Document jmbB6gjEJB5VX4pREGO51kk6R

American Chemical Society 1185 SIXTEENTH STREET. N W WASHINGTON. D.C 20036 Phone (202) 872*4450 7uesd i v i s i o n _ _ E f \ V v __rj._ PAPER AMERICAN CHEMICAL SOCIETY'S I84TH NATIONAL MEETING KANSAS CITY, MISSOURI SEPTEMBER 12-17, 1982 AUTHOR JOB TITLE _ ^ ___C V >f_________________ (Last Name) (First) i , C,\'&> < v*. Oss-______________ _______ A F F 1LI AT IO N <\ G < O.Q.tU C C^C" `\\C __________________ A D D R E S S ________ U l V . M > U U VAl U_____ S" (C j j) U VA\Pq u B U S I N E S S P H O N E ^ (o ^ 00^ IkS X ((_______________ HOME P H ONE llG cfl <3W f 0 T I T L E O F P R E S E N T A T I O N ? o Va C V \ v oAc<L U p TUfvJS , ( L i U v . X o u^ o'A'OLX ^(v^1nvjul C.VoCO. <XK O'vnt G."V C L ^' .vwxAL - Ei o Lv-j_K.cx\ \ cv\A<iL V*C M. y K A N S A S C I T Y A D D R E S S D U R I N G M E E T I N G _________________ ^______ ______ __________ K A N S A S C I T Y P H O N E N U M B E R __________________________________________ _____ _____ A R R I V A L D A T E IN K A N S A S C I T Y ___ S_C<A_ ____________________________________ D E P A R T U R E D A T E F R O M K A N S A S C I T Y Zry-'<___ _______________________________________ THIS DOCUMENT IS (Circle One): 1. Paper 2. Summary 3. News Release 4. Other .. IspecITy) TIME y DATE OF PRESENTATION _ _ i P l L am/^w) Sept. 1_2_, 13 ,(1 1_5, 16, 17 (Indicate hour r (Circle^Datej _ PLACE OF PRESENTATION C o H y)tn40 ______ ROOM I___ 0^0$ ,, ^ cvJt> I (Note to Correspondents: Release time is the time of presentation) CONTACTS: Geraldine Sanderson ................. (202) 872-4450 Nancy Enright ............... .......... (202) 872-4448 NfcV 0 36 505 \ 'S _ne_ws release POLYCHLORINATED DIOXINS, DIBENZOFURANS AND OTHER POLYNUCLEA? AROMATICS FORMED DURING INCINERATION AND PCB FIRES Christoffer Rappe, Stellan Marklund, Per-Anders Bergquist and Marianne Hansson Department of Organic Chemistry University of Umei S-901 87 Umed, Sweden The occurrence of polychlorinated dioxins (PCDDs) and dibenzofurans (PCDFs) in fly ash is veil documented. There is much less data reported on levels in other incineration products like flue gas and particulate. Due to the extreme toxicity of some of the PCDD and PCDF iscr.ers and the large variation in toxicity and biological potency between closely related isomers, a risk evaluation should be based on the levels of ,the.highly toxic isomers^ However, isomer specific ana lyses have only been made in a few cases, in most studies the results have been given in terms of tetra-CDDs, tetra-CFFs, hexaCDDs etc. The number of isomers in this type of samples is quite large, more than 30 PCDDs and 60 PCDFs have been found. 03650 c RESULTS M unicipal incineration, fluidized bed (Sweden) We have investigated a municipal incinerator working with a flui dized bed. The samples analyzed were extracts of particulates and condensates taken at two different sampling occasions. We found: 1. large variation between the two sampling occasions depending on the conditions in the fluidized bed (temperature, retention time, oxygen excess) 2. higher levels in the condensate than in the particulates indi cating that the major source of PCDDs and PCDFs is the flue g&= 3. a marked predominance for the tetra-, penta- and hexa-SDFs over the corresponding PCDDs 1), a dominance of octa-CDD over octa-CDF 5. tetra-CDFs is the dominating chlorination level among the ?CDI- = 6. oeta-CDDs is the dominating chlorination levei among -he PCDDs 7* tetra-CDDs (and 2,3*78-tetra-CDD) couild only be four.i 5r. one of the four samples, a condensate. The level of 2,37,3-tetraCDD is about 0.3 ng/m3. 8. a large number of tetra-CDF isomers could be identified 9. in addition to PCDDs and PCDFs we could find other polychlorir.E.*.ed polynuclear aromatics (like chloropyrenes, chlorochrysenes and chlorobenzopyrenes) in these samples. The biological effects cf these compounds have not been investigated. NEV 0 3 6 5 0 7 3 Industrial boiler (USA) - PCF incineration Samples of bottom ash and baghouse ash from an industrial boiler burning pentachlorophenol (PC?) contaminated waste were analyzed. A multitude of PCDDs and PCDFs were identified and the total levels of PCDDs were about 5 ppm ana of PCDFs about 2.5 ppm. In this_zase 2.3.7.8-tetra-CDD is only a very m inor peak and more than 9055 of the PCDDs are lower chlorinated congeners than octa-CDD, the expec ted PCP-dimerization product. The pattern of the tetra-, pente and hexachloro dioxins is in good agreement with the dioxin pattern found in samples of European fly-ash. Rotatory cement kiln (Norway) - ?CB incineration We have analyzed a series of samples taken during a test stud;.* of thermal destruction of PCB in a rotatory cement kiln in Norway. The kiln is 150 m long with a diameter of 3.5 m. It' has a so railed "wet11 oven operating at 1^50 C in the solid material and at 2 jZj C in the flames. During the test period li m 3 of PCB was burned at a feeding rate of 50 kg/h. The samples analyzed include condensates, particulates and cement. All the samples were negative for PCIFs and PCDDs. Accidental PCB-fires a) Capacitor fire, SkOvde, Sweden In March 1982 a fire broke out in a capacitor battery (liOO V' serving a high-frequency oven. The dielectricum in the capacitors consisted of mineral oil or PCB and the two types of capacitors were NEV 0 3 6 5 0 6 I mixed at random. The fire started in a capacitor containing r.inertl oil, and about 2 h elapsed until the fire was completely extinguished. The building, a foundry, was very veil ventilated. Wipe tests were taken and analyzed. Che results show that levels exceeding 111 ng/r2 could only be found in ar. area close to the fire. The highly toxic 2 ,3 ,7 ,8-tetra-CDF is one of the major dibenzofuran isomers. In addition to the PCI;?5 the samples contained a series of poly chlorinated pyrenes, but no dioxines or biphenylenes could be fount in the samples from this fire. b) Capaoiior fires StookhoVm> Sweden Soot samples were collected from an accidental ?CH-fire in Stockholm, Sweden, in August 1951. Here, capacitors filled with PC3 was ignited probably due to electrical misfailure (10 kV). The extract contai ning the planar polychlorinated polynuclear aromatics was analyzed and the major peaks were a series of chlorinated biphenylenes, but other compounds found were the highly toxic 2 ,3,7,8-tetra- and 2,3,^,7,8-penta-CDF. Ito dioxines could be found. o) Transformer fire, zinohomton, USA The dielectricun in the Binghamton fire was a mixture of 65y: Aroclor 125*4 and 35/> chlorobenzenes. Soot samples from this fire were analyzed and the dominating products were the PC3?s, more than 2000 ppm of total PClPs. The highest levels were found for per.taand hexa-CDFs, 700 ppm and 1000 ppm respectively. The highly toxia isomers were the dominating isomers. In addition to PCDFs we also found a series of PCZiUs. the dominating NEV 03 6 5 0 9 I BOmers were the highly toxic 2,3,7,8-tetra-CDD (0.6 p;n) ar.d l2,3,78-penta-CDP (2.5 ppm). CONCLUSIONS In addition to polychlorinated dioxins and diben zc fura:.=, ve have found several other products like polychlorinated biphe-ylenes, pyrenes, benzopyrenes and chrysenes. Much interest has been given the observation of polychlorinated dioxins in incineration products. It has been suggested by Low Chemicals that dioxins are ubiquitous and formed in de r.ovo reacttions. The data reported here shows a much more complicated picture. 1. The dioxins are only one part of the problem of thf forr.ation of toxic polychlorinated polynuclear aromatics (PC*.'iAs) during incineration and other thermal reactions. The same interest should be given to the polychlorinated dibenzofurar.s. 2. The highest levels of PCPNAs are found when technical products are thermally converted directly into dioxins or dibenzofurans. Exan\ples of precursors are: chlorophenols - dioxins PCBs - dibenzofurans, biphenylenes chlorobenzenes - dioxins, dibenzofurans chlorodiphenyl ethers - dioxins, dibenzofurans 3. Dechlorination of octachlorodioxin to hepta-, hexa- and ether lower chlorinated dioxins is another major pathway. I4. Lower chlorinated compounds like mono-, di- and tri:hlore deri vatives of dioxins, dibenzofurans, pyrenes, bensopyrenes and NV 036510 \ c chrysenes car. be formed in a de novo formation similar to the formation of benzo(a)pyrene and other polynuclear aro matics in most incineration reactions. 5 . Under special conditions flue gas is the major source of