1. Distributions of 3,3 ’,4,4 ’,5-PeXB in FeCl 3 tetra-, penta-, hexa-, and hepta-XB. in FeCl 3 Etching liquid Etching waste Steel plant converter dust iron powder Recycle plant FeCl 3 FeCl 2 Cl 2 Etching plant Fe Cu water treatment Ni Coagulant printed circuit board etching plant #169 HxCB FeCl 3 STD DETECTION OF POLY HALOGENATED BIPHENYLS IN THE FeCl 3 MANUFACTURING PROCESS Nakano T, Matsumura C, Tsurukawa M, and Moriguchi Y Hyogo Prefectural Institute of Public Health and Environmental Sciences, 3-1-27 Yukihira-cho, Suma-ku, Kobe, 654-0037 Japan (A) (B) (C) Fe Cu Br Pb Fe Zn Ni Mn Cr Fe Zn Ni Mn Fe Zn Ni Mn Cu Pb Cr (A) (B) (C) Fe Cu Br Pb Fe Zn Ni Mn Cr Fe Zn Ni Mn Fe Zn Ni Mn Cu Pb Cr Etching FeCl 2 FeCl 3 Figure 1 GC/MS chromatogram in contaminated FeCl 3 Co-PXB: #126,#169,#189 （ monobromo substituted ） Figure 2 GC/MS chromatogram in contaminated FeCl 3 Co-PXB: #126 （ PeCB, MBrTeCB, DiBrTrCB ） Figure 3 Fluorescent X-ray analysis of liquid samples (A) used etching waste, (B) FeCl 2, (C) FeCl 3 Figure 4 PBrDPE in strongly acidic solution in presence of HCl, FeCl 2 and CuCl 2. Figure 5 TEQ contributions (%) of co-PCB in FeCl 3 Figure 6 Distributions of 3, 3’, 4, 4’, 5-PeXB in FeCl 3. Figure 7 tetra-, penta-, hexa-, and hepta-XB. in FeCl 3 Unique distributions of major PCB congeners from 3,3’-dichloro benzidine related sites. PCB concentrations in waste water treatment system. FeCl 3 manufacturing process. Figure GC/MS chromatogram in contaminated FeCl 3 (Co-PCB: #126) Figure GC/MS chromatogram in contaminated FeCl 3 (Co-PCB: #169 ） FeCl 3 manufacturing process and metal recovery process. FeCl 3 as coagulant Coprecipitation involves removal of two or more constituents by a precipitation reaction. Coprecipitation of element with Fe(OH) 3 is an effective treatment process: FeCl 3 + 3H 2 O = Fe(OH) 3 + 3H + + 3Cl - FeCl 3 as etching liquid Ferric Chloride (FeCl 3 ) is used to etch away copper that isn't protected by the remaining photoresist coating on the PC board (Printed circuit board). To recover copper and nickel from a spent FeCl 3 etching solution, these chemicals are recycled. Introduction In recent years it was found that several organic and inorganic food and feed additives can be contaminated with PCDD/PCDF and other persistent organic pollutants. One known example is the PCDD/PCDF contamination of chicken from contaminated ball clay used as food additives. Recently the EU have enacted a law with limits for PCDD/PCDF and PCB concentration for food and feed including food additives. Currently inorganic food/feed additives are screened and evaluated in this respect in the EU. In Japan a research project was performed evaluating POPs in FeCl 3. FeCl 3 is used partly as food/feed additive but a much larger share of FeCl 3 is used for purification of water. A common used waste water treatment step using FeCl 3 is coagulation following by a sedimentation step. A part of the FeCl 3 is produced from recycled materials. One of the recycling processes use the Fe recovered from etching liquid of printed circuit board from and waste acids from steel mills. The aim of this study was to evaluate if the FeCl 3 used for water treatment can be contaminated with persistent organic pollutants. This first study revealed that FeCl 3 can be highly contaminated with dioxin-like PCBs and chlorinated-brominated PXBs calling for further investigations and possibly actions on international level. Materials and Methods GC/MS analysis : The analysis was carried out using a HP 6890 gas chromatograph connected to a JMS-800D mass spectrometer (JEOL Ltd. Japan) operating at a resolution >10 000. Co-PCB, Co-PXB and PXDF were analyzed using HT8-PCB column. Temperature program used for congener specific separation of the PCB, PXB and PXDF on HT8-PCB column: 120C, 20C/min. to 180C, 2C/min. to 260C. 5C/min. to 300C, 5 min. isothermal. Monitoring ions for GC/MS analysis are listed in Table. Standards: Commercially-available native/labeled standards were obtained from CIL as authentic standard/mixtures for crosschecking the assignment., 4’-bromo- 3, 3’, 4, 5- tetrachloro biphenyl was obtained from CIL for a PXB standard. Results and Conclusion - Some lots of FeCl 3 produced and used for water purification were found to be highly contaminated with PCBs (ng-TEQ/L) and chlorinated-brominated PXBs. The contaminated lots of FeCl 3 stem from a process using partly FeCl 3 as a recyling product from etching of printed circuit boards. - As PCB contaminants mainly the toxic coplanar PCB congeners having dioxin-like properties and assigned TEQ values were found (#126 > #169 > #189). - In addition to the chlorinated PCBs also monobrominated- polychlorinated s of Co-PCB #126, #169 and #189 were detected in slightly lower concentrations (Figure 7). - Possible pathways for the formation of the PCBs are proposed: either from brominated flame retardant contamination from the etching process (e.g. PBDE; Figure 4) or formation from certain aromatic organics forming PCBs during the chlorination steps in the process of FeCl 3. - The finding of highly dioxin-like PCB contaminated FeCl 3 used for waste purification is alarming and need to be highlighted and investigated as possible contamination source for drinking water and waste water sludge. Since the FeCl 3 is used worldwide in water purification, investigations should be initiated with an international perspective. HCl, FeCl 2, CuCl 2 PBrDPE References 1. Grabda M, Oleszek-Kudlak S, Shibata E, Nakamura T, Organohalogen Comp 2006; 68:1983.