Distributions of 3,3 ’ ,4,4 ’ ,5-PeXB in FeCl 3

1. DETECTION OF POLY HALOGENATED BIPHENYLS IN THE FeCl3 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 References 1. Grabda M, Oleszek-Kudlak S, Shibata E, Nakamura T, Organohalogen Comp 2006; 68:1983. 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 usingHT8-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. 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 FeCl3. FeCl3 is used partly as food/feed additive but a much larger share of FeCl3 is used for purification of water. A common used waste water treatment step using FeCl3 is coagulation following by a sedimentation step. A part of the FeCl3 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 FeCl3 used for water treatment can be contaminated with persistent organic pollutants. This first study revealed that FeCl3 can be highly contaminated with dioxin-like PCBs and chlorinated-brominated PXBs calling for further investigations and possibly actions on international level. FeCl3 as coagulantCoprecipitation involves removal of two or more constituents by a precipitation reaction. Coprecipitation of element with Fe(OH)3 is an effective treatment process: FeCl3 + 3H2O = Fe(OH)3 + 3H+ + 3Cl- Steel plantconverter dust printed circuit board etching plant Fe iron powder Cu Recycle plant Etching waste Ni PCB concentrations in waste water treatment system. FeCl2 Etching plant Cl2 Coagulant #169 FeCl3 as etching liquidFerric Chloride (FeCl3) 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 FeCl3 etching solution, these chemicals are recycled. FeCl3 water treatment HxCB Etching liquid Figure GC/MS chromatogram in contaminated FeCl3(Co-PCB: #126) STD #169 FeCl3 FeCl3 manufacturing process. Figure GC/MS chromatogram in contaminated FeCl3 (Co-PCB: #169） Distributions of 3,3’,4,4’,5-PeXB in FeCl3 Cu Cu (A) (A) Etching FeCl3 manufacturing process and metal recovery process. Cu Cu Fe Fe Fe Fe Mn Mn Pb Pb Cr Cr Ni Ni Br Br Zn Zn Results and Conclusion - Some lots of FeCl3 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 FeCl3 stem from a process using partly FeCl3 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 FeCl3. - The finding of highly dioxin-like PCB contaminated FeCl3 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 FeCl3 is used worldwide in water purification, investigations should be initiated with an international perspective. FeCl2 (B) (B) Fe Fe Figure 2 GC/MS chromatogram in contaminated FeCl3 Co-PXB: #126（PeCB, MBrTeCB, DiBrTrCB） Fe Fe Mn Mn Zn Zn Ni Ni Figure 1 GC/MS chromatogram in contaminated FeCl3 Co-PXB: #126,#169,#189（monobromo substituted） FeCl3 (C) (C) Fe Fe Cu Cu Fe Fe Cu Cu Pb Pb Mn Mn Cr Cr Zn Zn Ni Ni HCl, FeCl2, CuCl2 PBrDPE Figure 4 PBrDPE in strongly acidic solution in presence of HCl, FeCl2 and CuCl2. Figure 5 TEQ contributions (%) of co-PCB in FeCl3 Unique distributions of major PCB congeners from 3,3’-dichloro benzidine related sites. tetra-, penta-, hexa-, and hepta-XB. in FeCl3 Figure 3 Fluorescent X-ray analysis of liquid samples (A) used etching waste, (B) FeCl2, (C) FeCl3 Figure 6 Distributions of 3, 3’, 4, 4’, 5-PeXB in FeCl3. Figure 7 tetra-, penta-, hexa-, and hepta-XB. in FeCl3