDEs) and polychlorinated biphenyls (PCBs). Discrepancies have been found between intake and accumulated levels of POPs, where fish consumers have had similar levels of POPs to the general population. Similarly fish oil consumption has been found to reduce accumulation of POPs. This study examined the accumulation of BDE47 or PCB153 in mice fed diets with different nutritional composition, using female mice with pre-weanling pups exposed through gestation and lactation. A fish-based diet was compared to a standard casein-based rodent diet. All diets had low background levels of environmental contaminants and were spiked with BDE47 or PCB153 to levels representing a realistic (∼0.004 μmol kgbw⁻¹ d) or a high dietary exposure (∼1.3 μmol kgbw⁻¹ d). Accumulation of BDE47 or PCB153 in offspring tissues after 18 d lactation reflected the maternal exposure levels. However, the pups of dams fed a fish-based diet had consistently lower BDE47 accumulation in liver, fat and stomach than pups from casein-fed dams. Similarly the pups of dams fed a high dose of PCB153 in a fish diet also accumulated less PCB153 than pups of the dams fed a casein diet, although not significant. In conclusion, the fish based diets seemed to reduce transfer of BDE47 and PCB153 from dams to pups. The study highlights that in-depth knowledge about nutritional impact on toxicokinetics is of great interest to vulnerable consumers.     

Treatment of polychlorinated biphenyls in two surface soils using catalyzed H₂O₂ propagations

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H₂O₂ propagations (CHP—modified Fenton’s reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (<40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (>24 h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94% in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures >40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment.     

Polychlorinated biphenyls (PCBs) in indoor air and in serum among older residents of upper Hudson River communities

A study was conducted to evaluate the association between PCBs in residential indoor air and in the serum of older, long time residents of three upper Hudson River communities. Samples of indoor air and of serum were collected from 170 persons 55 to 74 years of age, and analyzed for PCBs using glass capillary gas chromatography. After adjusting for age, BMI, cigarette smoking, and Hudson River fish consumption with multiple linear regression analysis, the results indicated statistically significant associations between concentrations in indoor air and serum for PCB-28, a lightly chlorinated congener common in air that accumulates in serum, and PCB-105. Duration of exposure was an important factor, since among persons who had lived in their home for 39 years or more, 11 of the 12 most commonly detected congeners were significantly correlated, as was their sum (∑ PCB). Significant associations between indoor air and serum PCB concentrations also were more likely when collected in cooler months and if the two samples were collected within 20 d of each other. The study is among the first to indicate that PCB concentrations characteristic of residential indoor air are associated with a detectable increase in body burden.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.