Enantiomeric Excess of POPs in the Environment Hiramoto S 1, Tsurukawa M 2, Matsumura C 2, Nakano T 2, Kunugi M 3 1 Hyogo Environmental Advancement Association 2 Hyogo Prefectural Institute of Public Health Association 3 National Institute for Environmental Studies

Introduction

Purpose To identify the behavior of POPs Enantiomeric compositions of chiral POPs in seawater and air were investigated. The results of chiral analysis were shown using Enantiomeric Excess (EE). * In this study, (+) or (-) enantiomer does not identified.

Enantiomeric Excess(EE) Changes in physicochemical status, It is possible to distinguish between newly caused pollution and preserved by monitoring EE Changes in metabolic status, the EE value does not change. the EE value changes. Metabolites showed enantioselective degradation of (+) or (-) enantiomer.

Materials and Methods Materials and Methods

S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 May ～ June 2006 Sampling Sites (Seawater) ～ South China Sea ～

P-1 P-2 P-3 P-4 P-5 P-6 P-7 Sampling Sites (Seawater) ～ Pacific Ocean (West) ～ August ～ September 2005

P-8 P-9 P-10 P-11 August ～ September 2005 UNITED STATES San Francisco Sampling Sites (Seawater) ～ Pacific Ocean (East) ～

N-1 N-2 N-3 N-4 May ～ June 2005 Sampling Sites (Air) ～ North Atlantic Ocean ～

Marine pollution observation system Solid Phase Extraction unit Control Unit Extraction Column Filter unit

Sample Preparation for Analysis Exchange to hexane Clean up with silica gel Sample （ PUF ＋ ACF ） Soxhlet Extraction 3hr with acetone 24hr for dichloromethane Soxhlet Extraction 3hr with acetone 24hr for dichloromethane Concentration Concentration, Dehydration HRGC/HRMS Concentration Polyurethane foam （ PUF ） Glass holder Active carbon fiber filter （ ACF ） Spiked with 13 C-labeld POPs Spiked with 13 C-labeld POPs Air 400m 3 Seawater 100L

Target Analytes trans - Chlordane Heptachlor α - HCH Heptachlor epoxide Oxychlordane o,p’ - DDT o,p’ - DDE cis - Chlordane Technical compounds o,p’ - DDD Metabolites

HRGC/HRMS GCMS Device ： HP-6890N(HP) Column ： BGB-172*(BGB Analytik) 30m, 0.25mm i.d. film thickness 0.25μm Carrier Gas ： He 1.5mL/min Device ： JMS-800D (JEOL) Ionization ： EI Ion source temperature ： 260 ℃ Resolution : >10,000 Temperature Program ： 120 ℃ (2min) → 2 ℃ /min →250 ℃ (3min) Injector temperature ： 230 ℃ Injection Volume ： 2μL ＊ BGB-172 （ 20% tert-butyldimethylsilyl-β-cyclodextrin dissolved in 15% diphenyl- polysiloxane and 85% dimethylpolysiloxane ）

HP-5 α β γ δ α β γ δ BGB-172

Enantiomeric Excess Enantiomeric Excess (EE) EE(%) = *100 Enantiomeric Excess (EE) EE(%) = *100 E L -E S E L +E S E L : amount of larger enantiomer E S : amount of smaller enantiomer (+) (-) (+) (-) (+) (-) (+) (-) (+) (-) EE= 0 %

Results

HCH alpha- beta- gamma- delta- EE = 1% EE = 6% EE = 10% EE = 3% standard Seawater ( South China Sea) Seawater ( Pacific Ocean) Air (North Atlantic Ocean) RACEMIC

Chlordane trans- cis- EE = 1% trans- EE = 4% cis- EE = 7% standard Air (North Atlantic Ocean) trans- EE = 4% cis- EE = 1% Seawater ( Pacific Ocean) RACEMIC trans- EE = 4% cis- EE = 5% Seawater ( South China Sea)

Heptachlor epoxide endo- exo- EE = 1% EE = 39% EE = 28% EE = 44% standard Seawater ( South China Sea) Seawater ( Pacific Ocean) Air (North Atlantic Ocean) NON RACEMIC

DDD o,p’- p,p’- EE= 1 % EE = 51% EE = 58% standard Seawater ( South China Sea) Seawater ( Pacific Ocean) Air (North Atlantic Ocean) NON RACEMIC

Oxychlordane EE=1% standard Seawater ( South China Sea) Seawater ( Pacific Ocean) Air (North Atlantic Ocean) RACEMIC

Metabolite Technical compound

Metabolite Technical compound

Metabolite Technical compound

Conclusion(1) EE of chiral POPs in seawater and air samples have been investigated. The metabolites; heptachlor exo- epoxide and o,p’-DDD exist non racemic. Enatiomeric composition of alpha-HCH, trans-,cis-chlordane were near racemic. However, oxychlordane is the metabolite, it exists as racemic.

Conclusion(2) By monitoring enantiomeric composition, better understanding for the mechanism of environmental pollution will be provided. Further studies about global scale observations of chiral signatures are necessary.

EE values (South China Sea)

S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 EE values (South China Sea)

EE values (Pacific Ocean)

P-1 P-2 P-3 P-4 P-5 P-7 P-6 P-8 P-9 P-10 P-11 EE values (Pacific Ocean)

EE values (North Atlantic Ocean)

N-1 N-2 N-3 N-4 EE values (North Atlantic Ocean)

Persistent Organic Pollutants (POPs) ① Toxic ② Persistent in the environment ③ Bioaccumulative through the food web ④ Long-range transportable ① Toxic ② Persistent in the environment ③ Bioaccumulative through the food web ④ Long-range transportable Stockholm Convention (May 2001) Take measures to eliminate Reduce the release into the environment Stockholm Convention (May 2001) Take measures to eliminate Reduce the release into the environment

Results EEs of alpha-HCH, trans-,cis-chlordane in air samples and seawater samples range from 0.1 to 15.9% and 0.5 to 38.4%, respectively. EEs of metabolites heptachlor exo- epoxide in air samples and seawater samples range from 7.6 to 43.8% and 6.5 to 38.8%, respectively. The range of EEs of metabolites o,p’- DDD in seawater samples were from 20.7 to 64.4%.

trans- cis- MC5 EE= 5 % EE= 7 %

S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 EE values (South China Sea)

P-1 P-2 P-3 P-4 P-5 P-7 P-6 P-8 P-9 P-10 P-11 EE values (Pacific Ocean)

N-1 N-2 N-3 N-4 EE values (North Atlantic Ocean)