Shimadzu Techno-Research Inc., Japan - UNEP Chemicals

Waters TOF Meeting at Dioxin2008, Tokyo 

Experiences from JAPAN 

Part 2 ; Technical aspect 

Capability and Analytical techniques for 

organohalogen compounds 

using GC-HRMS GC HRMS Dioxin, POPs, POPs, 

BFR and 

other PTSs, PTSs 

Prof. Dr. Dr. Dr.hc hc. Takumi Takasuga 

Shimadzu Techno-Research Techno Research Inc, 

Kyoto , JAPAN 

Center for Marine Environmental Studies (CMES), 

Ehime University, Matsuyama, Matsuyama, 

Japan 

�� 

�� 

main contents 

SHIMADZU TECHNO RESEARCH, Inc. 

�� Introduction of Shimadzu Techno-Research Techno Research as one of the biggest commercial 

Dioxin lab. in Japan 

11 GC-HRMS GC HRMS (9 Waters/Micromass 

Waters/ Micromass, , 1 JEOL and 1 MAT-95XL) MAT 95XL) 

�� Stockholm convention POPs (2004,17,May) & PTS (Persistent Organic 

Polutant) Polutant) 

, History, Trends and Analysis 

�� Investigation of analytical method for POPs & PTS using HRGC-HRMS 

HRGC HRMS 

techniques 

�� POPs monitoring for ultratrace analysis by HRMS 

�� Sampling, Clean-up Clean up method and HRMS technique for POPs & BFR analysis 

�� Other Organohalegen compounds 

�� Toxaphene, Toxaphene, 

BFR, PCA with GC-MS GC MS (NCI) technique 

�� LC-MS/MS LC MS/MS technique for BFR 

�� GC-TOFMS GC TOFMS technique 

�� Environmental Specimen Bank for Global Monitoring 

SHIMADZU TECHNO RESEARCH, Inc.

Shimadzu Corporation 

Shimadzu Corporation the research company established by the 

First President “Genzou Shimadzu” in the year 1875 (133yr). 

Thus it is one of the most oldest scientific organization in the 

world. Not only scientific machines but also we involved with 

manufaucturing of medical and aviation instruments. According 

to Shimadzu, the concern was established with ultimate goal of 

obtain environmental conservation. 

Apart from his dream, exactly 127 years after, Nobel Laureate 

Mr. Koichi Tanaka for Chemistry in 2002 was selected from our 

Shimadzu Corporation for the quality and dedicated work. 

It is one of milestone for Shimadzu Corporation 

http://www.shimadzu.com 

http:// www.shimadzu.com 


Introduction of 

SHIMADZU TECHNO-RESEARCH TECHNO RESEARCH INC INC.. 

�� Shimadzu Techno Research (STR) is Shimadzu Corporation’s 

Corporation 

daughter concern founded in 1972 in which head quarters located 

in Kyoto. 

�� STR holding a Japanese biggest lab. for the organic contaminants 

analysis from the environment with highly sophisticated 

instruments. Besides, STR also accepts the environmental 

consulting jobs. 

�� STR has been certified/awarded with ISO 9001, ISO 17025 (12 

sample items for dioxins) by JCLA and MLAP by METI (Japanese 

Ministry of Economy Trading and Industry) 

�� Particularly, STR got the license from Japanese Ministry of 

Environment (MOE) for toxic contaminants analysis as a pioneer 

qualifiers of environmental analysis. 


Summary of our capability 

�� 11 separate HRGC-HRMS HRGC HRMS (9 Waters/Micromass 

Waters/ Micromass, , 1 JEOL 

and 1 MAT-95XL) MAT 95XL) 

�� 12, 000 samples/year for dioxin analysis, this number is 

10% of country’s country s entire dioxin analysis. 

�� We analyze low concentration, moderate concentration 

and high concentration samples in separate machines in 

order to get quality data. 

�� Classify and separate GC/HRMS for environmental 

samples, biotic samples and abiotic samples. 

Furthermore for PCBs, POPs and BFRs. BFRs 

�� Pharmaceutical work with GLP lab. lab. 

by LC/MS/MS. LC/MS/MS 

�� We offer high quality environmental technical service 

(environmental information, waste re-cycle re cycle society 

information, society system formation) in order to 

provide comfortable environment. 


It is worth indicating 

�� we analyze variety of samples; samples; 

flue gas, incinerator gas, air, 

water from different aquatic ecosystems, drinking water, 

sewage sludge, sewage treatment plant, soil, sediment, 

plastics, transformer oil, used oil, waste oil, vegetation, fish, fish 

food, milk, human breast milk, human hair and human blood. 

Furthermore, we also conduct analysis of samples of exposed 

humans and non-exposed non exposed humans at particular conditions. 

�� actively participate inter-laboratory 

inter laboratory and inter-calibration 

inter calibration 

program annually (since ( since 1 st Round). Round). 

And continuously keep 

median (Z score

�� Comprehensive analytical laboratory in Japan as well as in 

the world. 

�� Update our work our research team participate in DIOXIN 

Conference (International Symposium on Halogenated 

Environmental Organic Pollutants and POPs) every year and 

presented several of our reports and new methodology 

developments. 

�� In addition to international meetings, we presented our 

analytical results and new methodology developments in the 

scientific meeting conducted in Japan, especially Symposium 

on Environmental Chemistry. 

�� We received a honorable prize of 2nd Technical prize of 

Environmental Chemistry in 1993, 1993, 

and Prize of Academic for 

Environmental Chemistry in 1996. 1996 

�� Furthermore, we collaboration with scientists from several 

universities and institute from Japan as well as from abroad 

as Joint research program for Government. 


Target Compounds and techniques 

HRGC-HRMS(EI); HRMS(EI); 

�� HRGC 

PCDDs/DFs, PCDDs/DFs PBDDs/DFs, PBDDs/DFs PXDDs/DFs, PXDDs/DFs, 

PCBs, PCNs 

Dioxins;PCDDs/DFs & Dioxinlike PCBs 

POPs; POPs 

DDTs(p,p‘- DDTs(p,p o,p’-DDT/DDD/DDE) 

o,p DDT/DDD/DDE) 

Chlordanes��cis 

Chlordanes cis/trans /trans-Chlordane, 

Chlordane, c/t-Nonachlor 

c/t Nonachlor, Oxychlordane��Heptachlor, 

Oxychlordane Heptachlor, cis/trans cis/trans- 

Heptachlor epoxide�� epoxide 

Cyclodienes(Aldrin, Cyclodienes(Aldrin Dieldrin, Dieldrin Endrin) Endrin 

HCB 

Mirex 

Toxaphene 

HCHs��-,��-,��-,��-HCH 

HCHs 

HCH��, , HCB, Mirex 

PAHs��CBz 

PAHs CBz, CPh 

Organo Tin ; phenyl Tin, Buthyl Tin, Octyl Tin 

BFR��PBDE 

BFR PBDE, PBB, PBB, 

HBCD, PBBz, PBBz PBPh, PBPh, 

TBBPA, DBDPE, BTBPE�� BTBPE�� 

Additionally 

Methabolite OH-PCB, OH PCB, OH-PBDE, OH PBDE, Tribromoanisole, Tribromoanisole, 

TBBPA dimethylether�� 

dimethylether 

Natural formation OMe-PBDE, 

OMe PBDE, OMe-PBB OMe PBB 

HRGC-HRMS( HRMS(NCI NCI); ); 

�� HRGC 

Toxaphene, Toxaphene Polychlorinated n-Alkanes Alkanes (PCAs PCAs), Short (C10-C13) (C10 C13) Chain, Chain Endsulfan, 

Endsulfan 

LC-MS/MS MS/MS 

�� LC 

PFOS/PFOA, PFOS/PFOA Chlordecone, Chlordecone PCAs (medium & long chain C14-) C14 ) , Polar comp. PPCP, 

HRGC-HRTOFMS; HRTOFMS; full characterization for unknown compounds 

�� HRGC 


New New POPs POPs proposed POPs 

�� PBDE (Pentabromodiphenylether 

( Pentabromodiphenylether) 

�� HBB (Hexabromobiohenyl 

( Hexabromobiohenyl) 

�� Chlordecone 

�� -HCH HCH (Lindane ( Lindane) 

�� PFOS (and precursor) 

�� OBDE (Octabromodiphenylether 

( Octabromodiphenylether) 

�� PeCB (Pentachlorobenzene 

Pentachlorobenzene) 

�� Short-chain Short chain chlorinated Paraffins 

�� /��-HCH HCH 

�� Endosulfane 


DIOXIN Symposium (#presentation) 

International International Symposium Symposium on on Halogenated Halogenated Organic Organic 

Pollutants Pollutants and and Persistent Persistent Organic Organic Pollutants Pollutants 

�� 1980 Rome Italy (52) 

�� 1998 Stockholm Sweden 

�� 1981 Arlington USA(55) 

�� 1999 Venice Italy (641) 

�� 

�� 

�� 

�� 

�� 

1982 Salzburg Austria (48) 

1984 Ottawa Canada (64) 

1985 Bayreuth Germany (201) 

1986 Fukuoka Japan (159) 

1987 Las Vegas USA (178) 

�� 

�� 

�� 

2000 Monterey USA (527) 

2001 Kyongju Korea (582) 

2002 Barcelona Spain 

(580) 

�� 1988 Umeå Ume Sweden (285) 

�� 2003 Boston USA (750) 

�� 1989 Toronto Canada (308) 

�� 2004 Berlin Germany(670) 

�� 

�� 

�� 

�� 

�� 

1990 Bayreuth Germany (430) 

�� 

1991 Noth Carolina USA (400) 

�� 

1992 Tampere Finland (313) 

�� 

1993 Vienna Austria (195) 

1994 Kyoto Japan (327) 

�� 

2005 Toronto Canada(801) 

2006 Oslo Norway(700) 

2007 Tokyo Japan(763) 

2008 Birmingham UK 

�� 1995 Edmonton Canada (379) 

�� 2009 2009 Beijing Beijing China China 

�� 

�� 

1996 Amsterdam The Netherlands 

�� 

(385) 

�� 

1997 Indianapolis USA (399) 

2010 2010 USA USA Texas Texas 

2011 2011 Bergen 

Bergen 


HRGC-HRMS Annual consumption Introduction of HRGC-HRMS in Japan 

in Japan 1987 to 2002 

Univ. �� 20, Gov. Lab. 83, Commercial Lab. 318 

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JEOL 261, Waters(Micromass) 159, Thermoelectron(MAT) 38 -->458 


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Sample Number and Instruments of Dioxin Analysis in 

Shimadzu Techno-Research 

Techno Research 

Sample 

16000 

14000 

12000 

10000 

8000 

6000 

4000 

2000 

0 

Sample Number of Dioxin Analysis 

and Instrument Number in STR 

67 98 90 110 140 175 255 665 956 591 917 554 1070 

1983 

1984 

Sample Number 

GC-MS 

1985 

1986 

1987 

1988 

1989 

1990 

1991 

HRMS 

1992 

1993 

1994 

1995 

2450 

1996 

3982 

1997 

7339 

6511 

1998 

�� 

12500 

13855 

12432 

10 

11040 11148 

11621 

11384 

11622 

1999 

2000 

2001 

2002 

2003 

2004 

2005 

GC-MS 

2006 

2007 

12 


8 

6 

4 

2 

0

Control by Database system 

�� All information are under control of database 

system which established our lab. 

�� Record: Sample info. Sample ID#, Extraction, 

Cleanup, Analysis Log, All GCMS data, Data 

processing, quick report date, Report date, etc. 

�� Who ? extracted, cleanup, GCMS data process. 

Data checking, report 


Factors which affect data reliability 

�Human �� 

�Environment �� 

�Method validation �� 

�Instrumentation �� 

�Traceability �� 

�Sampling and method dealings �� 

�� 

Should appropriate to the object of measurement 


Research Group on Ultra Trace Analyses 

�UTA� established July. 2003 

http://uta.jemca.or.jp/ 

belong to the Japan Environmental Measurement & Chemical 

Analysis Association (JEMCA) 

Chairman : Dr. Takumi TAKASUGA 

80 commercial lab.members, accredited to MLAP system 

UTA members HRMS introduction 

JEOL : 88 1.6 /Lab.(55) 

Micromass : 84 2.3 /Lab.(37) 

Thermoquest : 11 1.2 /Lab.( 9) 

SUM 183 2.23/Lab.(82) 

Excellent > # 4 Lab.�13 Lab. 

JEOL : 13 

Micromass : 47 

Thermoquest : 4 


Dioxin2008 P-31 

EVALUATION OF INTERLABORATORY 

STUDY FOR PCDDs, PCDDs PCDFs AND DIOXIN 

LIKE PCBs IN THE SOIL REFERENCE 

MATERIAL 

Takumi TAKASUGA1* , Kenji OTSUKA2* , Kazuo IWAKI3* , 

Kiichiro TANAKA4* , Toru MIYAZAKI5* *:Research Group on Ultra Trace Analyses(UTA) http://uta.jemca.or.jp/ 

Japan Environmental Measurement & Chemical Analysis Association (JEMCA) 

http://www.jemca.or.jp/ 

1) Shimadzu Techno Research, 

2-13, Nishinokyo-Sanjo-Bocho, Nakagyo-ku, Kyoto 604-8435, Japan, 

2) JFE Techno Research, 3) Ohu University, 

4) Toray Research Center, 5) Nittech Research

median, NIQR, CV% rob, min., max., average and RSD% 

PCDD/DF congeners Median NIQR CV%rob Min. Max. Average 

RSD% 

2,3,7,8-TeCDD 0.71 0.11 15.37 0.51 1.60 0.74 0.14 

1,2,3,7,8-PeCDD 5.58 0.57 10.31 3.50 7.10 5.56 0.65 

1,2,3,4,7,8-HxCDD 5.35 0.57 10.74 3.50 7.80 5.37 0.65 

1,2,3,6,7,8-HxCDD 9.60 1.00 10.42 6.20 12.75 9.38 1.10 

1,2,3,7,8,9-HxCDD 9.85 0.67 6.77 6.70 12.00 9.71 0.97 

1,2,3,4,6,7,8-HpCDD 51.00 5.19 10.17 37.00 61.50 50.38 5.00 

OCDD 87.00 6.49 7.46 68.25 107.50 87.59 7.03 

2,3,7,8-TeCDF 2.10 0.19 8.83 1.50 3.18 2.09 0.30 

1,2,3,7,8-PeCDF(all� 4.40 1.04 23.59 2.20 6.20 4.14 0.84 

1,2,3,7,8-PeCDF(separete� 3.20 0.32 9.85 2.20 6.20 3.30 0.66 

1,2,3,7,8-PeCDF(co-elute� 4.63 0.33 7.11 3.80 5.50 4.64 0.42 

2,3,4,7,8-PeCDF 5.20 0.54 10.34 3.58 7.63 5.08 0.62 

1,2,3,4,7,8-HxCDF(all� 6.15 0.80 12.96 4.10 8.80 6.18 0.78 

1,2,3,4,7,8-HxCDF(separate� 5.63 0.48 8.57 4.10 8.80 5.65 0.78 

1,2,3,4,7,8-HxCDF(co-elute� 6.51 0.52 7.97 5.40 8.20 6.51 0.58 

1,2,3,6,7,8-HxCDF 6.55 0.43 6.51 4.50 9.55 6.52 0.70 

1,2,3,7,8,9-HxCDF 0.68 0.10 14.69 0.40 5.33 0.74 0.55 

2,3,4,6,7,8-HxCDF 7.70 0.78 10.11 5.40 10.13 7.63 0.83 

1,2,3,4,6,7,8-HpCDF 22.00 2.22 10.11 17.00 25.75 21.48 1.92 

1,2,3,4,7,8,9-HpCDF 3.50 0.33 9.53 2.10 6.55 3.46 0.51 

OCDF 11.00 1.11 10.11 8.70 18.25 10.90 1.32 


median, NIQR, CV% rob, min., max., average and RSD% 

PCDDs/DFs Homologue Median NIQR CV%rob 

Min. Max. Average RSD% 

Total TeCDD 120.00 14.83 12.36 92.50 170.00 117.73 14.55 

Total PeCDD 130.00 14.83 11.40 86.50 230.00 131.47 18.75 

Total HxCDD 145.00 14.83 10.22 100.00 190.00 143.55 15.36 

Total HpCDD 91.75 8.52 9.29 67.00 112.50 89.59 8.66 

OCDD 88.00 6.49 7.37 68.25 107.50 87.62 7.03 

Total TeCDF 64.00 5.19 8.11 45.00 80.00 64.09 6.31 

Total PeCDF 68.00 5.19 7.63 47.25 87.00 67.71 7.09 

Total HxCDF 65.00 5.19 7.98 46.00 84.00 64.42 6.41 

Total HpCDF 38.00 3.15 8.29 29.00 47.75 37.84 3.75 

OCDF 11.00 1.11 10.11 8.70 18.25 10.89 1.32 

DL-PCBs Median NIQR CV%rob Min. Max. Average RSD% 

3,4,4',5-TeCB(#81) 4.00 0.41 10.19 3.35 7.65 4.10 0.64 

3,3',4,4'-TeCB(#77) 68.25 3.89 5.70 59.00 89.00 68.83 5.90 

3,3',4,4',5-PeCB(#126) 6.75 0.65 9.61 5.40 9.90 6.88 0.80 

3,3',4,4',5,5'-HxCB(#169) 1.28 0.20 15.99 0.88 3.50 1.29 0.31 

2',3,4,4',5-PeCB(#123) 7.40 0.65 8.77 4.88 10.43 7.37 0.91 

2,3',4,4',5-PeCB(#118) 350.00 24.09 6.88 290.00 455.00 353.22 31.43 

2,3,3',4,4'-PeCB(#105) 170.00 14.83 8.72 140.00 222.50 172.81 14.95 

2,3,4,4',5-PeCB(#114) 11.50 1.26 10.96 9.13 19.00 11.54 1.66 

2,3',4,4',5,5'-HxCB(#167) 24.00 2.59 10.81 19.00 31.00 24.31 2.61 

2,3,3',4,4',5-HxCB(#156) 64.00 4.63 7.24 52.00 82.00 64.65 6.68 

2,3,3',4,4',5'-HxCB(#157) 14.75 1.67 11.31 11.00 19.00 14.78 1.75 

2,3,3',4,4',5,5'-HpCB(#189) 6.60 0.59 8.99 5.23 8.48 6.59 0.59 


CV%rob 

��Trends Trends of CV % rob of round robin study in 

soil sample 

30% 

25% 

20% 

15% 

10% 

5% 

0% 

123789-HxCDD 

1234678-HpCDD 

OCDD 

2378-TeCDF 

12378-PeCDF 

23478-PeCDF 

123478-HxCDF 

123678-HxCDF 

123789-HxCDF 

234678-HxCDF 

1234678-HpCDF 

1234789-HpCDF 

OCDF 

344'5-TeCB(#81) 

2378-TeCDD 

12378-PeCDD 

123478-HxCDD 

123678-HxCDD 

Isomer 

33'44'-TeCB(#77) 

33'44'5-PeCB(#126) 

33'44'55'-HxCB(#169) 

2'344'5-PeCB(#123) 

23'44'5-PeCB(#118) 

233'44'-PeCB(#105) 

2344'5-PeCB(#114) 

23'44'55'-HxCB(#167) 

233'44'5-HxCB(#156) 

233'44'5'-HxCB(#157) 

233'44'55'-HpCB(#189) 

TOTAL TEQ 

2nd round robin study 4th round robin study 5th round robin study 


different results of 1,2,3,7,8-PeCDF using different GC phase 

Type of GCcolumn 

SP-2331, CP- 

Sil88 

BPX-DXN, DBtype, 

RH-12MS 

Lab.No. Average 

(pg/g) 

Max Min SD Median NIQR CV% 

rob 

48 4.64 5.50 3.80 0.42 4.63 0.33 7.11 

29 3.30 6.20 2.20 0.66 3.20 0.32 9.85 

different results of 1,2,3,4,7,8-HxCDF using different GC phase 

Type of GCcolumn 

SP-2331, CP- 

Sil88 

BPX-DXN, DBtype, 

RH-12MS 

Differences of analytical results by different GC phase 

Lab.No. Average 

(pg/g) 

Max Min SD Median NIQR CV% 

rob 

48 6.51 8.20 5.40 0.58 6.51 0.52 7.97 

29 5.65 8.80 4.10 0.78 5.63 0.48 8.57 

These results indicates that different GC phase shows different results especially for 

1,2,3,7,8-PeCDF. The main causes of this differences are due to co-eluting congeners for 

polar GC phase (SP-2331 or CP-Sil88) 


pg-TEQ 

900 

850 

800 

750 

700 

650 

600 

Youden prot TEQ (n-1 & n-2) 

550 

550 600 650 700 

pg-TEQ 

750 800 850 900 

Youden plot for TEQ in R-3 study 

Cross point of each axis indicate median of each injection 

400 

350 

300 

250 

200 

1,2,3,7,8-PeCDF 

Cyanopropyl phase(SP-2331, CP-Sill88) 

non polar & medium polar phase (DB-5, BPX-DXN, DB-17, RH-12) 

150 

150 200 250 300 350 400 


Youden plot for 1,2,3,7,8-PeCDF in R-3. 



220 

200 

180 

160 

140 

120 

1,2,3,4,7,8-HxCDF 

Cyanopropyl phase(SP-2331, CP-Sill88) 

non polar & medium polar phase (DB-5, BPX-DXN, DB-17, RH-12) 

100 

100 120 140 160 180 200 220 

Youden plot for 1,2,3,4,7,8-HxCDF in R-3. 


DMSO or DMF 

Florisil dry column 

H2SO4 H2SO4 /Silica gel 

Alkali 

KOH /Silica gel 

Clean up techniques 

Method Removals 


Mineral oil, aliphatic hydrocarbons 

Most of matrix, PAHs�Phthalate� 

some organohalogen comp. 

phenols�acidic comp.�Lipid�Peptide 

OCDF 

AgNO3 /Silica gel,Ag2O/Silica, Cu Sufur(S8),DDE, aliphatic hydrocarbons 

Silica gel Polar comp.�colored material � 

organohalogen comp. 

Aluminium oxide or Florisil Less polar comp., PCB, PCN, 

organohalogen comp. 

Carbon Planar comp. fractionation�PCDE, PBDE� 

biological matrix 

HPLC, GPC, on-line HPLC, 

Porous graphitized carbon(PGC), 

PYE,NPE 

fractionation 


Typical Interferences in Dioxin anal. 

Positive/Negative, Sensitivity change, GC column Adsorption 

�� Cleanup step��Phthalate, step Phthalate, adsorbent blank 

�� Waste gas/ash��PAHs 

gas/ash PAHs, , sulfur (S8), org. halogen. 

�� Air��PAHs Air PAHs, , Pesticides, hydrocarbons 

�� Soil/Sediment :vegetable lipid, Pesticides 

�� Sediment/Sludge��S8(adsorb Sediment/Sludge S8(adsorb GC col.��, col. , Pesticides, 

PCB, PCDE, Oil, Hydrocarbons 

�� Biota, Fish, Milk��Lipids, Milk Lipids, Biological matrix, 

Pesticides, PCB 

�� Waste��Plastics, Waste Plastics, BFR, Additives 

�� Waste Oil��mineral Oil mineral oil 

Comparison extraction method 

�� C 

C PCB recovery in Sediment 

Soxhlet 

Alkali Alkali Alkali 


�� toluene 

�� 

Average(n=8) 

�� 

�� 80� 

average(n=4) 

�� 

�� 80� 

��10�� 

�� 

room �� h temp 

averagee(n=4) 

� � � � 

13 

C-T4CB #77 96.6 88.0 90.2 98.5 

13 

C-T4CB #81 93.0 88.3 93.6 96.5 

13 

C-P5CB #126 97.0 88.5 95.8 97.5 

13 

C-H6CB #169 95.4 73.0 94.0 92.5 

13 

C-P5CB #123 91.6 93.3 97.0 100.0 

13 

C-P5CB #118 92.4 93.5 97.6 100.0 

13 

C-P5CB #105 91.8 91.5 107.0 99.0 

13 

C-P5CB #114 91.9 90.0 98.2 96.0 

13 

C-H6CB #156 92.3 86.3 91.2 100.5 

13 

C-H6CB #157 91.4 88.8 105.0 101.0 

13 

C-H6CB #167 92.1 92.5 92.4 93.5 

13 

C-H7CB #189 99.0 75.8 76.4 94.0 

13 

C-M1CB #3 30.0 2.0 37.0 52.5 

13 

C-D2CB #15 65.5 78.0 84.2 79.0 

13 

C-T3CB #28 80.8 94.0 117.0 105.0 

13 

C-T4CB #52 89.8 92.5 96.4 89.5 

13 

C-P5CB #101 91.0 94.5 87.6 94.5 

13 

C-H6CB #153 93.5 93.5 96.2 102.0 

13 

C-H7CB #180 97.4 89.8 87.0 105.5 

13 

C-O8CB #194 86.3 65.5 70.2 103.5 

13 

C-N9CB #206 109.0 16.5 33.0 82.0 

13 

C-D10CB #209 106.5 0.5 14.8 85.0 


Herbicide sample 

CNP (chloronitrophen) 

Total PCDD/DF Fraction 

Herbicide sample 

CNP (chloronitrophen) 

Specially designed cleanup for 2378-TCDD 

TCDDs HR-SIM chromatogram 

GC column;SP-2331 

magnified 

TCDDs HR-SIM chromatogram 

GC column;SP-2331 


magnified 


100% 

90% 

80% 

70% 

60% 

50% 

40% 

30% 

20% 

10% 

0% 

1368TCDD 

5%DCM/Hex 

Fr.11 

5%DCM/Hex 

Fr.12 

5%DCM/Hex 

Fr.13 

2378TCDD, 2378TCDF, 

123789HxCDD, 123789HxCDF, 

23478HxCDF, 1234678HpCDD, 

1234789HpCDF, OCDD, OCDF 

5%DCM/Hex 

Fr.14 

1379TCDD 

5%DCM/Hex 

Fr.15 

5%DCM/Hex 

Fr.16 

5%DCM/Hex 

Fr.17 

5%DCM/Hex 

Fr.18 

5%DCM/Hex 

Fr.19 

5%DCM/Hex 

Fr.20 

100%DCM 

Fr.21 

100%DCM 

Fr.22 

After hexane100ml, 5%DCM/hexane each10ml Fr., 

2378-TCDD recovered 100% DCM 

ICN Alumina B-Super I (DCM:dichloromethane) 

Specially desined cleanup for 2378-TCDD 

Interferences 

1368TCDD 

1379�� 

2378TCDD 

1234TCDD 

1369/1378TCDD 

1247/1248TCDD 

1268/1478TCDD 

1279/1237/1238TCDD 

2378TCDF 

12468/12479PeCDD 

12378PeCDD 

12378PeCDF 

23478PeCDF 

123478HxCDD 

123678HxCDD 

123789HxCDD 

123478HxCDF 

123678HxCDF 

234678HxCDF 

123789HxCDF 

1234678HpCDD 

1234678HpCDF 

1234789HpCDF 

OCDD 

OCDF 


Accurate mass Molecular formula Resolution 

TeCDD M + 319.8965 C12 H 12 4 Cl Cl4 O 13 C12 

12-TeCDF TeCDF (M+4) 2 R > 8,100 

+ 319.9360 

13 C12 

12 H4 Cl Cl4 O 

OCDD (M+2) + 13 C12 

12-OCDF OCDF (M+6) 457.7377 C12 Cl 12 Cl8 

O2 R > 11,600 

+ OCDD (M+12) 457.7772 

13 C12 

12 Cl 8 O 

+ 13 C12 

12-OCDD OCDD M 

467.7230 C12 Cl 12 Cl8 

O2 R > 8,080 

+ PnCDD n=5 (M+4) 467.7809 

13 C12 

12 Cl 8 O2 + 357.8517 C12 H 12 3 Cl Cl5 O P(n+1)CB M 

2 R > 49,000 

+ TeCDD M 

357.8444 C12 H 12 4 Cl 4 Cl6 

+ Methyl-TeCDF 

Methyl TeCDF (M+2) 319.8965 C12 H 12 4 Cl 4 Cl4 

O2 R > 17,900 

+ 319.9143 C13 H 13 4 Cl Cl4 O 

13 C12 

12- TeCDD M + 331.9368 

13 C12 

12 H4 Cl Cl4 O Dimethyl-TeCDF 

Dimethyl TeCDF M 

2 R > 85,100 

+ 331.9329 C14 H 14 8 Cl Cl4 O 

TeCDD M + 319.8965 C12 H 12 4 Cl Cl4 O Cl4-Dibenzotiophene 

Cl Dibenzotiophene M 

2 R > 18,000 

+ 319.8788 C12 H 12 4 Cl Cl4 S 

TeCDD M + 319.8965 C12 H 12 4 Cl Cl4 O Cl4-Xanthene 

Cl4 Xanthene (M+2) 2 R > 17,800 

+ 319.9144 C13 H 13 6 Cl Cl4 O 

13 C12 

12-TeCDF TeCDF M + 315.9419 

13 C12 

12 H4 Cl 4 O R > 14,100 

Cl4-Phenanthrene 

Cl Phenanthrene (M+2) + 315.9195 C14 14 H6 Cl 4 

P(n)CDF M + same impossible 

Cl(n+2) Diphenylether (M-Cl2) (M Cl2) + 

Pn5DD Pn DD (M+2) + 355.8546 C12 H 12 3 Cl Cl5 O Cl6-Acenaphthylene 

Cl Acenaphthylene M 

2 R > 13,700 

+ 355.8287 C12 H 12 2 Cl Cl6 P(n)BrDF M + same impossible 

Br(n+2) Diphenylether (M-Br2) (M Br2) + 


Interferences 

Accurate mass Molecular 

formula 

Resolution 

TeBrDD M + 495.6945 C12 12 H4 Br 4O2 R > 11,900 

TeBrDF (M+4) + 495.7360 

13 C12 

12 H4 Br 4 O 

PeBrDD M + 573.6050 C12 12 H4 Br 5 O2 R > 13,800 

PeBrDF (M+4) + 573.6465 

13 C12 

12 H4 Br 5 O 

HpCDF M + 405.7847 C12 12 H Cl 7 O R > 67,600 

Br5-Diphenylether 

Br Diphenylether (M+4 - Br2) + 405.7853 C12 12 H5 Br 3 O 

PeCB (M+2) + 325.8805 C12 12 H5 Cl 5 R > 85,700 

Br4-Diphenylether 

Br4 Diphenylether (M+2 - Br2) + 325.8767 C12 12 H6 Br 2 O 

P(n)CB n=4 M + 289.9224 C12 12 H6 Cl 4 R > 15,600 

P(n+2)CB (M+2-Cl2) (M+2 Cl2) + 289.9038 C12 12 H4 Cl 4 

P(n)CB n=4 M + 289.9224 C12 12 H6 Cl 4 R > 65,800 

P(n+1)CB M-Cl Cl 289.9178 C12 12 H5 Cl 4 

DiBrDD M + 339.8735 C12 12 H6 Br 2 O2 R > 24,300 

PeCDF (M+2) + 339.8598 C12 12 H3 Cl 5 O 

DiCB (M+2) + 223.9975 C12 12 H8 Cl 2 R > 21,700 

PFK M + 223.9872 C6F8 TeCDF, TeCDF, 

PeCDF M + nearly close C12 H 12 4 Cl Cl4 O2 impossible 

Chlordane compounds M + complex fragment 

ions 

C12 H 12 4 Cl Cl4 S 

PCNs M + same or nearly close C12 H 12 4 Cl Cl4 O2 impossible 

Chlordane compounds (M+2) + C13 H 13 6 Cl Cl4 O 

TeCDF M + 315.9419 

13 C12 

12 H4 Cl 4 O R > 81,000 

DDE M + 315.9380 C14 14 H8 Cl 4 

13 C12 

12-TeBrDF 13 C12 

12-PeBrDF 13 C12 

12-TeCDF 0 

�� 

SP2331 column 

PCDFs Incineration Sample 


030516LS8024 3: SIR of 15 Channels EI+ 

100 

% 

0 

13C12-HpCDF 419.8220 

8.34e6 

030516LS8024 

100 

% 

0 

1,2,3,4,6,7,8-HpCDF 

3: SIR of 15 Channels EI+ 

407.7818 

2.51e6 

HpCDFs 


100 

% 

0 

13C12-HxCDF 385.8610 

8.01e6 


100 

373.8208 

% 

0 

HxCDFs 

2.25e6 


100 

351.9000 

% 

0 

13C12-PeCDF 1,2,3,7,8,9-HxCDF 

1.11e7 


100 

% 

0 

PeCDFs 

339.8597 

3.36e6 


100 

% 

0 

13C12-TCDF 317.9389 

6.51e7 


100 

% 

305.8987 

7.56e6 

TeCDFs 

16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 

Time 

40.00 


PCB fragment ion and PCDD ion 

P(n) (n)CB CB [M] �� P(n+2) (n+2)CB CB [M-2Cl] [M 2Cl] R>15,500 (n=6) 

P(n) (n)CB CB [M] �� P(n 

(n-1) 

P(n) (n)CB CB [M] �� P(n+1) (n+1)CB CB [M-Cl [M Cl] 

1)CDD CDD [M+4] R>49,000 (n=6) 

R>36,000 (n=4,5) 

TeCB �� PeCB R>65,800 (n=4) 

PeCB �� HxCB R>72,400 (n=5) 

OCB (M+4) + 

429.7606 

HpCB (M+2) + 

393.8025 

HxCB (M+2) + 

359.8415 

#167 #156 #157 #169 

13 C12-HxCB (M+2) + 

371.8817 


12378-PeCDD 

#196 #203 

#190 

Interferences from predominant PCB congeners 

Sample ; Technical PCB KC-600 GC Column : HT8-PCB 


DDT 

HCH 

Chlordane 

(CHL) 

HCB 

PCBs 

Cl 

Cl 

Cl 

Cl 

Cl Cl 

Cl 

Cl 

Persistent Organochlorines 

H 

C 

Cl C Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl Cl 

m + n = 1 ~ 10 n 

m 

Cl 

Cl 

Cl 

Cl Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Aldrin 

C12H8Cl6 ; 364.93 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl Cl 

Cl 

Cl 

Cl 

Heptachlor 

C 10 H 5 Cl 7 ; 373.3 

Cl 

Cl 

Toxaphene Group 

T 12 , Toxicant A c 

Parlar 50 

Production and usage 

1950 1960 

1970 

1980 1990 

Widly used in developed 

countries 

Production started 

General information on organochlorines from 

an environmental point of view 

Large production 

Continuing usage in 

developing countries 

Usage restricted 

Worldwide use 

Persistency Bioaccumulative nature 

Highly toxic 

Endocrine disrupting effects 

POPs/Pesticides 

POPs/Pesticides 

O 

Cl 

Cl 

Cl 

Cl 

Cl 

Dieldrin 

C12H8Cl6 O; 380.93 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Chlordane 

C 10 H 6 Cl 8 ; 409.7 

Cl 

Cl 

Cl 

Cl 

HCB, C6H6, 284.79 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Immunotoxicty 

Carcinogenicity etc. 


Cl 

Cl 

Cl 

Cl 

Cl 

O 

Cl 

Endrin 

Cl Cl 

Cl 

Mirex 

Cl 

C Cl 

CH 

o,p, p,p’- DDT 


Cl 

Cl 

Cl 

Cl 

Cl Cl

Usage in Japan (ton) 

1946-1972 

1,000,000 

100,000 

10,000 

Production of POPs in Japan 

1,000 

100 

10 

1 

3,252 

Aldrin 

683 

Dieldrin 

1,470 

Endrin 

262 

Chlordane 

12,894 

1,489 

Chlordane 

(Termite) 

Heptachlor 

44,467 

DDTs 

389,000 

HCHs 

59,000 

PCBs 


Target LOQ in POPs Monitoring by 

MOE(Ministry of Environment, Japan) 

HRMS analysis since 2002 

Air < 1 pg/m 3 

Water 1�10 pg/L� 

coastal water

High 

volume 

sampler 

� 

� 

� 

� 

� 

� 

� 

� 

� PUF 

�diameter90mm�thickness 

50mm� 

� Quartz fiber filter 

� Active carbon fiber felt 

�diameter84mm�thickness 

3mm� 

Air sample 

Quartz fiber filter 

(QFF) 

Poly urethane foam 

(PUF) 

Active carbon fiber felt 

(ACF) 

Composition of air sampling adsorbents 

in POPs monitoring 

Fortify 13 C surrogate 

13 C12 - PCBs mix 

13 C-POPs Mix 

Sampling spike 


POPs distribution ratio in high volume air sampler 

�� 

� �� 

0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 

MCBs 

DiCBs 

TrCBs 

TeCBs 

PeCBs 

HxCBs 

HpCBs 

OCBs 

NCBs 

DeCB 

HCB 

a-HCH 

b-HCH 

g-HCH 

d-HCH 

Heptachlor 

cis-Heptachlor epoxide 

trans-Heptachlor epoxide 

o,p'-DDT 

p,p'-DDT 

o,p'-DDE 

p,p'-DDE 

o,p'-DDD 

p,p'-DDD 

trans-Chlordane 

cis-Chlordane 

trans-Nonachlor 

cis-Nonachlor 

Oxychlordane 

Dieldrin 

Aldrin 

Endrin 

Mirex 

HBBz 

Toxaphene Parlar #26 




POPs concentrations in air sample 

�� 

MCBs 

DiCBs 

TrCBs 

TeCBs 

PeCBs 

HxCBs 

HpCBs 

OCBs 

NCBs 

DeCB 

� �� 

�� 

�� 

�� 

�� 

�� 

�� 

HCB 

a-HCH 

b-HCH 

g-HCH 

d-HCH 

�� 

�� 

�� 

Heptachlor 



�� 

� 

�� 

o,p'-DDT 

p,p'-DDT 

o,p'-DDE 

p,p'-DDE 

o,p'-DDD 

p,p'-DDD 

�� 

�� 

�� 

�� 

�� 

�� 


cis-Chlordane 


cis-Nonachlor 

Oxychlordane �� 

�� 

Dieldrin 

Aldrin 

Endrin 

�� 

�� 

�� 

Mirex �� 

HBBz 

�� 

Toxaphene Parlar #26 �� 

Toxaphene Parlar #50 �� 

Toxaphene Parlar #62 � 

� �� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

pg/m3 


POPs Recovery in HV sampling 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 


Quartz fiber 

filter 

Soxhlet Ext. 

Conc. 

Conc. 

Fortify 13 C surrogate 

13 C12 - PCBs mix 

13 C-POPs Mix 

Sampling spike 

�Acetone 300ml, 1 hr� 

�Toluene 300ml, >16 hr� 

�dehydration 

For PCBs anal. 

�Acetone 300ml >16 hr� 

Conc. 

�water 100ml 

Transfer Hexane 

Hex. 

Conc. 

Crude 

Extract 

Multilayer silica gel clean up 

(�) 10%(w/w)AgNO3/Silica 

silica 

22%(w/w)H2SO4/Silica 

44%(w/w)H2SO4/Silica 

Silica 

2%(w/w)KOH/Silica 

Silica 

�Syringe spike 

13 C12 -PCB (7 Mix) 

conc 

* Hexane 

HRGC/HRMS SIM 

PCBs 

PUF 

Soxhlet Ext, 

�water wash�2 


Crude extract 

(hex. 50ml, X2) 

Conc. 

water 

Extraction of 

Air sample 

*20%-DCM/Hex. 

HRGC/HRMS SIM 

HCB, Aldrin, Chlordanes, 

Heptachlor, trans- 

Heptachlorepoxide 

Nonachlor, Oxychlordane, 

DDT, DDE, DDD, 

Toxaphene,(PCB) 

Active carbon 

fiber felt 

Soxhlet Ext. 

Conc. 

Conc. 

�Acetone 300ml, 1hr� 

�Toluene 300ml, >16hr� 


Other POPs anal. 

Florisil clean up 

�Syringe spike 

13 C12 -PCB(#19,#70) 


*DCM 

Conc. 

HRGC/HRMS SIM 

Dieldrin�Endrin� 

cis-Heptachlorepoxide 


HRGC/HRMS 

Micromass 

Autospec Ultima 

SP2331, DB-17HT, 

DB-5MS, HT-8PCB 

�dichloromethane) 

PCBs,POPs,PBDEs 

PCBs, PBDEs, 

(less polar) POPs 

HRGC/HRMS SIM 

PCBs, PBDEs, 

HCHs, HCBz, 

Aldrin, Heptachlor, 

Chlordanes, 

DDTs 

sample 

�Na2SO4) homogenize 

Soxhlet extract. 

16hr 

concentration 

Crude ext. 

portion 20% 

Lipid 

determination 

For 

PCDDs/DFs 

analysis 

Crude ext. 

Portion 20% 

Florisil cleanup 

Extraction & cleanup 

Biological sample 

dichloromethane 

DMSO partitioning 

Florisil cleanup 

13 C-PCBs Mix 

13 C12 -PBDE� 

(syringe spike) 

13C12-2378-TeCDD�OCDD 13C12-2378-TeCDF�OCDF 13C12-PCB� 22mix 

13C-POP� 3mix 

13C12-PBDE� 9mix 

�cleanup spike� 

portion 20% 

For 

PCBs/POPs/PBDEs 

analysis 


13 C-POPs Mix 

Cleanup spike 

20%-Dichloromethane in Hexane 100% -Dichloromethane 

POPs (polar) 

HRGC/HRMS SIM 


Heptachlor epoxide 


DL-PCBs 

and PCDD/DF 

Cleanup 

Recovery (%) 

100 

80 

60 

40 

20 

0 

Hex 0-20ml 

2% Dichloromethane 

in Hexane (35 mL) 

Multilayer-Silicagel Column 

Chromatography 

Alumina oxide column 

Analysis 

HRGC/HRMS 

Crude ext. 

Portion 50% 

Mono-ortho PCBs 

�� Hexane 



13C6-alpha-HCH 13C6-beta-HCH 

13C6-ganma-HCH 13C6-delta-HCH 

13C6-HCB 13C12-Aldrin 

13C12-Dieldrin 13C12-Endrin 

13C10-Heptaclor 13C10-Heptaclor epoxide 

13C10-Oxychlordane 13C10-trans-Chlordane 

13C10-trans-Nonachlor 13C10-cis-Nonachlor 

13C12-o,p'-DDE 13C12-p,p'-DDE 

13C12-o,p'-DDT 13C12-p,p'-DDT 

Hex 20-30ml 

Hex 30-40ml 

Hex 40-50ml 

Hex 50-60ml 

Hex 60-70ml 

Hex 70-80ml 



Silicagel-dispersed 

Carbon column 

Injection Standard 

Non-ortho PCBs 

PCDD/DFs 

Hex 80-100ml 

20%DCM/Hex 0-30ml 


20% DCM/Hex. 

Toluene 

300 mL 

Analysis 

HRGC/HRMS 






DCM 0-100mL 

Elution profile of POPs in Florisil column 

DCM 


Native Standard Internal Standard 

o,p'-DDT 

p,p'-DDT 

o,p'-DDE 

p,p'-DDE 

o,p'-DDD 

p,p'-DDD 


cis-Chlordane 


cis-Nonachlor 

Oxychlordane 

Dieldrin 

Aldrin 

Endrin 

Heptachlor 



HCB 

Mirex 

�-HCH 

�-HCH 

�-HCH 

�-HCH 

13 C12-o,p'-DDT 

13 C12-p,p'-DDT 

13 C12-o,p'-DDE 

13 C12-p,p'-DDE 

13 C12-o,p'-DDD 

13 C12-p,p'-DDD 

13 C10-trans-Chlordane 

13 C10-trans-Chlordane 

13 C10-trans-Nonachlor 

13 C10-cis-Nonachlor 

13 C10-Oxychlordane 

13 C12-Dieldrin 

13 C12-Aldrin 

13 C12-Endrin 

13 C10-Heptachlor 

13 C10-cis-Heptachlor epoxide 

13 C10-Oxychlordane 

13 C6-HCB 

13 C10-Mirex 

13 C6-�-HCH 

13 C6-�-HCH 

13 C6-�-HCH 

13 C6-�-HCH 

13 C12-#15-DiCB * 

13 C12 -#70-TeCB * 

* sampling or extraction spike, ** syringe spike 

CIL (USA) 

NEW POPs 

Standards 

* syringe spike 


CIL NEW Calibration mixture of POPs 

CS1 CS2 CS3 CS4 

(pg/�L) CS5 CS6 CS1~CS6 

(pg/�L) o,p'-DDT 0.4 2 10 40 200 800 13 C 12-o,p'-D D T 20 

p,p'-DDT 0.4 2 10 40 200 800 13 C 12-p,p'-D D T 20 

o,p'-DDE 0.4 2 10 40 200 800 13 C 12-o,p'-D D E 20 

p,p'-DDE 0.4 2 10 40 200 800 13 C 12-p,p'-D D E 20 

o,p'-DDD 0.4 2 10 40 200 800 13 C 12-o,p'-D D D 20 

p,p'-DDD 0.4 2 10 40 200 800 13 C 12-p,p'-D D D 20 

trans-Chlordane 0.4 2 10 40 200 800 13 C 10-trans-Chlordane 20 

cis-Chlordane 0.4 2 10 40 200 800 ( 13 C 10-trans-Chlordane) � 

trans-Nonachlor 0.4 2 10 40 200 800 13 C 10-trans-Nonachlor 20 

cis-Nonachlor 0.4 2 10 40 200 800 13 C 10-cis-Nonachlor 20 

Oxychlordane 0.4 2 10 40 200 800 13 C 10-Oxychlordane 20 

Dieldrin 0.4 2 10 40 200 800 13 C 12-D ieldrin 20 

Aldrin 0.4 2 10 40 200 800 13 C 12-Aldrin 20 

Endrin 0.4 2 10 40 200 800 13 C 12-Endrin 20 

Heptachlor 0.4 2 10 40 200 800 13 C 10-Heptachlor 20 

cis-Heptachlor epoxide 0.4 2 10 40 200 800 13 C 10-cis-Heptachlor epoxide 20 

trans-Heptachlor epoxide 0.4 2 10 40 200 800 � 13 C 10-Oxychlordane� � 

HCB 0.4 2 10 40 200 800 13 C 6-HC B 20 

Mirex 0.4 2 10 40 200 800 13 C 10-Mirex 20 

� -HC H 0.4 2 10 40 200 800 13 C 6-� -HC H 20 

� -HC H 0.4 2 10 40 200 800 13 C 6-� -HC H 20 

� -HC H 0.4 2 10 40 200 800 13 C 6-� -HC H 20 

� -HC H 0.4 2 10 40 200 800 13 Native Standard Internal Standard 

C 6-� -HC H 20 

13 

C 12-#15-DiCB * 20 

0.4 2.0 10 40 200 800 pg/uL 20 pg/uL 

13 C 12-#70-TeCB * 20 


HRGC/HRMS Condition 

GC HP 6890 Series GC System (Agilent) 

Injector 

7683 Series Injector (Agilent) 

Auto Sampler 7683 Series Auto Sampler (Agilent) 

He flow rate 1.0 mL/min 

Injector On-column injector 

Injection Volume 2mL 

GC Column DB-17HT(J&W) 30m x 0.32mmi.d. (0.15um) 

120�(1 min)-20�/min-160�(0 min)-3�/min-220�(0 min)- 

10�/min-300��3min) 

Column DB-17HT 

DB-5MS 

MS Micromass Autospec Ultima or Premier (Waters) 

Ionization mode EI 

Ionization Volt. 35-40eV 

Accel. Volt. 8kV 

Ion source Temp. 300 o C 

Interface Temp. 300 o C 

Resolution M/�M > 10,000 (10% Valley) 

POPs* PBDEs PCBs 

DB-5MS 

POPs Monitor Ion 

120�(0.1 min)-100�/min-300�(15 min) 

DB-5MS 

HT-8 PCB 

OH-PCBs 

DB-5MS 


M + [M+2] + [M+4] + 

DDD(M-CHCl 2), DDT(M-CCl 3) 235.0081 237.0053 

13 C12-DDD(M-CHCl 2), 13 C 12-DDT(M-CCl3) 247.0483 249.0454 

DDE(M-Cl2) 246.0003 247.9975 

13 C12-DDE(M-Cl2) 258.0405 260.0376 

Chlordane(M-Cl) 372.8260 374.8231 

+10 mass 

13 C10-Chlordane(M-Cl) 382.8595 384.8565 

Nonachlor(M-Cl) 406.7870 408.7841 

+10 mass 

13 C10-Nonachlor(M-Cl) 416.8205 418.8175 

Oxychlordane(M-Cl) 386.8053 388.8024 

+10 mass 

13 C10-Oxychlordane(M-Cl) 396.8387 398.8358 

Aldrin(M-C5H6Cl), Dieldrin, Endrin(M-C5H6ClO) 262.8570 264.8541 

13 

C12-Aldrin(M-C5H6Cl), 13 C12-Dieldrin, Endrin(M-C5H6ClO) 269.8804 271.8775 

Heptachlor(M-C5H5Cl) 

13 

C10-Heptachlor(M-C5H5Cl) 

+5 mass 

269.8131 

274.8299 

271.8102 

276.8269 

273.8072 

278.8240 

Heptachlor epoxide(M-Cl) 352.8442 354.8413 

+10 mass 

13 C10-Heptachlor epoxide(M-Cl) 362.8777 364.8748 

HCB 283.8102 285.8073 

+6 mass 

+7 mass 

13 

C6-HCB 289.8303 291.8273 

Mirex(M-C5Cl6) 

13 

C10-Mirex(M-C5Cl6) 

+5 mass 

269.8131 

274.8299 

271.8102 

276.8269 

273.8072 

278.824 

HCH(M-H2Cl3) 180.9379 182.9349 

+6 mass 

13 

C6-HCH(M-HCl2) 186.9580 188.9550 

13 

C12-DiCB* 234.0406 236.0376 

13 

C12-TeCB* 301.9626 303.9597 


1.20 

1.10 

1.00 

0.90 

0.80 

0.70 

0.60 

o,p'-DDT 

p,p'-DDT 

o,p'-DDE 

p,p'-DDE 

RRF �� & RSD% � �� of POPs cal. mix 

RRF RSD 

9.0% 

8.0% 

7.0% 

6.0% 

5.0% 

4.0% 

3.0% 

2.0% 

1.0% 

0.0% 

13C12-o,p'-DDT 

13C12-p,p'-DDT 

13C12-o,p'-DDE 

o,p'-DDD 

p,p'-DDD 

13C12-p,p'-DDE 

13C12-o,p'-DDD 


cis-Chlordane 


cis-Nonachlor 

Oxychlordane 

Dieldrin 

Aldrin 

Endrin 

Heptachlor 

RRFrs�� 

to syringe #15-DiCB #70-TeCB 

13C12-p,p'-DDD 

13C10-trans-Chlordane 

RRFrs CV% 

RSD >5% sensitivity variation POPs : 

DDT, DDD, Endrin, Endrin, 

Heptachlor 

13C10-trans-Nonachlor 

13C10-cis-Nonachlor 

13C10-Oxychlordane 

13C12-Dieldrin 

13C12-Aldrin 

13C12-Endrin 

RRFcs1 

�� 


HCB 

Mirex 

�-HCH 

�-HCH 

�-HCH 

�-HCH 

13C10-Heptachlor 

13C10-cis-Heptachlor epoxide 

13C6-HCB 

5.0% 

4.5% 

4.0% 

3.5% 

3.0% 

2.5% 

2.0% 

1.5% 

1.0% 

0.5% 

0.0% 


13C10-Mirex 

13C6-a-HCH 

13C6-b-HCH 

13C6-g-HCH 

13C6-d-HCH 


Average RRF 

RSD (%) 

2.0 

1.5 

1.0 

0.5 

0.0 

10 

8.0 

6.0 

4.0 

2.0 

0.0 

T4CB #77 

RRF and RSD% of PCBs Cal. Mix. 

T4CB #81 

P5CB #126 

H6CB #169 

P5CB #105 

P5CB #114 

P5CB #118 

P5CB #123 

H6CB #156 

H6CB #157 

H6CB #167 

H7CB #189 

H7CB #170 

H7CB #180 

M1CB #3 

D2CB#8 

D2CB #15 

T3CB #18 

T3CB #31/#28 

T3CB #33 

T4CB #44 

T4CB #52 

T4CB #66 

T4CB #70 

P5CB#95 

P5CB #101 

P5CB #110 

H6CB #138 

H6CB #149 

H6CB #153 

H7CB #174 

H7CB #187 

O8CB #194 

O8CB #199 

O8CB #203 

N9CB #206 

IUPAC Numbers 

Average RRF and RSD (%) in two monitor ions by 

mono- through deca-PCBs 

Takasuga, et. al., Arch. Environ. Contam. Toxicol., 49(3), 385–395 (2005) 

D10CB #209 


PBDE RRF, RSD and detection/quantification limit 

Native 

13 

C-Internal Mass RRF RSD(%) DL* STDEV IDL (3s) IDQ (10s) 

Standard Standard Native Internal (n=15) n=5 (pg/�L� 

MoBDE-3 MoBDE-3 249.982 262.022 1.05 2.6 0.437 0.017 0.052 0.175 

DiBDE-7 DiBDE-15 327.892 339.932 0.51 3.5 0.397 0.016 0.048 0.159 

DiBDE-15 DiBDE-15 327.892 339.932 0.98 3.8 0.394 0.007 0.022 0.075 

TrBDE-17 TrBDE-28 405.803 417.843 0.89 4.7 0.388 0.015 0.045 0.152 

TrBDE-28 TrBDE-28 405.803 417.843 1.02 4.0 0.405 0.020 0.061 0.202 

TeBDE-49 TeBDE-47 485.711 497.751 0.67 3.0 0.409 0.016 0.049 0.164 

TeBDE-71 TeBDE-47 485.711 497.751 0.65 3.7 0.428 0.009 0.026 0.086 

TeBDE-47 TeBDE-47 485.711 497.751 1.03 4.0 0.400 0.004 0.013 0.044 

TeBDE-66 TeBDE-47 485.711 497.751 0.60 4.7 0.419 0.008 0.025 0.082 

TeBDE-77 TeBDE-47 485.711 497.751 0.97 3.9 0.402 0.015 0.045 0.148 

PeBDE-100 PeBDE-99 563.622 575.662 1.30 5.8 0.396 0.024 0.072 0.241 

PeBDE-119 PeBDE-99 563.622 575.662 0.82 5.6 0.400 0.027 0.080 0.268 

PeBDE-99 PeBDE-99 563.622 575.662 0.95 5.5 0.392 0.028 0.085 0.283 

PeBDE-85 PeBDE-99 563.622 575.662 0.76 6.0 0.388 0.028 0.083 0.276 

PeBDE-126 PeBDE-99 563.622 575.662 1.05 7.3 0.395 0.021 0.064 0.212 

HxBDE-154 HxBDE-154 483.696 495.736 0.91 4.8 0.398 0.014 0.041 0.136 

HxBDE-153 HxBDE-153 483.696 495.736 0.95 5.5 0.401 0.012 0.035 0.116 

HxBDE-138 HxBDE-153 483.696 495.736 0.72 6.3 0.389 0.006 0.017 0.055 

HpBDE-183 HpBDE-183 561.606 573.646 0.86 5.6 0.407 0.035 0.105 0.350 

OBDE-197 OBDE-197 641.515 653.555 0.95 3.2 2.39 0.047 0.142 0.475 

OBDE-196 OBDE-197 641.515 653.555 0.91 11.9 2.17 0.064 0.193 0.642 

NBDE-207 NBDE-207 719.425 731.465 1.00 4.3 2.43 0.036 0.107 0.357 

NBDE-206 NBDE-207 719.425 731.465 0.69 16.9 1.91 0.080 0.240 0.801 

DeBDE-209 DeBDE-209 799.334 811.374 1.02 5.1 2.66 0.058 0.173 0.576 

*DL=detection limit for 0.42pg/mL or 2.5pg/mL standard; Only Ion-1 monitoring data have been shown 

Takasuga, et. al., Chemosphere, SHIMADZU 57, 795 TECHNO –811 RESEARCH, (2004) 

Inc.

pg 

100 

10 

1 

0.1 

0.01 

0.02 0.02 

TCDD 

TCDF 

GC-MS GC MS Sensitivity 

0.04 0.04 

HxCDD 

HxCDF 

0.09 

OCDD 

0.07 

OCDF 

0.04 

TeCB #77 

0.05 

HxCB #169 

0.08 

HpCB #189 

LRMS QP-1 

LRMS QP-2 

LRMS QP-3 

LRMS 3D QP 

MS/MS 

LRMS QP MS/MS 

LRMS Iontrap 

MS/MS-1 

LRMS Iontrap 

MS/MS-2 

Sector MRMS 

HRMS 

(5 lab. Averaged) 


Comparison of POPs separation in GC column 

a-HCH 

HCB 

DB-5MS 

HCB 

g-HCH 

b-HCH 

a-HCH 

d-HCH 

DB-17HT 

g-HCH 

b-HCH 

Heptachlor 

Heptachlor 

d-HCH 

Aldrin 

Aldrin 


+ Oxychlordane 

t-Chlordane 

o,p’-DDE 

c-Chlordane 

t-Nonachlor 

p,p’-DDE 

Oxychlordane 


t-Chlordane 

t-Nonachlor 

c-Chlordane 

o,p’-DDE 

Dieldrin 

p,p’-DDE 

Dieldrin + o,p’-DDD 

Endrin 

c-Nonachlor 

+ p,p’-DDD 

o,p’-DDD 

c-Nonachlor 

o,p’-DDT 

p,p’-DDD 

Endrin 

o,p’-DDT 

p,p’-DDT 

p,p’-DDT 


100 

100 

% 

% 

0 

0 

#154 

Comparison of clean-up method in serum 

General methods 

(acid/base silica) 

13 C-HxBDE 

14.00 14.25 14.50 14.75 15.00 

22.5 25.0 27.5 30.0 

493.7377 

1.012e+006 

#139(syringe spike� 

#153 

13 C-DeBDE 

min 

809.3757 

1.090e+004 

min 

Additional 

clean-up 

100 

% 

0 

100 

% 

0 

#154 

Additional clean-up 

(H 2SO 4-Silica) 

13 C-HxBDE 

#153 

14.00 14.20 14.40 14.60 14.80 

13 C-DeBDE 

22.50 23.00 23.50 24.00 24.50 

493.7377 

7.264e+006 

#139(syringe spike� 

min 

809.3757 

1.072e+006 

insufficient clean-up cause to adsorption of PBDE in where 

Possible false negative data (N.D.) 

Necessary for individual 13 C 12-bromination congener 

min 


Technical DeBDE (comparison GC film thickness) 

NonaBDE 

(impurities) 

OctaBDE 

(impurities) 

DBDE 

100pg 

HRGC-HRMS: Micromass Autospec Ultima with a Hewlett Packard 

HP6980 

DB5-MS (30m, 0.25mm, 0.25�m) capillary column 

He Flow : 1.0ml/min 

100C(1min)-20C/min-200C(1min)-10C/min-300C(8min)-10C/min- 

330(22min) 

On Column Injection mode 110C(0.1min)-100C/min-300C(15min) 

resolution >10,000. 

M-2Br 

m/z 799.3334 

0.25�m 0.1�m 

NonaBDE 

(impurities) 

OctaBDE 

(impurities) 

HRGC-HRMS: Micromass Autospec Ultima with a Hewlett Packard 

HP6980 

DB5-MS (30m, 0.25mm, 0.1�m) capillary column 

He Flow : 1.0ml/min 

170C(1min)-20C/min-250C(0min)-10C/min-300C(24min) 

On Column Injection mode 170C(0.1min)-100C/min-300C(15min) 

resolution >10,000. 

DBDE 50pg 


Internal standard : 

different bromination 

Internal standard : same 

bromination congener 

Injection 

(pg) 

Injection 

(pg) 

DeBDE calibration data 

DBDE 

�native) 

peak area 

DBDE 

�native) 

peak area 

peak area 

/Injection 

peak area 

/injection 

Injection 

(pg) 

Injection 

(pg) 

Takasuga, et. al., Takasuga et.al. 

Chemosphere, 57, Chemosphere, 795 –811 (2004) (2004). 

13 C12-22'344'5'6-HpBDE 

peak area 

13 C12-DBDE 

peak area 

peak area 

/injection 

As/Ais X Cis/Cs 

100 29,407 294 500 153,999 308 0.9548 

500 184,079 368 500 188,720 377 0.9754 

2,000 1,009,048 505 500 258,297 517 0.9766 

10,000 8,460,610 846 500 433,062 866 0.9768 

50,000 55,126,640 1103 500 626,205 1252 0.8803 

(IS) 

peak area 

/Injection 

As/Ais X Cis/Cs 

200 25,871 129 20 24,998 1250 0.1035 

1,000 181,478 181 20 31,747 1587 0.1143 

4,000 891,597 223 20 25,149 1257 0.1773 

20,000 7,936,218 397 20 26,803 1340 0.2961 

100,000 46,898,724 469 20 23,540 1177 0.3985 

Great take care should be necessary for high brominated compounds 

because of poor linearity 

Necessary isotope dilution technique by GC-HRMS 

for high bromine PBDE,PBB analysis 

(IS) 

RRF 

RRF 


BFR (Brominated 

( Brominated Flame Retardants) 

�� Relatively High molecule 79/81 79/81Br Br 35/37 35/37Cl Cl 

�� Not stable : Active compounds 

Photo degradation, debromination 

Thermally unstable 

Higher Br comp. GC column adsorption & 

bad linearity 

necessary to use 13 13C-internal internal std. 


051214XM1002 

14-Dec-2005 09:47:27 

Magnet EI+ 

Sum 

100 

4.98e4 

% 

-2 

DB-17HT DB 17HT 30m, 0.32mm I.D., 0.15��m 0.15 

120 o C(1min)-20 o C/min-160 o C (0min)-3 o C/min-220(0min)-10 o C/min-300 o C�3min) 

HCB 

�-HCH 

�-HCH 

�-HCH 

Heptachlor 

�-HCH 

Ardrin 

Oxychlordane 


tans-Heptachlor epoxide 

trans-Chlordane + Endosulfan I 


cis-Chlordane 

o,p’-DDE 

p,p’-DDT 

Endrin aldehyde 

Endsulfan sulfate 

8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 Time 

Dieldrin 

p,p’-DDE 

o,p’-DDD 

Endrin 

cis-Nonachlor 

+ Endosulfan II 

o,p’-DDT 

p,p’-DDD 

Mirex 

Endrin ketone 

Methoxychlor 


BPX-50 BPX 50 30m, 0.32mm I.D., 0.15��m 0.15 

120�C(1min)-20�C/min-160�C (0min)-3�C/min-220(0min)-5�C/min-260�C�0min)-10�C/min-300�C (3min) 

051018XO1001 

18-Oct-2005 11:21:33 

Voltage SIR 32 Channels EI+ 

100 

TIC 

6.28e8 

% 

-2 

PeCBz 

Trifluralin 

HCB 

�-HCH 

#19-TrCB 

�-HCH 

�-HCH 

Heptachlor 

�-HCH 

Ardrin 

Octachlorstyrene 

Oxychlordane 

trans-Chlordane + 

trans-Nonachlor + 

#70-TeCB 



cis-Chlordane 

p,p’-DDT 


6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 Time 

o,p’-DDE 

p,p’-DDE 

Dieldrin 

o,p’-DDD 

+ cis-Nonachlor 

Endrin 

o,p’-DDT 

p,p’-DDD 

Mirex 

HBBz 


051019XO1001 

19-Oct-2005 14:39:45 

Voltage SIR 32 Channels EI+ 

100 

TIC 

7.90e8 

% 

-2 

DB-5MS DB 5MS 30m, 0.25mm I.D., 0.25��m 0.25 

120�C(1min)-20�C/min-180�C (0min)-3�C/min-240(0min)-10�C/min-300�C�5min) 

PeCBz 

HCB 

Trifluralin 

�-HCH 

#19-TrCB 

�-HCH 

�-HCH 

�-HCH 

Heptachlor 

Ardrin 

#70-TeCB 

Octachlorstyrene 

cis-Heptachlor epoxide + Oxychlordane 

o,p’-DDD p,p’-DDE 



o,p’-DDE 

cis-Chlordane 


cis-Nonachlor 

Endrin 

6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 Time 

p,p’-DDD 

o,p’-DDT 

Dieldrin 


p,p’-DDT 

Toxaphene 

HBBz 

Mirex 


Parlar-26 (EI) Parlar-50 (EI) Parlar-62 (EI) 

Parlar-26 (ECNI) Parlar-50 (ECNI) Parlar-62 (ECNI) 

[M-Cl] - [M-Cl] - [M-HCl-Cl] - 


Toxaphene Fish sample (sea bass) 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

Matsukami, H. et. al., Organohalogen Compounds, 66, 217-223 (2004) 


Toxaphene Comparison of resolution 

�� 

�� 

�� 

�� 

�� 

�� 

Still limitation 

R>10,000 

high levels of HpCB 

#185 >100pg 

Better to check HpCB 

#185 

�� 

�� 


MDL & MDL of air sample by HRMS 

sam p le volum e 1000m 3 � � � � � � 

pg/m 3 

pg/m 3 

o,p '-DDT 0.031 0.093 

p ,p '-DDT 0.074 0.22 

o,p '-DDE 0.012 0.037 

p ,p '-DDE 0.039 0.12 

o,p '-DDD 0.048 0.14 

p ,p '-DDD 0.018 0.053 

trans-Chlordane 0.23 0.69 

cis-Chlordane 0.19 0.57 

trans-Nonachlor 0.16 0.48 

cis-Nonachlor 0.024 0.072 

Oxy chlordane 0.042 0.13 

Dieldrin 0.11 0.33 

A ld rin 0 .0 5 0.15 

Endrin 0.048 0.14 

Hep tachlor 0.078 0.23 

cis-Hep tach lo r e p oxide 0.017 0.052 

trans-Hep ta c h lo r e p oxide 0.2 0.6 

HCB 0.37 1.1 

Mirex 0.017 0.05 

�-HCH 0.11 0.33 

� -HCH 0.041 0.12 

� -HCH 0.076 0.23 

�-HCH 0.05 0.15 

Toxap hene Parlar #26 0.066 0.2 




MDL & Blank of biological sample in HRMS & LRMS 

HRGC/HRMS� 

�� 

(MDL) 

HRGC/HRMS� 

�� (�� 

��) 

HRGC/LRMS 

�� 


� 

MDL 

Method Blank 

(pg/g) (pg/g) (ng/g) 

o,p'-DDT �� 

p,p'-DDT �� 

o,p'-DDE �� 

p,p'-DDE �� 

o,p'-DDD �� 

p,p'-DDD �� 

trans-Chlordane �� 

cis-Chlordane �� 

trans-Nonachlor �� 

cis-Nonachlor �� 

Oxychlordane �� 

Dieldrin � �� 

Aldrin �� 

Endrin �� 

Heptachlor �� 

cis-Heptachlor epoxide �� 

trans-Heptachlor epoxide � � � 

HCB �� 

Mirex �� 

�-HCH �� 

� -HCH � � � 

�-HCH �� 

� -HCH �� 

��

Cleanup of POPs 

Basically applied Florisil clean up 

�� H2SO SO4 or 22%-H 22% 2SO SO4/Silica /Silica��degradation degradation of 

Dieldrin and Endrin 

�� 44%- 44% H2SO SO4/Silica /Silica�� degradation of Aldrin and 

Heptachlor epoxide. 

Useful cleanup for Stable POPs(DDT & HCH etc) 

�� AgNO 3/Slica /Slica�� degradation of Heptachlor, low 

recovery of MoCB 

�� DMSO/Hex. partitioning��a partitioning a little low recovery of 

HCB and Aldrin 

�� Volatile POPs��HCB 

POPs HCB��HCHs HCHs��Heptachlor 

Heptachlor��Aldrin Aldrin�� 

MoCB 

Biological sample cleanup 


� Stable POPs compounds�H2SO4/slica is effective after 

Florisil cleanup, only stable POPs for acid 

� Florisil cleanup� less polar fraction 20%-DCM/Hex. & 

polar fraction (Heptachlor epoxide, Dieldrin, Endrin) 

DCM fr. (much better clean up compare to ether fr.) 

� High lipid content sample �insufficient cleanup cause to 

broad GC peak 

� DMSO/Hex. partitioning�effective for lipid & mineral oil 

& aliphatic hydrocarbons 

� LOD 0.05�0.2ng/g 


�� DMSO/Hex. partioning��effective partioning effective for air & sediment 

mineral oil & aliphatic hydrocarbons 

�� Ultra high level congeners��major congeners major PCB, p,p‘-DDE, p,p DDE, 

p,p’-DDD p,p DDD saturated peak, memory effects in the GC 

column, separate analysis for different analyte with 

cleanup factor 

�� Blank of POPs�� POPs HCB��Chlordane HCB Chlordane & BFR(HBB, DeBDE), 

endsulfan, great care should be taken for the 

laboratory dust 

�� HCB & chlordane has relatively high method blank 

level��pg level pg��on on the other hand low level in the biological 

sample 


Experiences of sample for POPs analysis 

by HRGC/HRMS 

Insufficient cleanup �� 

�� Broad GC peak shape : dirty Ion source & liner 

�� Variation of ionization efficiency, sensitivity, change 

of ion intensity of fragment ions, variation of monitor 

ions, degradation & adsorption in the GC column 

�� cleanup is most important for HRMS analysis 

Unstable POPs affect variation of sensitivity : 

Endrin, Endrin, 

Heptachlor, DDT 

�� Strongly recommended use of 13 13C C internal standards, 

standards 

but variation of sensitivity and recovery % should 

occur even though stable RRF 

�� interference of PBDE(Tetra) to PCB(Penta) on HT-8 HT 

GC column 


�� 

9.0% 

8.0% 

7.0% 

6.0% 

5.0% 

4.0% 

3.0% 

2.0% 

1.0% 

0.0% 

13C12-o,p'-DDT 

13C12-p,p'-DDT 

13C12-o,p'-DDE 

13C12-p,p'-DDE 

13C12-o,p'-DDD 

RRFrs�� 

to syringe #15-DiCB #70-TeCB 

13C12-p,p'-DDD 

13C10-trans-Chlordane 

13C10-trans-Nonachlor 

13C10-cis-Nonachlor 

RSD >5% sensitivity variation POPs : 

DDT, DDD, Endrin, Endrin, 

Heptachlor 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

� 

�� 

�� 

RRFrs CV% 

13C10-Oxychlordane 

POPs levels in air sample (median) 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

13C12-Dieldrin 

13C12-Aldrin 

13C12-Endrin 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

�� 

13C10-Heptachlor 

�� 

�� 

13C10-cis-Heptachlor epoxide 

13C6-HCB 

�� 

�� 

�� 

13C10-Mirex 

13C6-a-HCH 

13C6-b-HCH 

13C6-g-HCH 

13C6-d-HCH 


�� 

�� 

�� 

�� 

�� 

summer 

�� 

winter 

�� 

�� 

�� 

�� 

�� 

�� 


pg/g lipid 

Major POPs in Human Blood 

500,000 

450,000 

400,000 

350,000 

300,000 

250,000 

200,000 

150,000 

100,000 

50,000 

0 

TrCBs 

TeCBs 

PeCBs 

HxCBs 

Major POPs in Human serum 

HpCBs 

OCBs 

NCBs 

DeCB 

150,000 

Total PCBs 

o,p'-DDT 

p,p'-DDT 

470,000 

p,p'-DDE 


cis-Nonachlor 

Oxychlordane 

24,000 

HCB 

Mirex 

59,500 

b-HCH

Shimadzu Techno-Research Inc., Japan - UNEP Chemicals

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