Formation and chlorination of polychlorinated naphthalenes (PCNs) in the post-combustion zone during MSW combustion

Non- to octa-chlorinated naphthalenes (PCNs) were analyzed in flue gas samples collected simultaneously at three different temperatures (450 degrees C, 300 degrees C and 200 degrees C, respectively) in the post-combustion zone during waste combustion experiments using a laboratory-scale fluidized-bed reactor. PCN homologue profiles in all samples were dominated by the lower chlorinated homologues (mono- to triCN), with successive reductions in abundance with each additional degree of chlorination. The isomer distribution patterns reflected ortho-directionality behavior of the first chlorine substituent, and the beta-positions, i.e. the 2,3,6,7-substitution sites, seemed to be favored for chlorination. Injection of naphthalene into the post-combustion zone resulted in increased PCN levels at 200 degrees C, demonstrating the occurrence of chlorination reactions in the post-combustion zone. However, the increases were restricted to the least-chlorinated homologue (monoCN), probably because there was insufficient residence time for further chlorination. In addition, an episode of poor combustion (manifested by high CO levels) was accompanied by extensive formation of 1,8-diCN, 1,2,3- and 1,2,8-triCN; congeners with substitution patterns that are not thermodynamically favorable. These are believed to be products of PAH breakdown reactions and/or chlorophenol condensation. Overall, PCN formation is likely to occur via more than one pathway, including chlorination of naphthalene that is already present, de novo synthesis from PAHs and, possibly, chlorophenol condensation.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Highly toxic coplanar PCBs: occurrence, source, persistency and toxic implications to wildlife and humans

Isomer-specific determinations of PCB congeners in a wide variety of animal species such as fish, marine mammals (whale, dolphin and porpoise) and terrestrial mammals (dog, cat and human) revealed the environmental occurrence of highly toxic coplanar 3,3',4,4'-tetrachlorobiphenyl (T(4)CB), 3,3',4,4',5-pentachlorobiphenyl (P(5)CB) and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB) within a range of few pg g(-1) to several ten ng g(-1) in fat tissues (except fish) on a wet weight basis. Detection of these toxic residues in wild specimens collected from remote areas such as the North Pacific suggests the already widespread distribution of coplanar PCBs as in the case of general PCB pollution. The clear positive correlations between concentrations of total PCBs and each of the three coplanar PCBs obtained in all mammals analysed suggest that the sources of coplanar PCB contamination to the environment are mainly commercial PCB preparations. Comparison of the composition of three toxic coplanar PCBs in commercial PCB mixtures and in the various animals indicates the relative metabolisability of these congeners as follows: 3,3',4,4'-T4CB>3,3',4,4',5-P5CB>3,3',4,4',5,5'-H6CB. Moreover, marine mammals seem to have lower potency to metabolise the coplanar PCBs in comparison with terrestrial mammals. In human adipose tissues, the concentrations of coplanar PCBs were found to be much higher than 2,3,7,8-tetrachlorodibenzo-p-dioxin (T(4)CDD), 2,3,4,7,8-pentachlorodibenzofuran (P(5)CDF) and other toxic congeners. 'T(4)CDD-equivalent' analysis based on the enzyme induction potencies and the residues of these toxic chemicals indicates that 3,3',4,4',5-P(5)CB may impose a greater toxic threat than dioxins and furans to the humans and probably to wildlife also.     

Congener profiles of PCDDs, PCDFs, and dioxin-like PCBs in the breast milk samples in Tokyo, Japan

Exposure to dioxins has raised much public concern recently. We determined the congeners' distribution of polychlorinated-dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the breast milk samples collected in Tokyo, Japan. Breast milk was taken from 240 mothers, 30 days after delivery in 1999 and 2000 in Tokyo, Japan. The actual concentration and TEQ concentration of PCDDs (14 congeners), PCDFs (15 congeners), and dl-PCBs (12 congeners), and each congener's contribution to the total TEQ level were calculated. Among all the samples, PCDDs accounted for 34.8%, PCDFs accounted for 23.5%, dl-PCBs accounted for 41.7%, which was also similar in the breast milk from the primiparae and secundiparae. The main contributors to the total TEQ with increasing percentages were 2,3,4,7,8-PeCDF, 1,2,3,7,8-PeCDD and 3,3',4,4',5-PCB (#126), and they accounted for more than 65% of the total TEQ. Detailed congener analysis in breast milk samples is effective to understand dioxin sources.     

Polychlorinated biphenyl congener patterns in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed, western Massachusetts, USA, using a novel statistical approach

A novel application of a commonly used statistical approach was used to examine differences in polychlorinated biphenyl (PCB) congener patterns among locations and sample matrices in tree swallows (Tachycineta bicolor) nesting in the Housatonic River watershed in western Massachusetts, USA. The most prevalent PCB congeners in tree swallow tissue samples from the Housatonic River watershed were Ballsmitter Zell numbers 153, 138, 180, 187, 149, 101, and 170. These congeners were seven of the eight most prevalent congeners in Aroclor 1260, the PCB mixture that was the primary source of contamination in the Housatonic River system. Using paired-Euclidean distances and tolerance limits, it was demonstrated that congener patterns in swallow tissues from sites on the main stem of the Housatonic River were more similar to one another than to two sites upstream of the contamination or from a nearby reference area. The congener patterns also differed between the reference area and the two upstream tributaries and between the two tributaries. These pattern differences were the same in both pipper (eggs or just hatched nestlings) and 12-day-old nestling samples. Lower-chlorinated congeners appeared to be metabolized in nestlings and pippers compared to diet, and metabolized more in pippers compared to nestlings. Euclidean distances and tolerance limits provide a simple and statistically valid method to compare PCB congener patterns among groups.     

Isomer specific synthesis using the Suzuki-coupling. Polychlorinated terphenyls as standards for environmental analysis

Defined polychlorinated terphenyl (PCT) single congeners as reference standards are the prerequisite for the development of analytical methods for their determination and quantification in the environment. The selective synthesis of PCTs for environmental analytical purposes by application of the Suzuki-coupling reaction is described. Under easily modified standard reaction conditions of this coupling process the PCTs can be obtained by reaction of benzeneboronic acids with dibromobenzenes mostly in good yields, as described by the synthesis of following PCT congeners: p-PCT (3,3("),5,5(")-tetrachloro-, 2,2("),4,4(")-tetrachloro-, 2('),3,3("),5,5(")-pentachloro-); m-PCT (3,3("),5,5(")-tetrachloro-) and o-PCT (3,3("),5,5(")-tetrachloro-). The terphenyl congeners were characterized by NMR (1H, 13C)- and FT-IR-spectroscopy. Their purity was checked by GC/MS analysis. The experimental and quantum-chemically calculated FT-IR-spectra were compared and it was shown, that the determination of the chlorine substitution pattern in the terphenyl congeners by their typical absorption spectra is possible.     

Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--I. Concentrations and patterns of specific PCBs, chlorinated pesticides and polychlorinated dibenzo-p-dioxins and dibenzofurans

Blubber samples from beluga whales (Delphinapterus leucas) in the St Lawrence River estuary were analysed for PCB congeners (ortho- and non-ortho-substituted) and other persistent organochlorines as well as chlorinated dibenzo-dioxins/furans (PCDD/Fs). Major individual components (mean concentrations > 1 microg g(-1)) were 4,4'-DDE, -DDD and -DDT, T12 (a toxaphene-related compound), trans-nonachlor, oxychlordane, mirex, HCB, tris(p-chlorophenyl) methane and dieldrin. Concentrations of SigmaPCBs (8.3-412 microg g(-1)), SigmaDDT (3.36-389 microg g(-1)) and mirex (0.18-6.8 microg g(-1)) were particularly elevated relative to other odontocetes in Canadian waters. SigmaDDT, PCBs (as Aroclor), mirex and T12 concentrations were positively correlated with age of adult females (> 10 years) but only weakly, or not significantly, correlated with age of adult males. PCDD/Fs were present at low ng kg(-1) levels and consisted mainly of penta- and hexachlorofurans, and hepta- and octachlorodioxin. CB126 (3,3',4,4',5-PCB) was the most prominent non-ortho-substituted PCB congener in beluga blubber. Total TCDD toxic equivalents averaged 330 ng kg(-1) in females and 1400 ng kg(-1) in males and were dominated by CB126, and the mono-ortho-substituted congeners CB105 and CB118. Biomagnification factors (BMFs) for mirex and SigmaPCB from fish to beluga ranged from 11 to 16, and were similar to BMFs in Arctic animals, indicating that elevated levels in St Lawrence animals are a consequence of relatively high levels of recalcitrant organochlorines in prey of the beluga in the St Lawrence river system.     

Comparisons of PBDE composition and concentration in fish collected from the Detroit River,MI and Des Plaines River,IL

Polybrominated diphenyl ethers (PBDEs) were identified in fish collected from the Detroit River, MI and Des Plaines Rivers, IL. In the Detroit River fish, carp and large mouth bass, the congener patterns were dominated by the 2,2',4,4'-tetrabromo (BDE-47) congener, however, in Des Plaines River carp the dominant isomers were the heptabromo congeners BDE-181 and BDE-183 and lesser amounts of another heptabromo congener, BDE-190, and two hexabromo congeners, BDE-154 and BDE-153. Three possible sources exist for these less-commonly identified PBDE congeners: (a) waste discharge from manufacturing or discarded products near the river, (b) public owned treatment work (POTW) effluents which constitute more than 75% of the flow in the Des Plaines River, (c) or formation of these congeners by debromination of in-place deposits of decabromodiphenyl ether. Average concentration totals (sum of concentrations for seven of the dominant PBDE congeners) were similar on a wet weight bases for the carp (5.39 ng/g wet weight) and large mouth bass (5.25 ng/g) in the Detroit River samples; however, the bass were significantly higher, p = 0.01, when compared on a lipid basis (bass--163 ng/g vs. carp--40.5 ng/g lipid weight). Some of the PBDE congeners were positively correlated with increasing lipid levels in both fish species. Average total PBDE concentrations in the carp from the Des Plaines River (12.48 ng/g wet weight) were significantly higher, p = 0.01, than in carp from the Detroit River. The residues were isolated using standard organochlorine methods for fish and analyzed using gas chromatography/mass spectrometry-negative chemical ionization methods.     

Detailed PCB congener patterns in incinerator flue gas and commercial PCB formulations (Kanechlor)

In this study, we determined the detailed PCB congener patterns in flue gases from eight incinerators and four commercial PCB formulations (Kanechlors). About 160 PCB peaks were identified in samples using a DB-5 column and HRGC/HRMS. The concentration of incinerator stack emission gas ranged from 0.02 to 44 ngWHO-TEQ/Nm3. The ratios of dioxin-like PCBs in the total PCB concentration were from 3.4% to 25.7% and from 0.63% to 9.1% in stack emission gases and Kanechlor samples, respectively. The PCB congener profiles of Kanechlor samples were similar to those of previous studies. To determine characteristic congeners in flue gas and Kanechlor samples, principal component analysis (PCA) of the data was conducted using STATISTICA for Windows 5.0J (StatSoft, Inc.). As a result, we obtained four principal components (PCs) and accounted for 74% of the total variance. PC 1 was interpreted combustion, PC 2 and PC 3 were interpreted the difference in the number of substituted chlorines and, PC 4 could not be determined. Moreover, we obtained three groups according to the PCB congeners pattern among samples by PCA. These specific congeners that represent characteristics of each class were identified. These data will be useful for the source analysis of PCBs in the environment.     

Persistency of highly toxic coplanar PCBs in aquatic ecosystems: uptake and release kinetics of coplanar PCBs in green-lipped mussels (Perna viridis Linnaeus)

The bioaccumulation potential of three highly toxic coplanar PCB isomers [3,3',4,4'-tetrachlorobiphenyl (T(4)CB); 3,3',4,4',5-pentachlorobiphenyl (P(5)CB); and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB)] was investigated using green-lipped mussels (Perna viridis Linnaeus) as a bioindicator, through a transplantation experiment at two locations in Hong Kong waters. By contrast to the relatively rapid uptake and release of many other PCB isomers, the non-ortho chlorine substituted coplanar PCB congeners exhibited slow uptake and clearance. The kinetic parameters of coplanar PCBs based on lipid weight-related data, and the degree of bioaccumulation based on the proportion of coplanar PCBs in total PCBs in mussels, clearly indicate that coplanar PCBs are highly bioaccumulative in lower organisms. On the assumption that mussels are unlikely to be particularly unusual with respect to their bioaccumulation of coplanar PCBs, it appears most likely that these highly toxic and persistent PCB congeners are concentrated by all aquatic organisms, and may reach higher consumers (including humans) in quantities of toxicological concern.     

Elementary reaction path on polychlorinated biphenyls formation from polychlorinated benzenes in heterogeneous phase using ab initio molecular orbital calculation

We have investigated the elementary reaction path on the 3,3',4,4',5,5'-hexachlorinated biphenyl (HxCB) formation from two 1,2,3,5-tetrachlorobenzenes (TCBz) and the catalytic role of copper on this formation using ab initio molecular orbital calculation. The elementary reaction path on the 3,3',4,4',5,5'-HxCB formation from two 1,2,3,5-TCBzs has been shown to occur as follows: Step 1--the dissociation of Cl atom substituted at 5-position in 1,2,3,5-TCBz, Step 2--the association between Cl atom substituted at 5-position in another 1,2,3,5-TCBz and the Cl radical formed in Step 1, Step 3-the elimination of Cl2 molecule from the intermediate species formed in Step 2, and Step 4--the 3,3',4,4',5,5'-HxCB formation from the direct condensation of two 1,2,3-trichlorophenyl radicals formed in Step 1 and Step 3. The geometric factor, which decides the reactivity of this formation, is the C-Cl bond strength of 1,2,3,5-TCBz. The catalytic roles of copper are to stabilize the total energy in the adsorption of 1,2,3,5-TCBz onto the copper surface and to weaken the C-Cl bond strength due to the charge transfer from the 1,2,3,5-TCBz to the copper surface. Moreover, we have achieved the prediction of the minimum energy path on the formation of non- and mono-ortho polychlorinated biphenyls congeners for which TEFs have been determined.     

Polychlorinated biphenyls (PCBs) in sediments in Hong Kong: a congener-specific approach to the study of coplanar PCBs in aquatic ecosystems

Patterns of contamination by polychlorinated biphenyls (PCBs) were investigated in fourteen samples of coastal sediments from Hong Kong. Congener-specific analyses revealed nine sediment samples from Junk Bay to contain PCBs at concentrations ranging from 31 to 2200 ng g(-1) dry weight, concentrations generally increasing with distance north in the Bay. By contrast, five sediments from the Tolo area to the north-east of Hong Kong exhibited total PCB levels of only 6.6 to 45 ng g(-) dry weight. The patterns of relative abundance of PCB congeners in the northern Junk Bay sediments suggested the existence of ongoing source(s) of PCBs in this area; biphenyls of lower chlorination were present at high concentration in these samples. Three coplanar PCBs (3', 4, 4'-tetrachlorobiphenyl; 3,3',4,4',5-pentachlorobiphenyl; and 3,3',4,4',5,5'-hexachlorobiphenyl) were found to be present in Junk Bay sediments; these are highly toxic and are cause for concern in aquatic environments. The abundance of the three coplanar PCBs in the sediments studied was similar to that in commercial PCB mixtures, suggesting that these congeners are not enriched over other PCBs by the sediments of coastal ecosystems. It is concluded that the preferential enrichment of coplanar PCBs occurs in the biosphere, rather than in sediments.     

Structure elucidation of four possible biogenic organohalogens using isotope exchange mass spectrometry

The molecular structures of four unknown bioaccumulating halogenated compounds, C10H6N2Br3Cl3, C10H6N2Br4Cl2, C10H6N2Br5Cl, and C10H6N2Br6 were characterized using isotope exchange positive chemical ionization (IE-PCI) mass spectrometry (MS) and identified by comparison to synthesized standards. NH3 and ND3 were used as reagent gases for the IE-PCI-MS experiment. The shift in mass of the quasimolecular ion between the NH3 and ND3 PCI obtained spectra indicated the number of exchangeable hydrogens attached to the two nitrogen atoms in C10H6N2Br4Cl2, and thus the type of amines present (primary, secondary, or tertiary). 19 compounds (13 amines of varying degree of substitution; six containing no nitrogen) were used as reference compounds and controls in the experiment to validate the IE-PCI technique. The results of the IE-PCI-MS indicated the presence of two tertiary amine functional groups. The molecular structures of the four hexahalogenated compounds were then proposed to be 1,1'-dimethyl-3,3',4,-tribromo-4',5,5'-trichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole, and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole and subsequently synthesized. Comparison of retention times and electron capture negative ionization (ECNI) full scans on various gas chromatography (GC) columns between the synthesized bipyrroles and the corresponding unknown compounds in biota indicated that three of the unknown compounds--possible marine natural products--were the proposed halogenated dimethyl bipyrroles. The placement of the halogen atoms on the fourth compound, C10H6N2Br3Cl3 could not be unequivocally determined since the synthesized standard could not be fully characterized.     

Congener profiles of PCB and a proposed new set of indicator congeners

In this study, a new method for calculating total PCB and toxic equivalents (TEQ) of coplanar PCB (Co-PCB) was proposed, called the 'PCB dual method'. This method analysed various kinds of technical PCB, samples contaminated by technical PCB and byproduct PCB. In the PCB dual method, a data set of 15 indicator congeners was utilized for the calculations, having IUPAC nos. #3, #8, #28, #52, #77, #101, #105, #118, #126, #138, #153, #180, #194, #206 and #209. The 15 congener set was chosen from the major congeners, determined by HRGC/HRMS analysis, in 18 technical PCB, Kanechlor, Aroclor, Clophen and Chlorofen, and 20 other samples, such as indoor air, flue gases, emission gases, municipal solid waste (MSW), ash and sealant. To obtain total PCB and TEQ of Co-PCB, the intermediate sum for the concentration of the 15 congeners was multiplied by each multiplication factor. As a result, we obtained the average factor used to calculate total PCB in technical PCB and other samples. For technical PCB, the factor was 3.01, while for indoor air samples, flue and emission gases, MSW, ash and sealants, the factors were 3.92, 4.16, 3.68, 4.52 and 4.77, respectively. Moreover, the factor used to calculate the TEQ of Co-PCB in Kanechlor and other source samples were also obtained. The factors for Kanechlor, indoor air samples and emission gases from a cement plant were in the order of 10(-5), while the factor for flue gases in a MSW incinerator was in the order of 10(-3). These data were valuable for the rough estimation of the TEQ of Co-PCB without separation from other PCB before individual measurements.     

Polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and non-ortho,mono-ortho chlorine substituted biphenyls in Japanese human liver and adipose tissue

We measured PCDDs/DFs levels in Japanese human livers and adipose tissues in 1999, and TEQ were calculated with WHO TEF. The mean total levels of PCDDs/DFs in livers and adipose tissues were 57 pg TEQ/g on a lipid basis and 49 pg TEQ/g on a lipid basis, respectively. 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 1,2,3,4,6,7,8-HpCDF concentrations in livers considerably differed from those in 1989 (p < 0.05). The mean non-ortho-chlorine substituted biphenyls levels showed 20 pg TEQ/g on a lipid basis and 17 pg TEQ/g on a lipid basis in livers and adipose tissues, respectively. In livers, the mean of 3,3',4,4'-TCB concentrations was 131 pg/g on a lipid basis, and 7.7-fold higher than that in 1989. The mean total mono-ortho-chlorine substituted biphenyls level was 13.0 pg TEQ/g on a lipid basis in livers and 21.6 pg TEQ/g on a lipid basis in adipose tissues. 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB levels decreased in adipose tissues, and 3,3',4,4',5-PeCB level only decreased in livers. PCDDs, PCDFs, and mono- and non-ortho-chlorine substituted biphenyls levels may have decreased in livers and adipose tissues because of a governmental policy on dioxins discharge for the decade. Then, we estimated the correlations of PCDDs, PCDFs and the related compound levels between livers and adipose tissues. The correlative PCDDs congeners may have had a similar behavior to that between liver and adipose tissue. On the contrary, most PCDFs isomers may have different behavior between liver and adipose tissue, while 2',3,4,4',5-PeCB (IUPAC No. 123) may also have a different behavior between liver and adipose tissue.     

Effects of regional differences in waste composition on the thermal formation of polychlorinated aromatics during incineration

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.     

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

Patterns of contamination by organochlorines and mercury in the eggs of two river passerines in Britain and Ireland with reference to individual PCB congeners

Unhatched eggs were collected in 1988 and 1990 from nests of the Eurasian Dipper Cinclus cinclus and the Grey Wagtail Motacilla cinerea in Wales, eastern Scotland and south-western Ireland. Mercury concentrations in Dipper eggs (geometric means 0.45-0.91 ppm (microg g(-1)) dry mass) were significantly lower in eastern Scotland than in either south-western Ireland or Wales, where the incidence of detectable residues increased markedly between 1988 (2% of eggs) and 1990 (69%). By contrast, DDE (geometric means 0.63-3.54 ppm in lipid), TDE (<0.01-1.80 ppm), DDT (<0.01-0.65 ppm), total PCBs (3.99-10.47 ppm), HEOD (0.39-0.61 ppm) and HCB (0.02-0.13 ppm) were all significantly higher in Scottish eggs than others. Around 33-46% of the total PCB burden in Dipper and Grey Wagtail eggs could be accounted for by six congeners (IUPAC numbers 118, 180, 101, 153, 138 and 170). Amongst these attributable PCBs, Dipper eggs from eastern Scotland were dominated by congener 153 (2,2',4,4',5,5'-hexachlorobiphenyl), whilst Welsh and Irish eggs were dominated by congener 118 (2,3',4,4',5-pentachlorobiphenyl). With the latter exception, all the individual congeners were found at significantly higher concentrations in Scottish eggs than others. Grey Wagtail eggs were dominated by congeners 118 and 101 (2,2,4,5,5'-pentachlorobiphenyl). In general, these congeners are common, widespread, and dominant components in the eggs of other wild birds for which data are available. Consistent with the low to medium levels of contaminants found in Dipper eggs, there was only slight evidence of any toxic effects. These included moderate shell thinning in relation to increasing DDE, and some evidence that contaminants had contributed to egg failure.