3,3',4,4',5-PeXB 0 1 PCB-126 MonoBr DiBr X X X X X Br 0Cl 5 Br 1Cl 4 Br 2Cl 3 Distributions of 3,3 ’ ,4,4 ’ ,5- PeXB in FeCl 3 OH Br Br Br Br Br Br O Br Br Br Br Br Br X X X X X X O X X X X X X X X X X X H Cl,FeCl 2, CuCl 2 (C l >> Br) OH Br Br Br Br Br Br O Br Br Br Br Br Br X X X X X X O X X X X X X X X X X X H Cl,FeCl 2, CuCl 2 (C l >> Br) HCl, FeCl 2 , CuCl 2 PBrDPE tetra-XB penta-XB hexa-XB hepta-XB 3,3',4,4',5- 3,3',4,4',5,5'- 2,3,3',4,4',5,5'- 3,3',4,4'- X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X tetra-, penta-, hexa-, and hepta-XB. in FeCl 3 32 36 40 44 48 0 71442 Br2T3CB 32 36 40 44 48 0 1382993 BrT4CB 32 36 40 44 48 0 5678926 P5CB 32 36 40 44 48 R etention Tim e (m in) 0 1578810 13C-P 5 CB #126 M Br-#126 DiB r-#126 #126 #105 #114 #123 #118 32 36 40 44 48 0 71442 Br2T3CB 32 36 40 44 48 0 1382993 BrT4CB 32 36 40 44 48 0 5678926 P5CB 32 36 40 44 48 R etention Tim e (m in) 0 1578810 13C-P 5 CB #126 M Br-#126 DiB r-#126 #126 #105 #114 #123 #118 28 32 36 40 44 48 52 0 160936 BrH6CB 28 32 36 40 44 48 52 0 2691689 BrP5CB 28 32 36 40 44 48 52 0 2250853 BrT4CB 28 32 36 40 44 48 52 R etention Time (min) 1093 83433 BrT3CB M Br-#126 M Br-#169 M Br-#189 28 32 36 40 44 48 52 0 160936 BrH6CB 28 32 36 40 44 48 52 0 2691689 BrP5CB 28 32 36 40 44 48 52 0 2250853 BrT4CB 28 32 36 40 44 48 52 R etention Time (min) 1093 83433 BrT3CB M Br-#126 M Br-#169 M Br-#189 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X B rPeC D F:417.7706,419.7679 PeBrB iphenyl:547.6268,549.6247 B rTeC DF :383.8096,385.8070 TeB r4M C B:501.6792,503.6771 B rTrC D F :349.8487,351.8460 T rB rD iCB :457.7297,459.7274 B rH xCB :437.7523,439.7496 D iB rTrC B :413.7800,415.777 B rPeC B :403.7913,405.7886 M B rTeC B :367.8329,369.8303 B rTeC B :367.8329,369.8303 13C -PeC B :337.920,339.9178 B rTrC B :333.8718,335.8694 PeC B :325.8805,327.8775 M onitoring ions ofPX B /PXD F Etching liquid Etching waste Steel plant converter dust iron powder Recycle plant FeCl3 FeCl2 Cl2 Etching plant Fe Cu water treatment Ni Coagulant printed circuit board etching plant 13 C coPCB PC B -126 C o-PC B FeC l 3 STD PeCB Co-PCB 0.0 100.0 #81 #77 #126 #169 TEQ(%) /L Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl #16 9 #169 HxCB FeCl3 STD DETECTION OF Co-PCB IN THE FeCl 3 MANUFACTURING PROCESS Takeshi Nakano , Chisato Matsumura, Masahiro Tsurukawa, and Yuzo Moriguchi Hyogo Prefectural Institute of Public Health and Environmental Sciences, 3-1-27 Yukihira-cho, Suma-ku, Kob e, 654-0037 Japan Abstract Co-PCB and Co-PXB (Polyhalogenated Biphenyls) have been detected as contaminants in the production of FeCl3. Relative PCB concentrations were #126 > #169 > #189. Monobromo congeners of Co-PCB #126, #169 and #189 were also detected. The concentration order of Monobromo biphenyl that replaced Cl with Br of Co-PCB was #126 #169 > #189. The ≒ concentration order was #126 (pentachloro biphenyl) > #126 (Monobromo-Tetrachloro Biphenyl) > #126 (DibromoTrichloro Biphenyl). Tribromo substituted Biphenyls were not detected. PBrDPE in the printed circuit board might be decomposed to polybromophenol and polybromobenzene radical in strongly acidic solution in the presence of HCl, FeCl2 and CuCl2. Dimerization of polybromobenzene radical forms Co-PXB with selective debromination and Br-Cl substitution Introduction Liquid FeCl3 used for coagulating sedimentation in wastewater treatment is recycled, and at the same time copper and nickel are recovered, using etching liquid of printed circuit board from etching facility and waste acid from steel mills. Though limited to specific product lots, liquid FeCl 3 produced during a certain period have contained high concentrations of PCB and PXB. The congener distribution characteristics of PCB and PXB contamination in liquid FeCl3 was found, and the formation process was newly deduced. 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. (A) (B) (C) F e C u C u B r P b F e F e Z n N i M n C r F e Z n N i M n F e F e Z n N i M n C u C u P b C r (A) (B) (C) F e C u C u B r P b F e F e Z n N i M n C r F e Z n N i M n F e F e Z n N i M n C u C u P b C r Etching FeCl2 FeCl3 Results and Discussion Figure 1 shows the GC/MS-SIM chromatogram of the contaminated liquid FeCl3. Monobromo #126, #169 and #189 were detected. PCB concentration was #126 > #169 > #189. The relative concentrations of monobromo compounds that replaced Cl with Br was #126 #169 > #189. Figure 2 is the GC/MS- ≒ SIM chromatogram of Co-PXB. The concentration level was #126 (PeCB) > #126 (MBrTeCB) > #126 (DiBrTrCB), and Tribromo, Tetrabromo and others were not detected. Among MBrTeCB; 3,3’,4,4,5’- monobromo-tetrachloro biphenyl, only 4'-bromo- 3,3',4,5-tetrachloro biphenyl is commercially available. In Figure 2, #126 (MBrTeCB) was proposed to be 3'-bromo-3,4,4',5-tetrachloro biphenyl, 3'-bromo-3,4,4',5'-tetrachloro biphenyl, or 4'-bromo- 3,3',4,5'-tetrachloro biphenyl. Figure 3 shows the results of fluorescent X-ray analysis on used etching liquid, liquid FeCl2 and liquid FeCl3. The used etching liquid was found to contain a high concentration of Cu and a trace of Br in addition to Fe and Cl. The major PCB congeners in the contaminated liquid FeCl3 were 3,3',4,4',5-PeCB (#126), 3,3',4,4',5,5'-HxCB (#169). In the manufacturing process, metal iron is added to used etching liquid (FeCl 2 and FeCl 3 ) and recover Cu and Ni. The used etching liquid is then recycled by blowing chlorine into the reduced FeCl2. In the past, the printed circuit boards contained brominated flame retardant (tetra-bromo- bisphenol-A, PBrDPE) and epoxides of Tetrabromobisphenol-A (glycidyl-ether of phenolic OH group) were used. The existence of brominated compounds is predicted such as epoxide of Tetrabromobisphenol-A in used etching liquid. Etching liquid contains CuCl2 and brominated compounds, and has extremely low pH References 1. Grabda M, Oleszek-Kudlak S, Shibata E, Nakamura T, Organohalogen Comp 2006; 68:1983. NOON Cl Cl + H N Cl H N Cl HN Cl NHCl HSOHN Cl NHCl 2HCl Cl Cl HSOHCl PRO D U CT Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl raw water w arm ing bath contactoxidation nitrification denitrification re-aeration rapidly -stirring slow ly-stirring coagulation ba th neutralization sterilization bath 0 40 80 120 160 effluentbath H3PO4 NaO H H2SO4 N aO H N aO H M eO H FeC l 3 N aO H H2SO4 N aO H H2SO4 sodium hypochlorite N aClO [Al 2(O H) nCl 6-n] m 12.5m 3 224m 3 24m3 PCB ( pg-TEQ /L) distribution bath m aterial tank 50-120m3 ferrous chloride iron dissolution tank 2HC l+Fe FeCl 2+H2 2FeC l 3+Fe 3FeC l 2 waste H C l steelmill H C l+FeC l 2 E tching waste liquid FeC l 2+FeC l 3 Printcircuitboard scrap iron steelsheet,press scrap density control filtration filtrate tank chlorination 2FeC l 2+C l 2 2FeC l 3 producttank ferric chloride (FeC l 3)manufacturing flow Cl 2gas Cu-recovery w ater treatm ent Etching liquid Figure 1 GC/MS chromatogram in contaminated FeCl3 Co-PXB: #126,#169,#189 (monobromo substituted ) Figure 2 GC/MS chromatogram in contaminated FeCl3 Co-PXB: #126 (PeCB, MBrTeCB, DiBrTrCB ) Figure 3 Fluorescent X-ray analysis of liquid samples (A) used etching waste, (B) FeCl2, (C) FeCl3 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 FeCl3 Unique distributions of major PCB congeners from 3,3’-dichloro benzidine related sites. PCB concentrations in waste water treatment system. FeCl3 manufacturing process. Figure GC/MS chromatogram in contaminated FeCl3 (Co- PCB: #126) Figure GC/MS chromatogram in contaminated FeCl3 (Co- PCB: #169 ) FeCl3 manufacturing process and metal recovery process . FeCl 3 as coagul ant Coprecipitation involves remo val of two or more constituen ts by a precipitation reactio n. Coprecipitation of elemen t 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 (FeCl3) is use d to etch away copper that is n't protected by the remainin g photoresist coating on the PC board (Printed circuit boa rd). To recover copper and ni ckel from a spent FeCl3 etchin g solution, these chemicals are recycled.