Japan and relating NIES activities Noriyuki Suzuki, Akinori Takami, - PowerPoint PPT Presentation

Current atmospheric monitoring of mercury in Japan and relating NIES activities Noriyuki Suzuki, Akinori Takami, Yasuyuki Shibata [National Institute for Environmental Studies] Kohji Marumoto [National Institute for Minamata Disease] Akira Mizohata [Osaka Prefecture University] Norio Fukuzaki [Niigata Institute of Technology] Kazuaki Kawamoto [Nagasaki University] Kenji Doi [Ministry of the Environment, Japan] Hiromitsu Nagasaka, Tatsuya Hattori, Shuji Hoshi [IDEA Consultants, Inc.] 1

Contents  Long-term monitoring program for atmospheric mercury species and mercury in precipitation at background area (Cape Hedo, Japan)  New site started at Oga, Akita prefecture  Relating research project at NIES and NIMD collaboration 2

Measurement items, sampling, and analytical methods Cape Hedo, 2007-current Component Measurement items Sampling and analytical methods Mercury speciation Continuous measurement with (GEM, GOM, PBM) Tekran mercury speciation system Mercury 24 hours continuous sampling by Hg gold amalgamation method Atmosphere and followed by CVAAS Pb, Cd, Cu, Zn, As, 7 days continuous sampling by Particulate Cr, V, Ni, Se, Sb, Ba, the low-volume sampler and matter Co, Mn, Sn, Te, Tl, analyzed by ICP/MS Be, Al, Fe, Ca, Na, K Sampling by the automatic Precipitation Hg wet-only sampler and analyzed by CVAAS (EPA method 1631) 3

Mercury monitoring station in Okinawa, Japan Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS) 26.87N 128.26E 60m a.s.l. Okinawa 4

Sampling apparatus Model 1130&1135 Low Volume Sampler Tekran Instruments Wet-Only Sampler a glimpse of the monitoring site 5

S tandard O perating P rocedures for Atmospheric Mercury Analysis for Tekran mercury speciation system Develop the QA/QC procedure in hot and humid  conditions based on Draft USEPA’s SOP (Oct. 2008) GEM: Good correlation with MOEJ manual method*  * Measurement of gaseous mercury including GEM and GOM   Good Recovery of manual injected STD Hg gas  GOM, PBM: Good correlation with manually-operated offline method (Gaseous Elemental Mercury: GEM, Particle-Bound Mercury: PBM, Gaseous Oxidized Mercury: GOM) 6

Observations of mercury species Cape Hedo, FY2014 (Apr 2014-Mar 2015) GEM GOM PBM 8.0 0.08 7.0 0.07 GOM, PBM (ng/m3) 6.0 0.06 GEM (ng/m3) 5.0 0.05 4.0 0.04 3.0 0.03 2.0 0.02 1.0 0.01 0.0 0.00 13/04/01 13/05/01 13/05/31 13/06/30 13/07/30 13/08/29 13/09/28 13/10/28 13/11/27 13/12/27 14/01/26 14/02/25 14/03/27 7

Observations of mercury species Cape Hedo, FY2014 (Apr 2014-Mar 2015) Max GEM Average Min 8

Observations of mercury species Cape Hedo, FY2014 (Apr 2014-Mar 2015) Max GOM Average Min 9

Observations of mercury species Cape Hedo, FY2014 (Apr 2014-Mar 2015) Max PBM Average Min 10

Observations of mercury species Cape Hedo, FY2007-FY2014 GEM 2007 2008 2009 2010 2011 2012 2013 2014 11

Observations of mercury species Cape Hedo, FY2007-FY2014 GOM 2007 2008 2009 2010 2011 2012 2013 2014 12

Observations of mercury species Cape Hedo, FY2007-FY2014 PBM 2007 2008 2009 2010 2011 2012 2013 2014 13

Observations of mercury species Annual variations of GEM Statistics Hourly Mean of GEM Unit: ngm -3 FY2008 FY2009 FY2010 FY2011 FY2012 FY2013 FY2014 (Apr 2008 (Apr 2009 (Apr 2010 (Apr 2011 (Apr 2012 (Apr 2013 (Apr 2014 - Mar 2009) - Mar 2010) - Mar 2011) - Mar 2012) - Mar 2013) - Mar 2014) - Mar 2015) Mean 1.8 2.2 1.9 2.1 2.0 1.7 1.7 Median 1.8 2.0 1.9 1.6 1.7 Min 1.0 1.5 1.2 1.1 1.3 0.9 1.2 Max 5.2 5.2 6.0 4.7 7.3 4.8 3.9 Standard 0.5 0.5 0.5 0.5 0.5 0.3 0.3 Deviation 14

Mercury monitoring station in Akita , Japan To strengthen the capacity of the mercury-observation network in Japan, a new observation site was set up at Funakawa, Akita Prefecture, in September 2014. 39.89N 139.85E Funakawa, Akita Cape Hedo Okinawa 15

Sampling apparatus Model 1130&1135 Tekran Instruments Wet-Only Sampler 16

Observations of mercury species Cape Oga, FY2014 GEM 17

Observations of mercury species Cape Oga, FY2014 GOM 18

Observations of mercury species Cape Oga, FY2014 PBM 19

Observations of mercury species Annual variations of GEM At Oga site Statistics Hourly Mean of GEM Unit: ngm -3 FY2014 (Apr 2014 - Mar 2015) Mean 1.6 Median 1.6 Min 0.9 Max 6.8 Standard 0.4 Deviation 20

Observations of mercury species Cape Oga, FY2014 (Apr 2014-Mar 2015) Max GOM Average Min 21

Observations of mercury species Cape Oga, FY2014 (Apr 2014-Mar 2015) Max PBM Average Min 22

Fate processes of mercury in global atmosphere- ocean system Aqueous phase 3D Transport Ox-Red Emission to air Oxidation Adsorption Dry deposition Gas exchange Wet deposition Ocean Coastal 3D Transport 23

Analysis of mercury stable isotopes to reveal fate of mercury • General plan – Background and purpose • To analyze mass-dependent and mass-independent isotopic fractionation mainly in ocean-atmosphere system • Characteristic isotopic fractionation could imply specific chemical/physical process that the mercury species being suffered from ← volatilization, biological species transformation, etc. • ⇒ Expecting to reveal unknown location, medium and process of mercury fate in atmosphere-ocean system – MDF and MIF • To analyze MIF ( d 202 Hg, etc. ) and MDF ( D 199 Hg 、 D 201 Hg) in remote and coastal fish and sediments and discuss the location/medium and processes δ xxx Hg = {[( xxx Hg/ 198 Hg) sample ) / (( xxx Hg/ 198 Hg) std )] – 1 } x 1000 xxx = 199, 200, 201, 202 Δ 199 Hg = δ 199 Hg - (0.252 x δ 202 Hg) 24

Analysis of mercury stable isotopes to reveal fate of mercury ① Reveal sources of methyl mercury (Coastal or ocean or ?) ② Reveal inter-media fate process • Phase change （ Liquied → Gas ） D 199 Hg ≈ negative Ox -Red Atmosphere Ox-Red （ Hg 2+ ⇄ Hg 0 ） • Hg 0 Methylation （ Hg 2+ → CH 3 Hg + ） • Hg 2+ Hg 粒子 Demethylation （ CH 3 Hg + → Hg 2+ or Hg 0 ） • 気化 MMHg D 199 Hg ≈ pos. D 199 Hg ≈ neg. Ox-Red Hg 0 Hg 2+ Hg 0 Hg 0 Hg 2+ D 199 Hg ≈ 0 DMHg D 199 Hg ≈ 0 DMHg Hg 2+ MMHg MMHg DMHg D 199 Hg ≈ pos. Coastal/lake Ocean Methylation-demetylation 25

Global multimedia fate model for mercury Anshropogenic Satelite data sources Atmospherilong-range transport Bioaccumulationin fish  Atmospheric and oceanic transport, chemical reactions, bioaccumulation to be integrated  Methylation process and location

Summary  Continuous mercury measurement at Cape Hedo – Starting in 2007, now continuous speciated monitoring by Tekran – Extensive QA/QC maintained based on established SOP • Treand of observation – Around 1.8-2.0 ng/m 3 in average as GEM, maybe slight decreasing trend in recent a few years – New monitoring site Cape Oga opened this year, locating at northern part of Honshu island of Japan – Additional monitoring at Niiigata prefecture • Relating activity – Development of global multimedia fate model 27