PCB and PCN Fate and Source Takeshi Nakano

PCB and PCN Fate and Source Takeshi Nakano (Hyogo Pref. Inst. of Env. Sci. )

Sudden Death of Dr. Imagawa on 19 th Feb. 2001 It is truly a shame to lose him at such a young age, and I thank for his help to my study Dr. Imagawa / Dioxin symposium in Kyoto (1994)

Atmospheric PCN (pg-TEQ/m 3) in Japan (JEPA) 1 0. 01 0. 0001 0. 00001 0 1 2 3 4 5 6 7 8 9 10

0. 600 0. 500 0. 400 0. 300 0. 200 0. 100 0. 000 Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 7 Cl 8 Homologue distribution of PCN in Ambient air

Kobe On the mountain Industrial site Homologue distribution of PCN in Ambient air

0. 600 0. 500 0. 400 0. 300 0. 200 0. 100 0. 000 PCN (vapor+particle) Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 8 Cl 7 50 PUF 40 30 PCB(gas phase) 20 10 Homologue distribution in Ambient air D 10 CB N 9 CB O 8 CB Hp 7 CB Hx 6 CB P 5 CB Te 4 CB Tr 3 CB D 2 CB M 1 CB 0

0. 600 0. 500 0. 400 0. 300 0. 200 0. 100 0. 000 PCN Cl 1 Cl 2 Cl 3 Cl 4 Cl 5 Cl 6 Cl 8 Cl 7 50 PUF PCB 40 30 20 10 Homologue distribution in Ambient air D 10 CB N 9 CB O 8 CB Hp 7 CB Hx 6 CB P 5 CB Te 4 CB Tr 3 CB D 2 CB M 1 CB 0

Ambient air (pg/m 3) Total concentration Ambient air (pg-TEQ/m 3) TEQ concentration Atmospheric level of PCB/PCN/PCDD/PCDF

Air　・　Rain Water　・　sediment β Air Selected PCN isomers from result of PCA　

Daily variation of PCB in ambient air

Relation between distribution of gase and particulate-PCB with temperature (�C) and atmospheric pressure (h. Pa).

20 10 30 30 Tri 3, 4, 3’, 4’- Di 4, 4’ 3, 4, 3’ 3, 4, 4’- 3, 3’ 3, 4 -/ 3, 4’- 30 #11 #12/#13 #15 #37 #74 #70 #66 #80/#55 #56 #77 #107 #123 #118 #114 #105 #126 #157 #169 #180 #193 #191 #170 #190 #189 Co-PCB in air and technical PCB Tetra Penta Hexa Hepta KC 300 -600 0 20 10 0 PUF Gas phase QMF particulate 20 10 0

PCB

PCN

Isomer spescific analysis

Source estimation

PCB

production 60, 000 t in Japan

PCB l l Source Fate Sediment Ambient air

PCN l l source Fate Ambient air Congener profiles

4 -MCP 1, 2, 8 -Tr. CDF 3, 4 -DCP 2, 3, 8 -Tr. CDF

Om- 2 -MCP 3 -MCP 1, 4, 9 -Tr. CDF 1, 4, 6 -Tr. CDF 2, 5 -DCP 1, 4, 7 -Tr. CDF 1, 4, 8 -Tr. CDF 4 -MCP p- Authentic standard (1, 4, 7 - : NMR) Synthesis of 1, 4, X-T 3 CDF isomers from chlorophenol

13 C 12 -MCDF 13 C 12 -MCDD 13 C 12 -Di. CDF 13 C 12 -Di. CDD 13 C 12 -Tr. CDF 13 C 12 -Tr. CDD 12 -Te. CDF 13 C 13 C 12 -Pe. CDF 13 C 12 -Hx. CDF 12 -Hp. CDF 13 C 12 -OCDF 13 C 12 -Te. CDD 12 -Pe. CDD 13 C 12 -Hx. CDD 12 -Hp. CDD 13 C 12 -OCDD Breakthrough from PUF plug using High volume air sampler

PCB l l Source Fate Sediment Ambient air

PCN l l source Fate Ambient air Congener profiles

PCN congener distribution in ambient air.

PCN isomer distribution in air, dry-deposition, rain particle, Halowax, sediment and landfil sludge.

Air Sampling

Water Sampling 100 L High volume water sampler • Qurtz Micro Fiber for particulate • Poly Urethane Foam for dissolved

PCN congener distribution in ambient air.

PCN isomer distribution in air, dry-deposition, rain particle, Halowax, sediment and landfil sludge.

Analytical Method of Environmental Samples Sampling Extraction Cleanup Measurement Daily Variation L/L -> SPE Removal Interference GC/MS, LC/MS

Importance of Low chlorinated DD/DF Isomer distribution formation mechanism degration mechanism Bio degradation pathway Important information origin estimation on site analysis Monitoring of stack gas MCDF > TCDF Monitoring of Environment PCB PCN PCDD PCDF 水系、大気系

Contribution in TEQ value Air depo sediment water soil

Ambient air TEQ value Total conc. Contribution in TEQ value

Precursor of PCDD/DF formation

PCN isomer distribution

Annual inventory of Dioxin from Incinerator 1. Hyogo pref 2. Japan

Hyogo pref Emission (g-TEQ/year) Japan Emision (g. TEQ/year)

Homologue Distribution River water PCDD PCDF

Homologue Distribution River sediment PCDD PCDF

Homologue Distribution River sediment Incineration pattern PCDD PCDF

River sediment Homologue Distribution PCP CNP Pesticide pattern PCP Pesticide pattern CNP PCDD Incineration pattern PCDF

Homologue Distribution Sea sediment 燃焼系 PCDD PCDF

PCB concentration and TEQ value KC 300 KC 400 KC 500 KC 600 0. 7ｘ１０－５２ｘ１０－５６ｘ１０－５３ｘ１０－５

Source estimation KC３００ N. C. P. KC５００ Insulator capacitor Sediment A Sediment B KC４００ KC６００ Insulator Ship paint capacitor

Isomer distribution and Source estimation Sediment A Water A KC 300

Isomer distribution and Source estimation KC４ 00 KC５ 00 KC６ 00

Co-PCB in sediment and PCA P 1 ： #118, #105, #180 P 2 ： #180, #170 KC-600 P 3 ： #77, #105, #180

Co-PCB isomer distribution and PCA KC-300 KC-400 KC-600 KC-500 KC-600

Co-PCB isomer ratio and Source KC-300 flyash KC-400 Sediment A KC-500 Sediment B KC-600

Co-PCB isomer ratio in environmental sample

Important Isomer for origin estimation PCDD Incineration(FBI) : 2, 6 -Pe. CDD(xxx 68, xxx 79)pattern　 Incineration(stoker : 2, 3 -Pe. CDD pattern Pesticide(CNP) : PCDD(13 -, 136 -, 138 -, 137 -, 139 -, 1368, 1379 -, 12468 -, 12379 -) Pesticide(PCP) : OCDD, Hp. CDD(1234678 -) Pesticide(24 -D) : D 2 CDD (2, 7 - , 2, 8 -) PCB Incineration and PCB product(KC, AC) #118/#77 ratio、#77/#126 ratio PCN Incineration and PCN product(HALOWAX) (Incineration)1267 -N, 12367 -N, (PCN product)1248 -N

quick cleanup methods PCDD simultaneous analysis of low chlorinated DD/DF PCDF origin estimation PCB PCN Isomer distribution Incineration Pesticide 排出源毎の特徴的分布を蓄積 Homologue distribution PCB（KC３～６００） PCN（Halowax）

Production of N. C. P Annual production PCB concentration Sediment core Annual production and Vertical distribution in sediment

Horizontal distribution in sea sediment 播磨灘 nada Harima 大阪湾Bay Osaka スープ皿のような地形 like a soup dish Independent area 東半分：陸、西半分：海 western and eastern part Sea海底の地形・水深 bottom and water depth

Horizontal distribution in sea sediment Channel : fast stream sand silt sand Central part: slow stream Particle size in sea sediment

海域底質の粒度分布を考慮しない場合 Before normalization by particle size distribution coast High Low Inmost part channel High 濃度の単調減少 Harima nada Central part : High 鳴門 Low Osaka Bay NAKANO (1979) Horizontal distribution in sea sediment

海域底質の粒度分布を考慮した場合 After normalization by particle size distribution Constant恒流図と濃度分布 flow map and PCB distribution 粒径・微細粒子・比表面積で規格化海域底質中PCBの水平分布 Horizontal distribution in sea sediment

Horizontal distribution in sea sediment 海域底質の水平分布神戸港周辺 Around Kobe port Osaka bay 大阪湾 PCB濃度の距離減衰 PCB concentration and Distance from source

環境大気air Ambient

Ambient air Incineration (ｆlyash) 環境大気の異性体分布(MCDF～Tr. CDF) Isomer distribution of ambient air(MCDF-Tr. CDF)

Ambient air Incineration (ｆlyash) 環境大気の異性体分布(MCDD～Tr. CDD) Isomer distribution of ambient air(MCDD-Tr. CDD)

28 - 22337 - 37 -Di. CDF 27 - 23 -Di. CDF 28 -Di. CDF 238 - 128 -Tr. CDF 237 -Tr. CDF 128237 - 238 -Tr. CDF 1278 -TCDF 2378 -TCDF 塩素漂白パターンの異性体分布(MCDF～Tr. CDF) Isomer distribution of bleaching process(MCDF-Tr. CDF)

2 - 238 - 128 - 23727 - 塩素漂白パターンの異性体分布(MCDF～Tr. CDF) Isomer distribution of bleaching process(MCDF-Tr. CDF) Ambient air 24124 - Isomer 環境大気の異性体分布(MCDF～Tr. CDF) distribution of ambient air(MCDF-Tr. CDF)

Isomer農薬CNP中の異性体分布(MCDF～Tr. CDF) distribution of pesticide CNP (MCDF-Tr. CDF) 24 - 248 - 246 - pesticide CNP 24 - Ambient air 124 - Isomer 環境大気の異性体分布(MCDF～Tr. CDF) distribution of ambient air(MCDF-Tr. CDF)

Detail is as follows ISOMER SPECIFIC ANALYSIS OF MONO- TO TRICHLORINATED DIBENZO-DIOXINS AND DIBENZOFURANS - T. NAKANO and R. WEBER Organohalogen compounds, (2000)

TABLE II Resulting main PCDF fragments from the chlorophenols by pyrolysis at 400 C Fragment in resulting PCDF 0 used Phenol by H-Elimination Phenol by Cl-Elimination 2 -C-Phenol 1 3 - C-Phenol 2, 3 -C-Phenol 2 4 - C-Phenol 2, 4 -C-Phenol 3 3 - C-Phenol 2, 5 -C-Phenol 4 2 - C-Phenol 2, 6 -C-Phenol 12 3, 4 - C-Phenol 2, 3, 4 -C-Phenol 13 3, 5 - C-Phenol 2, 3, 5 -C-Phenol 14 2, 5 - C-Phenol 2, 3, 6 -C-Phenol 23 3, 4 - C-Phenol 2, 4, 5 -C-Phenol 24 2, 4 - C-Phenol 2, 4, 6 -C-Phenol 34 2, 3 - C-Phenol 2, 3, 6 -C-Phenol 123 3, 4, 5 - C-Phenol 2, 3, 4, 5 -C-Phenol 124 2, 4, 5 - C-Phenol 2, 3, 4, 6 -C-Phenol 134 2, 3, 5 - C-Phenol 2, 3, 5, 6 -C-Phenol 234 2, 3, 4 - C-Phenol 2, 3, 4, 6 -C-Phenol 1234 2, 3, 4, 5 - C-Phenol 2, 3, 4, 5, 6 -C-Phenol

TABLE III No. Sources of the PCDDs and PCDFs with 1 to 3 chlorines Isomer CA registry Sources and purity number MCDDs 1 1 39227 -53 -7 2 1 2 3 39227 -54 -8 12 13 14 4 16 5 6 7 19 8 9 10 17 18 23 29446 -15 -9 (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b) Pyrolysis(P+23 -Di. CP); (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b)Cambridge Isotope Lab. , USA; (c) Pyrolysis(P+24 -Di. CP); Di. CDDs Pyrolysis(2 -CP+234 -Tr. CP); Pyrolysis(2 -CP+246 -Tr. CP); Pyrolysis(2 -CP+236 -Tr. CP); Pyrolysis(23 -Di. CP+24 -Di. CP); Pyrolysis(23 -Di. CP); (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b)Cambridge Isotope Lab. , USA; 27 33857 -26 -0 (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b) Pyrolysis(24 -Di. CP) 28 38964 -22 -6 (a)Wellington Lab. , U. S. A. ; > 98%(GC/MS) (b) Pyrolysis(24 -Di. CP) Tr. CDDs 1 123 54536 -17 -3 (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b) Pyrolysis(2 -CP+2345 -Te. CP) 2 124 39227 -58 -2 (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b)Copyrolysis(2356 -Te. CP+2 -CP) 3 126 Pyrolysis(23 -Di. CP+234 -Tr. CP) 4 127 Pyrolysis(24 -Di. CP+234 -Tr. CP) 5 128 Pyrolysis(24 -Di. CP+234 -Tr. CP) 6 129 Pyrolysis(23 -Di. CP+234 -Tr. CP) 7 136 Pyrolysis(23 -Di. CP+246 -Tr. CP) 8 137 67028 -17 -5 Pyrolysis(24 -Di. CP+246 -Tr. CP) 9 138 Pyrolysis(24 -Di. CP+246 -Tr. CP) 10 139 Pyrolysis(23 -Di. CP+246 -Tr. CP) 11 146 Pyrolysis(23 -Di. CP+236 -Tr. CP) 12 147 Pyrolysis(24 -Di. CP+236 -Tr. CP) 13 178 Pyrolysis(23 -Di. CP+245 -Tr. CP) 14 237 33857 -28 -2 (a)Accu. Standard Inc. , U. S. A. ; 100%(GC/MS) (b) Cambridge Isotope Lab. , USA; (c)Pyrolysis(24 -Di. CP+245 -Tr. CP) Acronyms a CDD = chlorinated dibenzo-p-dioxins ; CDF = chlorinated dibenzofurans ; CP = chlorophenols; M= mono; Di = di; Tr = tri;

MCDD-Tr. CDD

Authentic standard H 2 ; H 3 H 9 H 6 NMR 1, 4, 7 -Tr. CDF H 8