Environmental Monitoring Report on Persistent Organic ... · 2 Environmental Monitoring Report on Persistent Organic Pollutants (POPs) in Japan 2002-2004 The information contained

1

Environmental Monitoring Report

on

Persistent Organic Pollutants (POPs)

in Japan

2002-2004

Environmental Health and Safety Division

Environmental Health Department

Ministry of the Environment of JAPAN (MOE)

September 2006

2

Environmental Monitoring Report on Persistent Organic Pollutants (POPs) in Japan 2002-2004

The information contained in this report was cited from the annual reports of the Ministry of the Environment of Japan (MOE),

“CHEMICALS IN THE ENVIRONMENT” (Japanese version) for FY2002, 2003 and 2004 and translated into English which is

not an official language in the Governemnt of Japan. Thus, it is advised to refer to the original reports for accuracy. MOE

disclaims any responsibility for possible inaccuracies or omissions and any related consequences that may transpire. MOE is not

liable for any injury, loss, damage or prejudice of any kind that may be caused by any persons who have acted based on their

understanding of the information contained in this report.

Material in this publication may be freely quoted or reprinted, but acknowledgement is requested together with a reference to the

document number. A copy of the publication containing the quotation or reprint should be sent to MOE.

Limited copies of this report are available from:

Environment Health and Safety Division

Environment Health Department

Ministry of the Environment of Japan

2-2, Kasumigaseki 1-chome, Chiyoda-ku, Tokyo 100-8975

Phone: +81-3-5521-8260

Fax: +81-3-3580-3596

E-mail: [email protected]

http://www.env.go.jp/en/

FY2003 Expert Group on POPs Monitoring (for FY2002 data) : Satoshi ARIMA, Masayuki IKEDA, Shin-ichi SAKAI, Hiroaki SHIRAISHI, Noriyuki SUZUKI, Shinsuke TANABE (Chair), Osami NAKASUGI, Takeshi NAKANO, Minoru FUKUSHIMA, Hideaki MIYATA, Masatoshi MORITA and Yasuyuki SHIBATA (Secretariat). Subgroup on Analytical Methods: Kiyoshi IMAMURA, Kiwao KADOKAMI, Kuniaki KAWADA, Hiroaki SHIRAISHI (Chair), Takeshi NAKANO, Minoru FUKUSHIMA and Yasuyuki SHIBATA (Secretariat).

FY2004 Expert Group on POPs Monitoring (for FY2003 data): Satoshi ARIMA, Masayuki IKEDA, Shin-ichi SAKAI, Hiroaki SHIRAISHI, Noriyuki SUZUKI, Shinsuke TANABE (Chair), Osami NAKASUGI, Takeshi NAKANO, Minoru FUKUSHIMA, Saburo MATSUI, Hideaki MIYATA, Masatoshi MORITA and Yasuyuki SHIBATA (Secretariat). Subgroup on Analytical Methods: Kiyoshi IMAMURA, Kiwao KADOKAMI, Kuniaki KAWADA, Katashi KENMOTSU, Hiroaki SHIRAISHI (Chair), Takeshi NAKANO, Minoru FUKUSHIMA and Yasuyuki SHIBATA (Secretariat).

FY2005 Expert Group on POPs Monitoring (for FY2004 data): Satoshi ARIMA, Taisen IGUCHI, Masayuki IKEDA, Shin-ichi SAKAI, Hiroshi SATO, Hiroaki SHIRAISHI, Noriyuki SUZUKI, Osami NAKASUGI, Takeshi NAKANO, Masatoshi YASUDA, Kumiko YONEDA and Yasuyuki SHIBATA (Secretariat). Subgroup on Analytical Methods: Kiyoshi IMAMURA, Kiwao KADOKAMI, Hiroaki SHIRAISHI, Takeshi NAKANO, Yoshifumi HANADA and Yasuyuki SHIBATA (Secretariat).

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Contents List of Acronyms 4

List of Tables 5

List of Figures 6

Foreward 8

Chapter 1 Environmental Monitoring of “12 Persistent Organic 9

Pollutants (POPs)” in Japan

Chapter 2 Environmental Survey and Monitoring of Other POPs 65

in Japan

Appendix Analytical Methods for “12 POPs” Monitoring 75

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List of Acronyms

Substances

HCB Hexachlorobenzene

DDT Dichlorodiphenyltrichloroethane

DDE Dichlorodiphenyldichloroethylene

DDD Dichlorodiphenyldichloroethane

PCBs Polychlorinated biphenyls

PCDDs Polychlorinated dibenzo-p-dioxins

PCDFs Polychlorinated dibenzofurans

HCH Hexachloro cyclohexane (Benzenehexachloride)

PFOS Perfluorooctane sulfonic acid

Others

FY Fiscal Year (from April to March)

GC/MS Gas Chromatography/Mass Spectrometry

LC/MS Liquid Chromatography/Mass Spectrometry

MOE Ministry of the Environment of Japan

MQL Method Quantification Limit

MDL Method Detection Limit

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List of Tables Table 1-2-1 Target Substances/Media for 12 POPs Monitoring in FY2002-2004 10 Table 1-4-1 Results of 12 POPs Monitoring (Air and Precipitation) in FY2002-2004 17 Table 1-4-2 Results of 12 POPs Monitoring (Wildlife) in FY2002-2004 18 Table 1-4-3 Results of 12 POPs Monitoring (Surface Water) in FY2002-2004 19 Table 1-4-4 Results of 12 POPs Monitoring (Bottom Sediment) in FY2002-2004 20 Table 2-1-1 Target Substances/Media for Other POPs Survey and Monitoring during FY2002-2004 65 Table 2-2-1 Results of Other POPs Survey and Monitoring (Air and Precipitation) during FY2002-2004 66 Table 2-2-2 Results of Other POPs Survey and Monitoring (Wildlife) during FY2002-2004 66 Table 2-2-3 Results of Other POPs Survey and Monitoring (Surface Water) during FY2002-2004 66 Table 2-2-4 Results of Other POPs Survey and Monitoring (Bottom Sediment) during FY2002-2004 67

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List of Figures

Figure 1-2-1 Sites for 12 POPs Monitoring for Atmospheric Air and 11 Precipitation Figure 1-2-2 Sites for 12 POPs Monitoring for Wildlife 12 Figure 1-2-3 Sites for 12 POPs Monitoring for Surface Water 13 Figure 1-2-4 Sites for 12 POPs Monitoring for Bottom Sediment 14 Figure 1-4-1 Detected Frequency and Detection Range of Aldrin 22 Figure 1-4-2 Detected Frequency and Detection Range of Dieldrin 24 Figure 1-4-3 Detected Frequency and Detection Range of Endrin 26 Figure 1-4-4-1 Detected Frequency and Detection Range of Heptachlors 28 (Heptachlor) Figure 1-4-4-2 Detected Frequency and Detection Range of Heptachlors 29 (cis-Heptachlor epoxide) Figure 1-4-4-3 Detected Frequency and Detection Range of Heptachlors 30 (trans-Heptachlor epoxide) Figure 1-4-5-1 Detected Frequency and Detection Range of Chlordanes 32 (cis-Chlordane) Figure 1-4-5-2 Detected Frequency and Detection Range of Chlordanes 34 (trans-Chlordane) Figure 1-4-5-3 Detected Frequency and Detection Range of Chlordanes 36 (Oxychlordane) Figure 1-4-5-4 Detected Frequency and Detection Range of Chlordanes 38 (cis-Nonachlor) Figure 1-4-5-5 Detected Frequency and Detection Range of Chlordanes 40 (trans-Nonachlor) Figure 1-4-6 Detected Frequency and Detection Range of HCB 42 Figure 1-4-7 Detected Frequency and Detection Range of Mirex 44 Figure 1-4-8-1 Detected Frequency and Detection Range of Toxaphenes 46 (Parlar-26) Figure 1-4-8-2 Detected Frequency and Detection Range of Toxaphenes 47 (Parlar-50) Figure 1-4-8-3 Detected Frequency and Detection Range of Toxaphenes 48 (Parlar-62) Figure 1-4-9 Detected Frequency and Detection Range of PCBs (total) 50

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Figure 1-4-10-1 Detected Frequency and Detection Range of DDTs 52 (p,p’-DDT) Figure 1-4-10-2 Detected Frequency and Detection Range of DDTs 54 (o,p’-DDT) Figure 1-4-10-3 Detected Frequency and Detection Range of DDTs 56 (p,p’-DDE)

Figure 1-4-10-4 Detected Frequency and Detection Range of DDTs 58 (o,p’-DDE)

Figure 1-4-10-5 Detected Frequency and Detection Range of DDTs 60 (p,p’-DDD)

Figure 1-4-10-6 Detected Frequency and Detection Range of DDTs 62 (o,p’-DDD) Figure 1-4-11 Detected Frequency and Detection Range of PCDDs/PCDFs 64 Figure 2-3-2-1 Detected Frequency and Detection Range of HCHs (α-HCH) 69 Figure 2-3-2-2 Detected Frequency and Detection Range of HCHs (β-HCH) 70 Figure 2-3-2-3 Detected Frequency and Detection Range of HCHs (γ-HCH) 71 Figure 2-3-2-4 Detected Frequency and Detection Range of HCHs (δ-HCH) 72

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Foreward Persistent organic pollutants (POPs) such as PCBs and DDTs are toxic, persistent and bioaccumlative and are transferred through the air, water and migratory species across international boundaries and deposited far from their location of emission and accumulate in terrestrial and aquatic ecosystems. It came to be internationally recognised that there are concerns about health impacts, inter alia, upon women and future generations due to exposure to POPs especially in developing countries. It had been increasingly stressed that actions by only a limited number of countries were insufficient for the worldwide elimination and reduction of POPs, thus the Stockholm Convention on Persistent Organic Pollutants (Stockholm Convention) was adopted at the Conference of Plenipotentiaries held in Stockholm in May 2001. The Stockholm Convention entered into force on 17 May 2004. The Governemnt of Japan had positively contributed to the work to establish the internationally-binding document, and acceded to the Stockholm Convention on 30 August 2002. According to Article 16 of the Strockholm Convention, its effectiveness shall be evaluated starting four years after the date of entry into force of the Stockholm Convention, i.e. before 17 May 2008. Comparable monitoring data on 12 POPs under the Stockholm Convention from national, regional and global monitoring programmes are needed for a scientifically sound and meaningful evaluation. In Japan, triggered by the environmental problems due to PCBs in the 1970s, the Ministry of the Environment of Japan (MOE) has systematically conducted the “Environmental Survey and Monitoring of Chemicals” Programme and identified actual existence/non-existence and/or temporal and spatial trends of 837 chemicals (as of the end of FY2004) including POPs in the environment over a 30-year period. Since FY2002, MOE has continued to refine the methodologies for sampling and analysing for 10 substance groups among 12 POPs listed in the Annexes to the Stockholm Convention – Aldrin, Dieldrin, Endrin, Heptachlors, Chlordanes, HCB, Mirex, Toxaphenes, PCBs and DDTs, following the renovations of sampling/analysis procedures for PCDDs/PCDFs in the 1990s, with reference to the outcome of the “Workshop to Develop a POPs Global Monitoring Programme (GMP) to support the Effectiveness Evaluation of the Stockholm Convention on POPs” held in Geneva in 2003. Thus, MOE has conducted the refined environmental monitoring of “12 POPs”since FY2002 as a part of the “Environmental Survey and Monitoring of Chemicals” Programme. MOE is convinced that the data on “12 POPs” obtained in the Programme will contribute to the effective evaluations of the Stockholm Convention. This report comprises two chapters. Chapter 1 shows monitoring data on the substances relevant to “12 POPs” listed in the Annexes to the Stockholm Convention, and Chapter 2 summerises the data on 5 substances that were proposed for listing in Annex A of the Stockholm Convention and considered at the firest meeting of the Persistent Organic Pollutants Review Committee (POPRC) held in November 2005 – Pentabromodiphenyl ether, Chlordecone, Hexabromobiphenyl, HCHs (although the proposal was for Lindane, this report includes data on alpha, beta, gamma and delta isomers of HCH.) and Perfluorooctane sulfonate (PFOS).

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CHAPTER 1

ENVIRONMENTAL MONITORING OF “12 PERSISTENT ORGANIC POLLUTANTS (POPs)” IN JAPAN 1. Purpose of the Monitoring In 1974, Ministry of the Environment of Japan (MOE) commenced the “Environmental Survey and Monitoring of Chemicals” Programme. Under this Programme, environmental survey and monitoring of chemicals including persistent organic pollutants (POPs) have been carried out in a systematic and uniform manner. The Programme consists of 2 parts: (1) environmental survey of various chemicals to elucidate the presence (i.e., existence/not existence in the environment); and (2) environmental monitoring of specific persistent and bioaccumulative substances to identify temporal and spatial trends in the environment. The data obtained and evaluations thereto in the Programme have been compiled and published as an annual report – “Kagaku-busshitsu To Kankyo” (chemicals in the environment). This Chapter extracts and summerises the emvironmental monitoring data on the substances relevant to the 12 POPs listed in Annexes A, B and/or C of the Stockholm Convention on the Persistent Organic Pollutants (hereinafter referred to as “Stockholm Convention”) which were obtained under the Programme supplemented with additional data of other surveys conducted by MOE for FY2002-2004. 2. Target substances and sites

The FY2002-2004 environmental monitoring under the “Environmental Survey and Monitoring of Chemicals” Programme targeted the total 25 substance groups (see Table 1-2-1) relevant to the 12 POPs listed in the Stockholm Convention. The focussed 25 substances were selected with reference to the “essential analytes” for the determination of POPs by the Workshop to Develop a POPs Global Monitoring Programme (GMP) to Support the Effectiveness Evaluation of the Stockholm Convention on POPs, held in Geneva from 24 to 27 March 2003. Within the scheme of the Programme, the Expert Group on POPs Monitoring reviewed the obtained data and its subgroup verified each of the actual sampling and analytical procedures. The data on PCDDs/PCDFs were also appraised by other expert groups.

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The monitoring sites are shown in Figures 1-2-1 to 1-2-4. The number of the sites for “12 POPs” environmental monitoring in FY2002-2004 were: 34 to 37 for atmospheric air and precipitation (Figure 1-2-1.); 21 to 23 for wildlife (bivalves, fish and birds) (Figure 1-2-2.); 38 to 40 for surface water (Figure 1-2-3); and 62 to 63 for bottom sediment (Figure 1-2-4.). Table 1-2-1 Target Substances/Media for 12 POPs Monitoring in FY2002-2004

Media

No. Target Substances Atmospheric Air &

Precipitation Wildlife Surface

Water Bottom

Sediment

1 Aldrin X X X X 2 Dieldrin X X X X 3 Endrin X X X X

4

Heptachlors Heptachlor cis-Heptachlor epoxide trans-Heptachlor epoxide

X X X X

5

Chlordanes cis-Chlordane trans-Chlordane Oxychlordane cis-Nonachlor trans-Nonachlor

X X X X

6 HCB X X X X 7 Mirex X X X X

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Toxaphenes Parlar-26 Parlar-50 Parlar-62

X X X X

9 PCBs (total) X X X X

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DDTs p,p’-DDT o,p’-DDT p,p’-DDE o,p’-DDE p,p’-DDD o,p’-DDD

X X X X

11 PCDDs X X X 12 PCDFs X X X

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Figure 1-2-1 Sites for 12 POPs Monitoring for Atmospheric Air and Precipitation (FY2002-2004) Legend to this Figure: The red-coloured sites mean the sites where the monitoring was conducted only in the indicated fiscal year(s) during FY2002-2004.

Sapporo City, Hokkaido Pref.

Nayoro City, Hokkaido Pref., FY2004

Shizukuishi Town, Iwate Pref.

Sendai City, Miyagi Pref.

Maebashi City, Gumma Pref. Mito City, Ibaraki Pref.

Koto Ward, Tokyo Met., Tokyo Pref. Ichihara City, Chiba Pref. Yokohama City, Kanagawa Pref.

Hiratsuka City, Kanagawa Pref. Fuji-Yoshida City, Yamanashi Pref. Nagoya City, Aichi Pref.

Yokkaichi City, Mie Pref. Tenri City, Nara Pref. Osaka City, Osaka Pref. Kobe City, Hyogo Pref. Chuo Ward, Kobe City, Hyogo Pref., FY2004 Tokushima City, Tokushima Pref. Takamatsu City, Kagawa Pref. Uwajima City, Ehime Pref. Miyazaki City, Miyazaki Pref. Udo City, Kumamoto Pref.

Kagoshima City, Kagoshima Pref.,FY 2004

Omuta City, Fukuoka Pref.

Saga City, Saga Pref.

Yamaguchi City, Y amaguchi Pref.

Mishima Is., Yamaguchi Pref. Hiroshima City, Hiroshima Pref.

Oki Is., Shimane Pref. Joyo City, Kyoto Pref.

Kanazawa City, Ishikawa Pref.

Nagano City, Nagano Pref. Tonami City, Toyama Pref.

Kagamihara City, Gifu Pref.

Niigata City, Niigata Pref.

Kunigami Village, Okinawa Pref.

Chichijima Is., Tokyo Pref., FY2003-2004 (Ogasawara Islands)

(Okinawa Islands)

Kushiro City, Hokkaido Pref., FY2002

Hakodate City, Hokkaido Pref., FY2003

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Figure 1-2-2 Sites for 12 POPs Monitoring for Wildlife (FY2002-2004) Legend to this Figure: The red-coloured sites mean the sites where the monitoring was conducted only in the indicated fiscal year(s) during FY2002-2004.

Japan Sea, Hokkaido Pref. Hexagrammos otakii (Greenling)

Kabu Is., Hachinohe City, Aomori Pref. Larus Crassirostris (Black-tailed Gull)

Yamada Bay, Iwate Pref. Hexagrammos otakii (Greenling) Mytilus edulis (Blue Mussel)

Matsushima Bay, Miyagi Pref. Lateolabrax japonicus (Sea Bass)

Tokyo Bay, Tokyo Pref. Kawasaki Bay, Kanagawa Pref. Lateolabrax japonicus (Sea Bass)

Osaka Bay, Osaka Pref., Lateolabrax japonicus (Sea Bass)

Naruto, Tokushima Pref., Mytilus coruscus (Asiatic Mussel)

Takamatsu Port, Kagawa Pref., Mytilus edulis (Blue Mussel), FY2004 Mouth of Riv. Shimanto, Kochi Pref., Lateolabrax japonicus (Sea Bass)

Hiroshima Bay, Hiroshima Pref.Lateolabrax japonicus (Sea Bass)

West coast of Satsuma Peninsula, Kagoshima Pref.Lateolabrax japonicus (Sea Bass)

Dokai Bay, Fukuoka Pref. (Blue Mussel) 2002-2003 (Purplish Bifurcate Mussel) FY2004

Shichirui Bay, Shimane Pref. Mytilus edulis (Blue Mussel)

Lk. Nakaumi, Shimane Pref., Lateolabrax japonicus (Sea Bass)

Adogawa, Lk. Biwa Shiga Pref. Tribolodon hakonensis (Dace)

Nakagusuku Bay, Okinawa Pref.Acanthopagrus sivicolus (Black Porgy)

(Ogasawara Islands)

(Okinawa Islands)

Mishima Is., Yamaguchi Pref. (Purplish Bifurcate Mussel), FY2002

Miura Peninsula, Kanagawa Pref. Mytilus edulis (Blue Mussel), FY2002

Morioka City, Iwate Pref. Sturnus cineraceus (Gray Starling)

Offshore of Joban, Ibaraki Pref. Cololabis saira (Pacific Saury)

Yokohama Bay, Kanagawa Pref. Mytilus edulis (Blue Mussel)

Cost of Noto Peninsula Ishikawa Pref. Mytilus edulis (Blue Mussel)

Offshore of Kushiro, Hokkaido Pref. Hexagrammos lagocephalus (Rock Greenling)

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Figure 1-2-3 Sites for 12 POPs Monitoring for Surface Water (FY2002-2004) Legend to this Figure: The red-coloured sites mean the sites where the monitoring was conducted only in the indicated fiscal year(s) during FY2002-2004.

Mouth of Riv. Ishikari

Riv. Tokachi (Obihiro City)

Riv. Toyosawa (Hanamaki City)

Matsushima Bay Onahama Port

Mouth of Riv. Tone

Mouth of Riv. Hanami Mouth of Riv. Sumida Kawasaki Port Yokohama Port

Riv. Tenryu (Ryuyo Town) Nagoya Port

Yokkaichi Port Riv. Katsura (Kyoto City) Mouth of Riv. Yamato Osaka Port

Kobe Port

Mouth of Riv. Yoshino Takamatsu Port Mouth of Riv. Shimanto

Mouth of Riv. Oyodo

Riv. Gotanda (Kushikino City)

Riv. Midori (Udo Cit y)

Imari Bay

Dokai Bay, FY2004

Offshore of Hagi Tokuyama Bay

Kure Port Offshore of Mizushima

Offshore of Himeji Miyazu Port

Lk. Biwa Offshore of Karasaki

Riv. Shonokawa, FY2004

Mouth of Riv. Sai

Mouth of Riv. Jintsu Lk. Suwa

Mouth of Riv. Mogami

Lk. Hachiro

Lk. Jusan

Naha Port

(Okinawa Islands)

(Ogasawara Islands)

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Figure 1-2-4 Sites for 12 POPs Monitoring for Bottom Sediment (FY2002-2004) Legend to this Figure: The red-coloured sites mean the sites where the monitoring was conducted only in the indicated fiscal year(s) during FY2002-2004.

Riv. Teshio (Bifuka Town) (Ogasawara Islands)

(Okinawa Islands)

Naha Port Riv. Tokachi (Obihiro City)

Tomakomai Port

Riv. Toyosawa (Hanamaki City)

Riv. Hirose (Sendai City) Matsushima Bay Onahama Port

Riv. Tagawa (Utsunomiya City) Mouth of Riv. Sumida Mouth of Riv. Tone Mouth of Riv. Arakawa Mouth of Riv. Hanami Coast of Ichihara and Anegasaki Kawasaki Port Yokohama Port Riv. Arakawa (Kofu City) Shimizu Port Riv. Tenryu (Ryuyo Town) Kinuura Port Toba Port Nagoya Port Yokkaichi Port Riv. Katsura (Kyoto City) Riv. Yamato (Oji Town) Mouth of Riv. Yodo Mouth of Riv. Yamato Osaka Port Outside Osaka Port Mouth of Riv. Kinokawa

Kobe Port Mouth of Riv. Yoshino

Takamatsu Port Niihama Port Mouth of Riv. Shimanto

Mouth of Riv. Oita Mouth of Riv. Oyodo Riv. Amo (Hayato Town)

Riv. Gotanda (Kushikino City)

Imari Bay

Hakata Bay Dokai Bay

Offshore of Ube Offshore of Hagi

Tokushima Bay Hiroshima Bay

Kure Bay Offshore of Mizushima

Offshore of Himeji Miyazu Port

Karasaki, Lk.Biwa

Minamihira, Lk.Biwa, FY2003-2004

Riv. Shonokawa (Tsuruga City)

Riv. Sai FY2002

Mouth of Riv. Jintsu

Riv. Yodo (Osaka City)

Lk. Suwa

Lower Riv. Shinano Mouth of Riv. Mogami

Lk. Hachiro

Lk. Jusan

Hayasaki, Lk.Biwa, FY2002

Mouth of Riv. Tama

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3. Methods of sampling/analysis (1) Selection of the monitoring sites The points where chemical substances were being released (i.e., near the outlet for waste water of a factory, etc. where the substances were being manufactured or used, or near points through which transportation facilities passed, etc.) and points directly affected by pollution were excluded from sampling sites. (2) Sampling methods The methodologies for sampling 12-POPs-relevant substances other than PCDDs/PCDFs in each of the targeted matrices were shown below. Collected samples were placed in bags or containers so that the samples would not elute or adsorb, and were analysed as soon as possible. For preservation, samples were kept in refrigerators or freezers, etc. in a manner according to the documented protocol.

A. Air and precipitation

Sampling should take place, in principle, between September and November when the weather is stable. Samples should be collected by adsorption to resin, glass fiber filters, etc. or sucked by canister. The sites for air sampling should be on the location where information on status of air is available. The sites significantly affected by a particular source of chemicals, by transportation facilities, etc. should be avoided. Information collected at sampling sites: Information on weather, temperature, humidity, wind direction, wind velocity, surrounding geography and traffic conditions at neighbouring roads during the sampling time should be recorded.

B. Wildlife In sea areas, a sea bass or young sea bass should be the first choice and, if not available, a goby, striped mullet or flatfish could be accepted. At lakes, marshes and rivers, a dace should be used and, if not available, a carp or crucian carp could be accepted as a standard sample. Although It is preferable to use a single body of the sample, pool of several bodies could be also allowed. In such a case, a small-bodied sample couls be used after sufficient cleansing. For fish, a collection of 3 samples from the site should be considered sufficient. Preparation of fish for analysis: Edible parts (muscles) should be used. Any part of the fish could be used, but more than approximately 100g should be ensured for analytical samples. In cases where the body weight of the fish is under 100g, the edible parts of several fish should be carved and homogenised.

Preparation of bivalves for analysis: Edible parts of the required quantity should be collected and homogenised for use as samples. Sludge should be removed to the most extent as possible.

For wildlife samples, lipid weight (%) is measured by the following method: Five grams of the sample is placed in a homogeniser cup, after which 20 mL of chloroform and 40 mL of methanol are added, and then homogenised for 2 minutes. An additional 20 mL of chloroform is added, followed by 2-minutes homogenising. The sample is then filtered with a Buchner funnel and homogenised with 80 mL of chloroform and methanol mixture (1:1). 60 mL

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of distilled water is added to the entire chloroform-methanol fraction placed in the separation funnel, and should be then shaken gently. The lower chloroform fraction is collected and dryed with anhydrous sodium sulfate, and the solvent should be evaporated using a rotary evaporator. The residue is dried using phosphorus pentoxide, and the weight is measured.

Information collected at sampling sites: Standard Japanese vernacular name should be confirmed, and body length (excluding tail), body weight and lipid weight should be recorded.

C. Surface water

Water sampling is conducted at a time when the days preceding the day of sampling has been relatively sunny and the water quality is stable. In monitoring, three samples should be collected at spots within a unit range of 500 square meters, so that they are collected in as widespread spots as possible. The depth for sampling point should be, in principle, 0–50 cm beneath the surface vertically under the spot selected within the unit range. However, water in 0–2 cm depth should be avoided for sampling so that floating garbage and oils should not be contained in the samples. Preparation for analysis: No filtration or centrifugal separation, etc. should be conducted. Information collected at sampling sites: Temperature, colour by visual (eye) observation, transparency and turbidity should be recorded.

D. Bottom sediment In monitoring, three samples should be collected within a unit range of 500 square meters so that they are collected in as widespread points as possible. In this case, the sample for bottom sediment is a mixture of samples from 3 spots in equal quantities. The bottom sediment collected using an Ekman-Birge bottom sampler or other proportionate bottom samplers is placed on a clean tray. The sampled sediment, after being removed from extraneous substances such as pebbles, shells and bits of animals and plants, should be sieved with a 16-mesh sieve (hole diameter: 1 mm) and provided for analysis. The sludge content (weight of sample through the sieve/weight of original sample) (%) is measured. Dry weight (105–110°C for about 2 hours) and ignition loss (600 ± 25°C for about 2 hours) should be measured for part of the samples. Samples for analysis should be, in principle, not air- or heat-dried, and the measured value per dry weight should be calculated. Information collected at sampling sites: Appearance, odour, foreign substance, depth of water at sampling point, water content, ignition loss and sludge content should be recorded.

(3) Analytical methods

The analytical methods utilised for the “12 POPs” monitoring in FY2002-2004 for each of the monitored matrices are shown in the Appendix.

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4. Monitoring results Summaries of the detection results of the FY2002-2004 monitorings are shown in Table 1-4-1 to 1-4-4. Table 1-4-1 Results of 12 POPs Monitoring (Air and Precipitation) in FY2002-2004

SubstanceAldrin <0 .020 3.2 0 .030(tr) w <0 .0077 28 1 .5 w <0 .05 14 0 12(tr)

c 0 .030 6 .9 0 .55 c <0 .05 13 0 .08(tr)Dieldrin 0 .73 110 5 .6 w 2 .1 260 19 w 1 .1 280 17

c 0 82(tr) 110 5 .7 c 0 .81 76 5 .5Endrin <0 .030 2 .5 0 22 w 0 .081 6 .2 0 .74 w 0 .054(tr) 6 .5 0 .64

c 0 .042 2 .1 0 .23 c <0 .048 1 .9 0 .23Heptachlors

Heptachlor 0 .20 220 11 w 1 .1 240 27 w 0 46 200 23c 0 .39 65 10 c 0 .53 100 11

cis -Heptachlor w 0 .45 28 3 .5 w 0 .65 9 .7 2 .8epoxide c 0 .49 6 .6 1 .3 c 0 .44 7 .0 1 .1trans -Heptachlor w <0 .033 0 .30 0 .036(tr) w <0 .2 0 .38(tr) <0 .2epoxide c <0 .033 0 .094(tr) <0 .033 c <0 .2 <0 .2 <0 .2

Chlordanescis -Chlordane 0 .86 670 31 w 6 .4 1,600 110 w 2 .3 1,000 92

c 2 .5 220 30 c 1 .2 290 29trans -Chlordane 0 .62 820 36 w 6 .5 2,000 130 w 2 .2 1,300 110

c 2 .5 290 37 c 1 .5 360 35Oxychlordane <0 .008 8 .3 0 .96 w 0 .41 12 2 .5 w 0 .41 7 .8 1 .9

c 0 .41 3 .2 0 .87 c 0 .27 3 .9 0 .80cis -Nonachlor 0 .071 62 3 .1 w 0 .81 220 12 w 0 .36 130 10

c 0 .18 23 2 .7 c 0 .087 28 2 .7trans -Nonachlor 0 .64 550 24 w 5 .1 1,200 87 w 1 .9 870 72

c 2 .1 180 24 c 0 .95 240 23HCB 57 3,000 99 w 81 430 150 w 47 430 130

c 64 320 94 c 51 390 98Mirex w 0 .047 0 .19 0 .11 w 0 .042(tr) 0 .16 0 .099

c 0 .091(tr) 0 .099 0 .044 c 0 .019(tr) 0 .23 0 .046(tr)Toxaphenes

Parlar-26 w 0 .17(tr) 0 .77 0 .31 w 0 .17(tr) 0 .46 0 .27c 0 .091(tr) 0 .27 0 .17(tr) c 0 .094(tr) 0 .50 0 .15(tr)

Parlar-50 w <0 .27 0 .37(tr) <0 .27 w <0 .4 <0 .4 <0 .4c <0 .27 <0 .27 <0 .27 c <0 .4 <0 .4 <0 .4

Parlar-62 w <0 .52 <0 .52 <0 .52 w <0 .81 <0 .81 <0 .81c <0 .52 <0 .52 <0 .52 c <0 .81 <0 .81 <0 .81

PCBs (total) 16 880 100 w 36 2,600 260 w 25 3,300 240c 17 630 110 c 20 1,500 130

DDTsp,p’ -DDT 0 .25 22 1 .9 w 0 .75 24 5 .8 w 0 .41 37 4 .7

c 0 .31 11 1 .7 c 0 .29 13 1 .8o,p’ -DDT 0 .41 40 2 .2 w 0 .61 38 6 .9 w 0 .54 22 5 .1

c 0 .43 6 .4 1 .6 c 0 .35 9 .4 1 .5p,p’ -DDE 0 .56 28 2 .8 w 1 .2 51 7 .2 w 0 .62 95 6 .1

c 1 .1 22 2 .8 c 0 .85 43 2 .9o,p’ -DDE 0 .11 8 .5 0 .60 w 0 .17 7 .5 1 .4 w 0 .14 8 .9 1 .1

c 0 .18 1 .7 0 .50 c 0 .14 3 .9 0 .53p,p’ -DDD <0 .006 0 .76 0 .12 w 0 .063 1 .4 0 .30 w 0 .036(tr) 1 .4 0 .24

c 0 .037(tr) 0 .52 0 .13 c 0 .025(tr) 0 .91 0 .12o,p’ -DDD <0 .006 0 .85 0 .14 w 0 .059 1 .3 0 .37 w 0 .052(tr) 2 .6 0 .31

c 0 .062 0 .42 0 .15 c <0 .048 0 .86 0 .14PCDDs/PCDFs 0 .021 0 .45 0 .16 0 .017 0 .20 0 .077 0 .021 0 .25 0 .074

Legend and Note to this TableUnit is pg/m3 whereas pg-TEQ/m3 was used for PCDDs/PCDFs. TEF was calculated according to WHO-TEF(1998).tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL), w = warm season (Aug.-Oct.), c = cold season (Nov.-Dec.)mean = geographical mean, whereas arithmetical mean for PCDDs/PCDFs, assuming the data less than MDL as a half of MDL.Total number of the sites was: 34 in FY2002; 35 (34 in cold season) in FY2003; and 37 in FY2004 for the substances excluding PCDDs/PCDFswhereas 48 sites for PCDDs/PCDFs.

MeanFY2003FY2002

MeanMin Max Min MaxFY2004

MeanMin Max

- - -

- - -

- - -

- - -- - -- - -- - -- - -

- - -

- - -

- - -

- - -

- - -

- - -- - -- - -

- - -- - -- - -- - -- - -- - -

- - -

- - -

- - -

Air & Precipitation

- - -

- - -

- - -

18

Table 1-4-2 Results of 12 POPs Monitoring (Wildlife) in FY2002-2004 WildlifeSubstanceAldrin v <1 .4 34 (tr) 1 .7(tr) v <0 .84 51 1 .6(tr) v <1 .3 46 1 .7(tr)

f <1 .4 2 .0(tr) <1 .4 f <0 .84 1 .9(tr) <0 .84 f <1 .3 2 .4(tr) <1 .3b <1 .4 <1 .4 <1 .4 b <0 .84 <0 .84 <0 .84 b <1 .3 <1 .3 <1 .3

Dieldrin v 7 (tr) 190,000 490 v 46 78,000 410 v 42 69,000 510f 46 2,400 280 f 29 1,000 210 f 23 (tr) 2,800 240b 820 1,700 1,200 b 790 2,200 1,300 b 370 960 590

Endrin v <6 12,000 44 v 6 .3 5,000 36 v 5 .7(tr) 4,600 54f <6 180 19 f <1 .6 180 14 f <4 .2 220 18b <6 99 22 b 5 .4 96 21 b <4 .2 62 11 (tr)

HeptachlorsHeptachlor v <1 .4 15 3 .6 v <2 .2 14 2 .8(tr) v <1 .4 16 3 .5(tr)

f <1 .4 20 4 .0 f <2 .2 11 <2 .2 f <1 .4 460 1 .9(tr)b <1 .4 5 .2 2 .1(tr) b <2 .2 <2 .2 <2 .2 b <1 .4 1 .5(tr) <1 .4

cis -Heptachlor v v 9 .7 880 42 v 9 .8(tr) 840 57epoxide f f 7 .0 320 42 f 3 .3(tr) 620 46

b b 370 770 520 b 190 350 270trans -Heptachlor v v <4 .4 48 <4 .4 v <4 55 4 .0(tr)epoxide f f <4 .4 <4 .4 <4 .4 f <4 10 (tr) <4

b b <4 .4 <4 .4 <4 .4 b <4 <4 <4Chlordanes

cis -Chlordane v 24 26,000 810 v 110 14,000 1,100 v 91 14,000 1,200f 57 6,900 580 f 43 4,400 490 f 68 9,800 580b 10 450 67 b 6 .8 370 47 b 5 .8(tr) 240 39

trans -Chlordane v 33 2,300 420 v 69 2,800 550 v 53 2,800 510f 20 2,700 180 f 9 .6 1,800 150 f 17 (tr) 5,200 190b 8 .9 26 14 b 5 .9(tr) 27 11 b <16 26 (tr) 14 (tr)

Oxychlordane v <1 .2 5,600 76 v 11 1,900 90 v 14 1,700 110f 16 3,900 160 f 30 820 140 f 25 1,500 150b 470 890 640 b 610 1,300 750 b 320 730 460

cis -Nonachlor v 8 .6 870 190 v 48 1,800 290 v 43 1,800 280f 46 5,100 420 f 19 2,600 350 f 48 10,000 410b 68 450 200 b 68 660 200 b 73 240 130

trans -Nonachlor v 21 1,800 510 v 140 3,800 780 v 110 3,400 710f 98 8,300 970 f 85 5,800 880 f 140 21,000 1,000b 350 1,900 880 b 350 3,700 1,100 b 390 1,200 680

HCB v 2 .4 330 23 v 21 (tr) 660 44 v 14 80 30f 19 910 140 f 28 1,500 170 f 26 1,800 220b 560 1,600 1,000 b 790 4,700 1,700 b 410 2,200 970

Mirex v v 1 .1(tr) 19 4 .8 v 1 .1(tr) 12 4 .5f f 1 .7(tr) 25 7 .9 f 3 .8(tr) 180 11b b 31 450 110 b 33 110 61

ToxaphenesParlar-26 v v <15 39 (tr) <15 v <14 32 (tr) <14

f f <15 810 29 (tr) f <14 1,000 40 (tr)b b <15 2,500 110 b <14 810 71

Parlar-50 v v <11 58 13 (tr) v <15 45 (tr) 16 (tr)f f <11 1,100 34 f <15 1,300 54b b <11 3,000 110 b <15 1,000 83

Parlar-62 v v <40 <40 <40 v <33 <33 <33f f <40 580 <40 f <33 870 <33b b <40 530 96 (tr) b <33 280 64 (tr)

PCBs (total) v 200 160,000 10,000 v 1,000 130,000 11,000 v 1,500 150,000 7,700f 1,500 550,000 14,000 f 870 150,000 11,000 f 990 540,000 15,000b 4,800 22,000 11,000 b 6,800 42,000 18,000 b 5,900 13,000 8,900

DDTsp,p’ -DDT v 38 1,200 200 v 49 1,800 290 v 48 2,600 280

f 6 .8 24,000 330 f 3 .7(tr) 1,900 210 f 5 .5 53,000 310b 76 1,300 380 b 180 1,400 540 b 160 700 330

o,p’ -DDT v 22 480 100 v 35 480 130 v 20 910 130f 6 (tr) 2,300 110 f 2 .9 520 80 f 3 .7 1,800 130b <4 58 10 (tr) b 8 .3 66 18 b 0 9(tr) 43 7 .7

p,p’ -DDE v 140 6,000 1,100 v 190 6,500 1,100 v 220 8,400 1,000f 510 98,000 2,500 f 180 12,000 2,000 f 390 52,000 2,500b 8,100 170,000 36,000 b 18,000 240,000 63,000 b 6,800 200,000 34,000

o,p’ -DDE v 13 1,100 88 v 17 460 84 v 19 360 70f 3.6 13,000 77 f <1 .2 2,500 48 f 0 .9(tr) 5,800 68b 20 49 28 b <1 .2 4 .2 2 .0(tr) b <0 .69 3 .7 1 .0(tr)

p,p’ -DDD v 11 3,200 340 v 7 .5(tr) 2,600 380 v 7 .8 8,900 300f 80 14,000 610 f 43 3,700 500 f 56 9,700 640b 140 3,900 560 b 110 3,900 590 b 52 1,400 310

o,p’ -DDD v 9 (tr) 2,900 130 v 6 .5 1,900 200 v 6 .0 2,800 160f <4 1,100 83 f <2 .0 920 73 f <1 .9 1,700 100b 8 (tr) 23 15 b 5 .0(tr) 36 14 b <1 .9 25 5 .6(tr)

PCDDs/PCDFs No data available

Legend and Note to this TableUnit is pg/g-wet.tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).v = bivalves (Mytilus edulis, Septifer virgatus or Mytilus coruscus).f = fish (Hexagrammos otakii, H. lagocephalus, Cololabis saira, Lateolabrax japonicus, Acanthopagrus sivicolus or Tribolodon hakonensis ).b = birds (Strunus cineraceus or Larus crassirostris ).mean = geographical mean, whereas arithmetical mean for PCDDs/PCDFs, assuming the data less than MDL as a half of MDL.Total numbers of the sites for bivalves, fish and birds were: 8, 14 and 2 in FY2002; 6, 14 and 2 in FY2003; and 7, 14 and 2 in FY2004.

- - -

- - -- - -

- - -

- - -- - -

- - -- - -

- - -

- - -- - -

-

- - -

- -- - -

MaxFY2002

- - -

- - -

-

-

MeanFY2003 FY2004

Min Max Mean Min Max Mean Min

- -

- -

19

Table 1-4-3 Results of 12 POPs Monitoring (Surface Water) in FY2002-2004

Surface WaterSubstanceAldrin <0 .2 18 0 .69 <0 .2 3 .8 0 .90 <0 .4 13 1 .5(tr)Dieldrin 3 .3 940 41 9 .7 510 57 9 430 55Endrin <2 .0 31 4 .7(tr) 0 .70 78 5 .7 0 .7(tr) 100 7Heptachlors

Heptachlor <0 .5 25 1 .1(tr) 1 .0(tr) 7 .0 1 .8(tr) <2 29 <2cis -Heptachlorepoxide 1 .2 170 9 .8 2 77 10

trans -Heptachlorepoxide <0 .4 2 <0 .4 <0 .3 <0 .3 <0 .3

Chlordanescis -Chlordane 2 .5 880 41 12 920 69 10 1,900 92trans -Chlordane 3 .1 780 32 6 410 34 5 1,200 32Oxychlordane <0 .4 41 2 .4 0 .6(tr) 39 3 .0 0 .7(tr) 47 3 .2cis -Nonachlor 0 .23 250 7 .6 1 .3 130 8 .0 0 .8 340 7.5trans -Nonachlor 1 .8 780 29 4 .0 450 26 3 (tr) 1,100 25

HCB 9 .8 1,400 36 11 340 29 11 (tr) 180 30Mirex <0 .09 0 .8 0 .13(tr) <0 .2 1 .1 <0 .2Toxaphenes

Parlar-26 <20 <20 <20 <3 <3 <3Parlar-50 <30 <30 <30 <7 <7 <7Parlar-62 <90 <90 <90 <30 <30 <30

PCBs (total) 60 11,000 460 230 3,100 530 140 4,400 630DDTs

p,p’ -DDT 0 .25(tr) 440 12 2 .8(tr) 740 14 <2 310 15o,p’ -DDT 0 .19 77 5 .1 1 .5(tr) 100 6 <2 85 4 .5(tr)p,p’ -DDE 1 .3 760 24 5 380 26 6 (tr) 680 36o,p’ -DDE <0 .3 680 2 .3 0 .42(tr) 170 2 .2 0 .6(tr) 170 3p,p’ -DDD 0 .57 190 15 4 410 19 2 .4(tr) 740 19o,p’ -DDD <0 .2 110 5 .5 1 .1 160 7 .1 0 .7(tr) 81 6

PCDDs/PCDFs 0 .018 2 .7 0 .27 0 .020 7 .0 0 .24 0 .011 2 .5 0 .22

Legend and Note to this TableUnit is pg/L whereas pg-TEQ/L was used for PCDDs/PCDFs. TEF was calculated according to WHO-TEF(1998).tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).mean = geographical mean, whereas arithmetical mean for PCDDs/PCDFs, assuming the data less than MDL as a half of MDL.Total number of the sites was: 38 in FY2002; 36 in FY2003; and 38 in FY2004 for the substances excluding PCDDs/PCDFswhereas 1,340 sites for PCDDs/PCDFs in FY2004.

FY2002 FY2003 FY2004Min Max Mean Min Max Mean Min

- - -

- - -

-

Max Mean

- -

-

- - -- - -

- -

20

Table 1-4-4 Results of 12 POPs Monitoring (Bottom Sediment) in FY2002-2004 Bottom SedimentSubstanceAldrin <2 570 12 <0 .6 1,000 17 <0 .6 390 9Dieldrin 4 .0 2,300 63 <2 9,100 59 1 .9(tr) 3,700 58Endrin <2 19,000 9 <2 29,000 11 <0 .9 6,900 13Heptachlors

Heptachlor <0 .6 120 3 .5 <1 160 2 .4(tr) <0 .9 170 2 .5(tr)cis -Heptachlorepoxide <1 160 4 <2 230 4 .4(tr)

trans -Heptachlorepoxide <3 <3 <3 <2 2 .5(tr) <2

Chlordanescis -Chlordane 1 .8 18,000 120 3 .6(tr) 19,000 170 4 36,000 140trans -Chlordane 2 .1 16,000 130 2 .4(tr) 13,000 120 3 26,000 95Oxychlordane <0 .5 120 2 .2 <0 .4 85 2 <0 .8 140 2 .0(tr)cis -Nonachlor <0 .7 7,800 66 <0 .9 6,500 59 0 .8(tr) 9,400 46trans -Nonachlor 3 .1 13,000 120 2 .0 11,000 100 3 23,000 83

HCB 7 .6 19,000 210 5 .0 42,000 140 6 (tr) 25,000 130Mirex <0 .4 1,500 1 .8(tr) <0 .5 220 2 .1Toxaphenes

Parlar-26 <30 <30 <30 <20 <20 <20Parlar-50 <50 <50 <50 <20 <20 <20Parlar-62 <2,000 <2,000 <2,000 <400 <400 <400

PCBs (total) 39 630,000 9,200 39 5,600,000 8,200 38 1,300,000 7,300DDTs

p,p’ -DDT 5 (tr) 97,000 270 3 .0 55,000 240 7 98,000 330o,p’ -DDT <2 27,000 58 <0 .3 3,200 43 1 .1(tr) 17,000 52p,p’ -DDE 8 .4 23,000 660 9 .5 80,000 710 8 39,000 630o,p’ -DDE <1 16,000 46 0 .5(tr) 24,000 43 <0 .8 28,000 35p,p’ -DDD 2 .2(tr) 51,000 540 3 .7 32,000 590 4 75,000 550o,p’ -DDD <2 14,000 140 1 .0(tr) 8,800 140 0 .7(tr) 16,000 120

PCDDs/PCDFs

Legend and Note to this TableUnit is pg/g-dry whereas pg-TEQ/g was used for PCDDs/PCDFs. TEF was calculated according to WHO-TEF(1998).tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).mean = geographical mean, whereas arithmetical mean for PCDDs/PCDFs, assuming the data less than MDL as a half of MDL.Total number of the sites was: 63 in FY2002; 62 in FY2003; and 63 in FY2004 for the substances excluding PCDDs/PCDFswhereas 961 sites for PCDDs/PCDFs in FY2004.

FY2002 FY2003 FY2004Min Max Mean Min Max Mean Min Max Mean

- - -

- - -

- - -

- - -

- - -- - -

21

5. Assessment of monitoring results The target substances analysed in this environment monitoring were Aldrin, Dieldrin, Endrin, three substances relevant to Heptachlors (heptachlor, cis-heptachlor epoxide and trans-heptachlor epoxide), five substances relevant to Chlordanes (cis-chlordane, trans-chlordane, oxychlordane, cis-nanochlor and trans-nanochlor), HCB, Mirex, three substances relevant to Toxaphenes (Parlar-26, Parlar-50 and Parlar-62), total PCBs and six substance relevant to DDTs (p,p’-DDT, o,p’-DDT, p,p’-DDE, o,p’-DDE, p,p’-DDD and o,p’-DDD). High-sensitivity analyses were carried out in FY2004, in succession from FY2002 and FY2003. The “12 POPs” were detected in all the media except that toxaphenes were not detected in surface water and bottom sediment. Results and assessment of the environment monitoring for each substance (group) are described below. (1) Aldrin

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in FY2004 were comparable to those in FY2002. In FY2003 the values were higher in warm season than in cold season, while the results in FY2004 showed no apparent differences between the warm season and cold season. The substance had been detected at approximately a half of the monitoring sites or more since FY2002, and its persistence in the atmospheric air and precipitation was still recognised in widespread areas. Wildlife: Bivalves: The persistent concentrations in FY2004 were comparable to those in FY2002 and FY2003. The substance was detected at about a half of the monitoring sites from FY2002 to FY2004, and its persistence in bivalves in the environment was still recognised in widespread areas. Fish: The substance was detected at two monitoring sites in FY2004, though the values were below the detection limit. The substance had been detected since FY2002: in one of the total 70 samples at one of the 14 sites (FY2002); in sixteen of the total 70 samples at seven of the 14 sites (FY2003); and in five of the total 70 samples at two of the 14 sites (FY2004). Its persistence in fish in the environment was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence in birds in the environment because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence in birds in the environment was still recognised. Surface water and bottom sediment: The substance was detected at almost all the monitoring sites from FY2002 to FY2004, and its persistence in surface water as well as bottom sediment was still recognised in widespread areas.

22

Figure 1-4-1 Detected Frequency and Detection Range of Aldrin

31

10

16/

0/

12/ 15/38 30

186 189

7016/ 5/70 70 10 10

178/ 170/

1/ 0/ 0/

149/189

93/ 34/ 33/

34 37

114 36 38

14/ V

B

A

W S

F

41/ 34/ 34/ 15/37102 35

Aldrin (Air and Precipitation)

0.080.120.551.50.0300

10

20

30

2002 2003(w) 2003(c) 2004(w) 2004(c)

Ald

rin (p

g/m

3)

Aldrin (Surface Water)

1.50.900.690

5

10

15

20

2002 2003 2004

Ald

rin (p

g/L)

Aldrin (Bottom Sediment)

917120

200

400

600

800

1,000

2002 2003 2004

Ald

rin (p

g/g-

dry)

Aldrin (Wildlife/Bivalves)

1.71.7 1.60

20

40

60

2002 2003 2004

Ald

rin (p

g/g-

wet

)Aldrin (Wildlife/Fish)

<1.3<0.84

<1.4

0.0

1.0

2.0

3.0

4.0

5.0

2002 2003 2004

Ald

rin (p

g/g-

wet

)

Aldrin (Wildlife/Birds)

<1.3<0.84

<1.4

0.0

1.0

2.0

3.0

4.0

5.0

2002 2003 2004

Ald

rin (p

g/g-

wet

)

23

(2) Dieldrin

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence atmospheric air and precipitation was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence in bivalves and fish was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence in birds because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance has been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

24

Figure 1-4-2 Detected Frequency and Detection Range of Dieldrin

35/35

70/ 70/70

36/36

37/37

114/114

34/34

37/37

102/102

38/38

70

189/189

186/186

10 10 10

189/189

38/ 30/ 31/

10/ 10/ 10/

38 30 31V

B

A

W S

F 70/70

Dieldrin (Air and Precipitation)

5.5175.7195.60

100

200

300

2002 2003(w) 2003(c) 2004(w) 2004(c)

Die

ldrin

(pg/

m3)

Dieldrin (Surface Water)

5557410

200

400

600

800

1,000

2002 2003 2004

Die

ldrin

(pg/

L)

Dieldrin (Bottom Sediment)

5859630

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

Die

ldrin

(pg/

g-dr

y)

Dieldrin (Wildlife/Bivalves)

5104104900

50,000

100,000

150,000

200,000

2002 2003 2004

Die

ldrin

(pg/

g-w

et)

Dieldrin (Wildlife/Fish)

240210280

0

1,000

2,000

3,000

2002 2003 2004

Die

ldrin

(pg/

g-w

et)

Dieldrin (Wildlife/Birds)

1,300

590

1,200

0

500

1,000

1,500

2,000

2,500

2002 2003 2004

Die

ldrin

(pg/

g-w

et)

25

(3) Endrin

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: In FY2004, the substance was detected in 57 of the 70 samples at 13 of the 14 monitoring sites. The substance had been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water and bottom sediment: The substance had been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

26

Figure 1-4-3 Detected Frequency and Detection Range of Endrin

F

V

B

34/ 37/ 36/37102 35 34A

W

90/ 35/37

38/189 186114 36 38

101/ 36/

54/ 10/ 5/67/ 57/

189

70 70 70 10 10

141/ 150/ 182/S

31

10

31/

7/

35/ 30/38 30

Endrin (Air and Precipitation)

0.220.74

0.23 0.64 0.230

2

4

6

8

2002 2003(w) 2003(c) 2004(w) 2004(c)

Endr

in (p

g/m

3)

Endrin (Surface/Water)

75.74.70

20

40

60

80

100

2002 2003 2004

Endr

in (p

g/L)

Endrin (Bottom/Sediment)

131190

10,000

20,000

30,000

2002 2003 2004

Endr

in (p

g/g-

dry)

Endrin (Wildlife/Bivalves)

5436440

2,000

4,000

6,000

8,000

10,000

12,000

2002 2003 2004

Endr

in (p

g/g-

wet

)

Endrin (Wildlife/Fish)

1814190

50

100

150

200

250

2002 2003 2004

Endr

in (p

g/g-

wet

)

Endrin (Wildlife/Birds)

11

2122

0

20

40

60

80

100

2002 2003 2004

Endr

in (p

g/g-

wet

)

27

(4) Heptachlors

Heptachlor cis- Heptachlor epoxide trans- Heptachlor epoxide

Atmospheric air and precipitation: The persistence of Heptachlor has been monitored since FY2002, and Heptachlor epoxides thereof since FY2003. The persistent concentrations of Heptachlor and cis-Heptachlor epoxide in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values of the two substances were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. Heptachlor and cis-Heptachlor epoxide had been detected in all the samples from all the monitoring sites since FY2002 and FY2003, and their persistence was still recognised in widespread areas. Wildlife: Bivalves: cis-Heptachlor had been detected in all the samples from all the monitoring sites since FY2003, and Heptachlor had been detected in most of the samples from almost all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas. Fish: cis-Heptachlor had been detected in all the samples from all the monitoring sites since FY2003, and Heptachlor had been detected in most of the samples from almost all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of their persistence because of variance of monitoring sites, in addition to the fact that only two sites had been monitored, their persistence was still recognised. Surface water and bottom sediment: The Heptachlor and cis-Heptachlor had been detected in most of the samples from almost all the monitoring sites since FY2002 and FY2003, and their persistence was still recognised in widespread areas.

28

Figure 1-4-4-1 Detected Frequency and Detection Range of Heptachlors (Heptachlor)

V

B

A

W S

F

102/ 35/ 34/ 37/37

36 38

37/

97/ 36/ 9/

102 35 34 37

189134/

57/ 0/ 1/

186 189

7029/

114

50/70 70 10 10

138/

31

10

167/

23/

7/

28/ 16/38 30

Heptachlor (Air and Precipitation)

11231027

110

100

200

300

2002 2003(w) 2003(c) 2004(w) 2004(c)

Hep

tach

lor (

pg/m

3)

Heptachlor (Surface Water)

1.81.1 <20

10

20

30

2002 2003 2004

Hep

tach

lor (

pg/L

)

Heptachlor (Bottom Sediment)

2.52.43.50

50

100

150

200

2002 2003 2004

Hep

tach

lor (

pg/g

-dry

)

Heptachlor (Wildlife/Bivalves)

3.52.83.6

0

5

10

15

20

2002 2003 2004

Hep

tach

lor (

pg/g

-wet

)

Heptachlor (Wildlife/Fish)

1.9<2.24.00

100

200

300

400

500

2002 2003 2004

Hep

tach

lor (

pg/g

-wet

)

Heptachlor (Wildlife/Birds)

2.1

<1.4<2.2

0

2

4

6

8

10

2002 2003 2004

Hep

tach

lor (

pg/g

-wet

)

29

Figure 1-4-4-2 Detected Frequency and Detection Range of Heptachlors (cis-Heptachlor epoxide)

-

- -

S

B

V

W

A 3734/ 37/

F -

-

35 34 3131/

10/ 10/

153/ 136/

70/ 70/70 70 10 10-

37

36/ 38/36 38

37/35/

186 189

30/30

cis -Heptachlorepoxide (Air and Precipitation)

1.12.81.3

3.5

0

10

20

30

2002 2003(w) 2003(c) 2004(w) 2004(c)

cis

-Hep

tach

lore

poxi

de (p

g/m

3)

cis -Heptachlorepoxide (Surface Water)

109.80

50

100

150

200

2002 2003 2004

cis

-Hep

tach

lore

poxi

de (p

g/L)

cis -Heptachlorepoxide (Bottom Sediment)

4.440

50

100

150

200

250

2002 2003 2004

cis

-Hep

tach

lore

poxi

de (p

g/g-

dry)

cis -Heptachlorepoxide (Wildlife/Bivalves)

57420

200

400

600

800

1,000

2002 2003 2004

cis

-Hep

tach

lore

poxi

de (p

g/g-

wet

)

cis -Heptachlorepoxide (Wildlife/Fish)

46420

200

400

600

800

2002 2003 2004

cis

-Hep

tach

lore

poxi

de (p

g/g-

wet

)

cis -Heptachlorepoxide (Wildlife/Birds)

520

270

0

200

400

600

800

2002 2003 2004

cis

-Hep

tach

lore

poxi

de (p

g/g-

wet

)

30

Figure 1-4-4-3 Detected Frequency and Detection Range of Heptachlors (trans-Heptachlor epoxide)

-

-

-V

- 36 38

A

W S

4/ 0/

4/ 0/

35 34 37 3718/ 3/

F - 0/ 0/2/70 B

186 189

-0/70 10

0/ 1/

10

5/30 31

9/

trans -Heptachlorepoxide (Air andPrecipitation)

0.036

<0.2<0.2

<0.0330.0

0.1

0.2

0.3

0.4

2002 2003(w) 2003(c) 2004(w) 2004(c)

tran

s-H

epta

chlo

repo

xide

(pg/

m3)

trans -Heptachlorepoxide (Surface Water)

<0.3<0.40

1

2

3

4

5

2002 2003 2004

tran

s-H

epta

chlo

repo

xide

(pg/

L)

trans -Heptachlorepoxide (Bottom Sediment)

<2<3

0

1

2

3

4

5

2002 2003 2004

tran

s-H

epta

chlo

repo

xide

(pg/

g-dr

y)

trans -Heptachlorepoxide (Wildlife/Bivalves)

4.0<4.40

20

40

60

2002 2003 2004 tran

s-H

epta

chlo

repo

xide

(pg/

g-w

et)

trans -Heptachlorepoxide (Wildlife/Fish)

<4<4.4

0

2

4

6

8

10

2002 2003 2004 tran

s-H

epta

chlo

repo

xide

(pg/

g-w

et)

trans -Heptachlorepoxide (Wildlife/Birds)

0.0

0.2

0.4

0.6

0.8

1.0

2002 2003 2004

tran

s-H

epta

chlo

repo

xide

(pg/

g-w

et)

<4.4 <4

31

(5) Chlordanes A. cis-chlordane

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

32

Figure 1-4-5-1 Detected Frequency and Detection Range of Chlordanes (cis-Chlordane)

189189/189

70/ 70/ 10/ 10/10 10 10

189/

31/

10/70/70 70 70

38 30 3138/

186/186

37/37

38/38

B

V

S

30/

114/114

36/36

34/34

37/37

102/102

35/35A

W

F

cis -Chlordane (Air and Precipitation)

299230110310

500

1,000

1,500

2,000

2002 2003(w) 2003(c) 2004(w) 2004(c)

cis-

Chl

orda

ne (p

g/m

3)

cis -Chlordane (Surface Water)

9269410

500

1,000

1,500

2,000

2002 2003 2004

cis-

Chl

orda

ne (p

g/L)

cis -Chlordane (Bottom Sediment)

1401701200

10,000

20,000

30,000

40,000

2002 2003 2004

cis-

Chl

orda

ne (p

g/g-

dry)

cis -Chlordane (Wildlife/Bivalves)

1,2001,1008100

10,000

20,000

30,000

2002 2003 2004

cis-

Chl

orda

ne (p

g/g-

wet

)

cis -Chlordane (Wildlife/Fish)

5804905800

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

cis-

Chl

orda

ne (p

g/g-

wet

)

cis -Chlordane (Wildlife/Birds)

394767

0

100

200

300

400

500

2002 2003 2004

cis-

Chl

orda

ne (p

g/g-

wet

)

33

B. trans-chlordane

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

34

Figure 1-4-5-2 Detected Frequency and Detection Range of Chlordanes (trans-Chlordane)

V

B

A

W S

F 70/ 70/70 70

31

10

31/

10/

38/ 30/38 30

10/ 5/

189 186 189

10 10

189/ 186/ 189/114 36 38

102 35 34 37

70

37/

114/ 36/ 38/

102/ 35/ 34/ 37/

70/

37

trans -Chlordane (Air and Precipitation)

3511037130360

500

1,000

1,500

2,000

2002 2003(w) 2003(c) 2004(w) 2004(c)

tran

s-C

hlor

dane

(pg/

m3)

trans -Chlordane (Surface Water)

3234320

500

1,000

1,500

2002 2003 2004

tran

s-C

hlor

dane

(pg/

L)

trans -Chlordane (Bottom Sediment)

951201300

10,000

20,000

30,000

2002 2003 2004

tran

s-C

hlor

dane

(pg/

g-dr

y)

trans -Chlordane(Wildlife/Bivalves)

510550420

0

1,000

2,000

3,000

2002 2003 2004

tran

s-C

hlor

dane

(pg/

g-w

et)

trans -Chlordane (Wildlife/Fish)

1901501800

2,000

4,000

6,000

2002 2003 2004

tran

s-C

hlor

dane

(pg/

g-w

et)

trans -Chlordane (Wildlife/Birds)

141114

0

10

20

30

2002 2003 2004

tran

s-C

hlor

dane

(pg/

g-w

et)

35

C. Oxychlordane

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples of all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in most of the samples from all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas.

Birds: Although it is difficult to grasp the tendency of the persistence because of variance of the sites, in addition to the fact that only two sites had been monoitored, its persistence was still recognised. Surface water: The substance had been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance has been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

36

Figure 1-4-5-3 Detected Frequency and Detection Range of Chlordanes (Oxychlordane)

V

B 10

A

W S

F 70/70 70 70

38/38

31

10 10

37/ 30/ 31/

10/ 10/ 10/

38 30

129/189

70/ 70/

153/189

158/186

36/36

37/37

96/114

34/34

37/37

101/102

35/35

Oxychlordane (Air and Precipitation)

0.801.90.96 0.87

2.5

0

5

10

15

2002 2003(w) 2003(c) 2004(w) 2004(c)

Oxy

chlo

rdan

e (p

g/m

3)

Oxychlordane (Surface Water)

3.23.02.40

10

20

30

40

50

2002 2003 2004

Oxy

chlo

rdan

e (p

g/L)

Oxychlordane (Bottom Sediment)

2.022.20

50

100

150

2002 2003 2004

Oxy

chlo

rdan

e (p

g/g-

dry)

Oxychlordane (Wildlife/Bivalves)

11090760

2,000

4,000

6,000

2002 2003 2004

Oxy

chlo

rdan

e (p

g/g-

wet

)

Oxychlordane (Wildlife/Fish)

1501401600

1,000

2,000

3,000

4,000

2002 2003 2004

Oxy

chlo

rdan

e (p

g/g-

wet

)

Oxychlordane (Wildlife/Birds)

460750640

0

500

1000

1500

2002 2003 2004

Oxy

chlo

rdan

e (p

g/g-

wet

)

37

D. cis-nonachlor

Atmospheric air and precipitation: Cis-nonachlor had been subject to the monitoring programme since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on the monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of their persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in most of the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

38

Figure 1-4-5-4 Detected Frequency and Detection Range of Chlordanes (cis-Nonachlor)

37 V

W

A 102/ 35/ 34/ 37/ 37/ 38/ 30/102 35 34 37

188/189

114/ 36/ 38/ S

70/F 10/ 10/B70/ 70/70 70 10

186 189

70 10 10

184/ 189/114 36 38

31/

10/

38 30 31

cis -Nonachlor (Air and Precipitation)

2.7102.7123.10

50

100

150

200

250

2002 2003(w) 2003(c) 2004(w) 2004(c)

cis-

Non

achl

or (p

g/m

3)

cis -Nonachlor (Surface Water)

7.58.07.60

100

200

300

400

2002 2003 2004

cis-

Non

achl

or (p

g/L)

cis -Nonachlor (Bottom Sediment)

4659660

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

cis-

Non

achl

or (p

g/g-

dry)

cis -Nonachlor (Wildlife/Bivalves)

280290190

0

500

1,000

1,500

2,000

2002 2003 2004

cis-

Non

achl

or (p

g/g-

wet

)

cis -Nonachlor (Wildlife/Fish)

4103504200

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

cis-

Non

achl

or (p

g/g-

wet

)

cis -Nonachlor (Wildlife/Birds)

130

200200

0

200

400

600

800

2002 2003 2004

cis-

Non

achl

or (p

g/g-

wet

)

39

E. trans-nonachlor

Atmospheric air and precipitation: Trans-nonachlor had been subject to the monitoring programme since FY2002. The persistent concentrations of the the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on the monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves and fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of the persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

40

Figure 1-4-5-5 Detected Frequency and Detection Range of Chlordanes (trans-Nonachlor)

37/

114/ 36/ 38/

102/ 35/ 34/ 37/

10 10

114 36 38 189 186 189189/ 186/ 189/

31

10

31/

10/

38/ 30/38 30

10/ 10/

37

W

A 102 35 34 37

70 7070F 70/ 70/ 70/

S

B

V

trans -Nonachlor (Air and Precipitation)

23722487240

500

1,000

1,500

2002 2003(w) 2003(c) 2004(w) 2004(c)

tran

s-N

onac

hlor

(pg/

m3)

trans -Nonachlor (Surface Water)

2526290

500

1,000

1,500

2002 2003 2004

tran

s-N

onac

hlor

(pg/

L)

trans -Nonachlor (Bottom Sediment)

831001200

5,000

10,000

15,000

20,000

25,000

2002 2003 2004

tran

s-N

onac

hlor

(pg/

g-dr

y)

trans -Nonachlor (Wildlife/Bivalves)

710780

510

0

1,000

2,000

3,000

4,000

2002 2003 2004

tran

s-N

onac

hlor

(pg/

g-w

et)

trans -Nonachlor (Wildlife/Fish)

1,0008809700

5,000

10,000

15,000

20,000

25,000

2002 2003 2004

tran

s-N

onac

hlor

(pg/

g-w

et)

trans -Nonachlor (Wildlife/Birds)

680

1,100880

0

1,000

2,000

3,000

4,000

2002 2003 2004

tran

s-N

onac

hlor

(pg/

g-w

et)

41

(6) HCB

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence in birds because of vairiance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

42

Figure 1-4-6 Detected Frequency and Detection Range of HCB

102/ 35/ 34/ 37/

70/

37

114 36

70

114/ 36/ 38/

102 35 34 37

189 186

10

189/

70/ 70/70 70

31

10

31/

10/

38/ 30/38 30

10/ 10/10

18938

F

189/ 186/W

A 37/

S

B

V

HCB (Air and Precipitation)

9813094150990

800

1,600

2,400

3,200

2002 2003(w) 2003(c) 2004(w) 2004(c)

HC

B (p

g/m

3)

HCB (Surface Water)

3029360

500

1,000

1,500

2002 2003 2004

HC

B (p

g/L)

HCB (Bottom Sediment)

1301402100

10,000

20,000

30,000

40,000

50,000

2002 2003 2004

HC

B (p

g/g-

dry)

HCB (Wildlife/Bivalves)

3044230

200

400

600

800

2002 2003 2004

HC

B (p

g/g-

wet

)

HCB (Wildlife/Fish)

2201701400

500

1,000

1,500

2,000

2002 2003 2004

HC

B (p

g/g-

wet

)

HCB (Wildlife/Birds)

1,700970

1,000

0

1,000

2,000

3,000

4,000

5,000

2002 2003 2004

HC

B (p

g/g-

wet

)

43

(7) Mirex

Monitoring has been carried out since FY2003 to investigate mirex persisting in each of all the media. Japan has never produced or imported mirex. In FY2003 and FY2004, however, it was detected in all the samples of wildlife (bivalves, fish and birds) and atmospheric air from all the monitoring sites, as well as in samples of surface water and bottom sediment from half of the monitoring sites. Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2003. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2003, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2003, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2003, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence in birds because of vairiance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in most of the samples from most of the monitoring sites since FY2003, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in most of the samples from most of the monitoring sites since FY2003, and its persistence was still recognised in widespread areas.

44

Figure 1-4-7 Detected Frequency and Detection Range of Mirex

A

W S

F

- 35/ 34/ 37/ 37/

25/36 38-

35 34 37

137/-

V

B

37

153/

- 10/ 10/70/ 70/70 70

18/186 189

-

-

10 10

30/30 31

31/

Mirex (Air and Precipitation)

0.11

0.044 0.046

0.099

0.00

0.10

0.20

0.30

2002 2003(w) 2003(c) 2004(w) 2004(c)

Mire

x (p

g/m

3)

Mirex (Surface Water)

0.13 <0.20.0

0.5

1.0

1.5

2002 2003 2004

Mire

x (p

g/L)

Mirex (Bottom Sediment)

2.11.80

500

1,000

1,500

2,000

2002 2003 2004

Mire

x (p

g/g-

dry)

Mirex (Wildlife/Bivalves)

4.54.8

0

5

10

15

20

2002 2003 2004

Mire

x (p

g/g-

wet

)

Mirex (Wildlife/Fish)

117.90

50

100

150

200

2002 2003 2004

Mire

x (p

g/g-

wet

)

Mirex (Wildlife/Birds)

61

110

0

100

200

300

400

500

2002 2003 2004

Mire

x (p

g/g-

wet

)

45

(8) Toxaphenes

The persistence of toxaphens in birds is believed to be attributable to their prey and habitat, because Japan has never produced or imported toxaphens and they had not been detected in surface water nor bottom sediment. Atmospheric air and precipitation: The persistence of the substances has been monitored since FY2003. The persistent concentrations of Parlar-26 in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. Parlar-26 had been detected in all the samples from all the monitoring sites since FY2003, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: Parlar-26 and Parlar-50 had been detected in approvimately a half of the samples from the monitoring sites since FY2003, and their persistence was still recognised in widespread areas. Fish: Parlar-26 and Parlar-50 had been detected in more than a half of the samples from the monitoring sites since FY2003. Parlar-62 had been also detected in less raio. Their persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of their persistence in birds because of vairiance of the sites, in addition to the fact that only two sites had been monitored, their persistence was still recognised. Surface water: The substances had not been detected in all the samples from all the monitoring sites since FY2003. Bottom sediment: The substances had not been detected in all the samples from all the monitoring sites since FY2003.

46

Figure 1-4-8-1 Detected Frequency and Detection Range of Toxaphenes (Parlar-26)

W

-

44/ 54/70F

36 38-

V

B

A -

70-

35 34 3711/30 31

15/

5/ 5/

-S 186 189

10 10

0/

37/

0/ 0/

35/ 34/ 37/37

-

0/

Parlar-26 (Air and Precipitation)

0.31

0.170.27

0.15

0.0

0.2

0.4

0.6

0.8

2002 2003(w) 2003(c) 2004(w) 2004(c)

Parla

r-26

(pg/

m3)

Parlar-26 (Surface Water)

<3<20

0

20

40

60

80

100

2002 2003 2004

Parla

r-26

(pg/

L)

Parlar-26 (Bottom Sediment)

<20<30

0

20

40

60

80

100

2002 2003 2004

Parla

r-26

(pg/

g-dr

y)

Parlar-26 (Wildlife/Bivalves)

<14<150

10

20

30

40

2002 2003 2004

Parla

r-26

(pg/

g-w

et)

Parlar-26 (Wildlife/Fish)

40290

500

1000

1500

2002 2003 2004

Parla

r-26

(pg/

g-w

et)

Parlar-26 (Wildlife/Birds)

711100

500

1,000

1,500

2,000

2,500

2002 2003 2004

Parla

r-26

(pg/

g-w

et)

47


-

-

-

0/37

0/

A

W S

F

0/37

360/38

70

-

-

-

0/186

2/35

0/34

59/70

0/

V

B

189

10 10

17/

5/ 5/

30 3115/

55/


<0.4<0.4<0.27

<0.27

0.0

0.1

0.2

0.3

0.4

2002 2003(w) 2003(c) 2004(w) 2004(c)

Parla

r-50

(pg/

m3)


<7

<30

0

20

40

60

80

100

2002 2003 2004

Parla

r-50

(pg/

L)


<20

<50

0

20

40

60

80

100

2002 2003 2004

Parla

r-50

(pg/

g-dr

y)


1613

0

20

40

60

2002 2003 2004

Parla

r-50

(pg/

g-w

et)


54340

500

1,000

1,500

2002 2003 2004

Parla

r-50

(pg/

g-w

et)


831100

1,000

2,000

3,000

2002 2003 2004

Parla

r-50

(pg/

g-w

et)

48


3735 34 37

S

F

V

B

A

W

9/

0/

70 10

0/30 31

0/

5/ 5/

189

- -

0/ 0/36 380/ 0/

10

186-

-

24/

0/ 0/ 0/

-

-

70


<0.81<0.81

<0.52<0.52

0.0

0.2

0.4

0.6

0.8

1.0

2002 2003(w) 2003(c) 2004(w) 2004(c)

Parla

r-62

(pg/

m3)


<30<90

0

100

200

300

400

500

2002 2003 2004

Parla

r-62

(pg/

L)


<400<2,000

0

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

Parla

r-62

(pg/

g-dr

y)


<33<40

0

20

40

60

80

100

2002 2003 2004

Parla

r-62

(pg/

g-w

et)


<33<400

200

400

600

800

1,000

2002 2003 2004

Parla

r-62

(pg/

g-w

et)


6496

0

200

400

600

2002 2003 2004

Parla

r-62

(pg/

g-w

et)

49

(9) PCBs

Atmospheric air and precipitation: The persistence of the substances was monitored during FY2002 to FY2004. The persistent concentrations of the substances in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substances were detected in all the samples from all the monitoring sites in FY2002, FY2003 and FY2004, and their persistence was still recognised in widespread areas. Wildlife: Bivalves: Comparable detection limits were used in FY2002 and later, which allow the continuous evaluation of the results. Changes were made to the monitoring sites as follows: two sites were excluded in FY2003 (Mytilus edulis galloprovincialis [blue mussel] at the Miura Peninsula, and Septifer virgatus [purplish bifurcate mussel] at Mishima); one site was added in FY2004 (Mytilus edulis galloprovincialis [blue mussel] at Takamatsu Port in Kagawa Prefecture); and monitored species were changed at one monitoring site (Mytilus edulis galloprovincialis [blue mussel] Septifer virgatus [purplish bifurcate mussel] at Dokai Bay in Kitakyushu City). The substances were detected in all the samples from all the monitoring sites during FY2002-FY2004, and their persistence was still recognised in widespread areas. Fish: The substances were detected in all the samples from all the monitoring sites during FY2002-FY2004, and their persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of their persistence in birds because of variance of the sites, in addition to the fact that only two sites had been monitored, their persistence was still recognised. Surface water: The substances were detected in all the samples from all the monitoring sites during FY2002-FY2004, and their persistence was still recognised in widespread areas. Bottom sediment: The geometric means showed decreases in FY2002, FY2003 and FY2004. The substances were detected in all the samples from all the monitoring sites during FY2002-FY2004, and their persistence was still recognised in widespread areas.

50

Figure 1-4-9 Detected Frequency and Detection Range of PCBs (total)

10

38/ 30/30 31

10 1010/70/

70 70 7070/ 70/ 10/ 10/

38/38

189/189

186/186

189/189

114/114

36/36

37/37

37/37A

W

F

S

102/102

35/35

34/34

31/38V

B

PCB (Air and Precipitation)

1302401102601000

1,000

2,000

3,000

4,000

2002 2003(w) 2003(c) 2004(w) 2004(c)

PCB

(pg/

m3)

PCB (Surface Water)

6305304600

3,000

6,000

9,000

12,000

2002 2003 2004

PCB

(pg/

L)

PCB (Bottom Sediment)

7,3008,2009,2000

2,000,000

4,000,000

6,000,000

2002 2003 2004

PCB

(pg/

g-dr

y)

PCB (Wildlife/Bivalves)

7,70011,00010,0000

50,000

100,000

150,000

200,000

2002 2003 2004

PCB

(pg/

g-w

et)

PCB (Wildlife/Fish)

15,00011,00014,0000

200,000

400,000

600,000

2002 2003 2004

PCB

(pg/

g-w

et)

PCB (Wildlife/Birds)

8,900

18,000

11,000

0

10,000

20,000

30,000

40,000

50,000

2002 2003 2004

PCB

(pg/

g-w

et)

51

(10) DDTs A. p,p’-DDT

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance has been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

52

Figure 1-4-10-1 Detected Frequency and Detection Range of DDTs (p,p’-DDT)

V

B

A

W S

F 70/ 70/70 70

31

10

31/

10/

38/ 30/38 30

10/ 10/

189 186 189

10 10

189/ 186/ 189/114 36 38

102 35 34 37

70

37/

114/ 36/ 36/

102/ 35/ 34/ 37/

70/

37

p,p' -DDT (Air and Precipitation)

1.95.8 1.8

4.71.7

0

10

20

30

40

2002 2003(w) 2003(c) 2004(w) 2004(c)

p,p'

-DD

T (p

g/m

3)

p,p' -DDT (Surface Water)

1514120

200

400

600

800

2002 2003 2004

p,p'

-DD

T (p

g/L)

p,p' -DDT (Bottom Sediment)

3302402700

20,000

40,000

60,000

80,000

100,000

2002 2003 2004

p,p'

-DD

T (p

g/g-

dry)

p,p' -DDT (Wildlife/Bivalves)

280290200

0

1,000

2,000

3,000

2002 2003 2004

p,p'

-DD

T (p

g/g-

wet

)

p,p' -DDT (Wildlife/Fish)

3102103300

20,000

40,000

60,000

2002 2003 2004

p,p'

-DD

T (p

g/g-

wet

)

p,p' -DDT (Wildlife/Birds)

380 330

540

0

500

1,000

1,500

2002 2003 2004

p,p'

-DD

T (p

g/g-

wet

)

53

B. o,p’-DDT

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water and bottom sediment: The substance had been detected in most of the samples from mostly all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

54

Figure 1-4-10-2 Detected Frequency and Detection Range of DDTs (o,p’-DDT)

S

V

B70/ 70/70 70

38

3737/

31

10

31/

8/

38/ 30/38 30

10/ 10/

189 186 189183/ 185/ 189/

10 10

W

102 35 34

70/

114 36

A

F 70

114/ 36/ 29/

102/ 35/ 34/ 37/37

o,p' -DDT (Air and Precipitation)

6.9 5.11.5

1.62.2

0

10

20

30

40

50

2002 2003(w) 2003(c) 2004(w) 2004(c)

o,p'

-DD

T (p

g/m

3)

o,p' -DDT (Surface Water)

4.565.1

0

20

40

60

80

100

2002 2003 2004

o,p'

-DD

T (p

g/L)

o,p' -DDT (Bottom Sediment)

5243580

10,000

20,000

30,000

2002 2003 2004

o,p'

-DD

T (p

g/g-

dry)

o,p' -DDT (Wildlife/Bivalves)

130130

100

0

200

400

600

800

1,000

2002 2003 2004

o,p'

-DD

T (p

g/g-

wet

)

o,p' -DDT (Wildlife/Fish)

130801100

500

1,000

1,500

2,000

2,500

2002 2003 2004

o,p'

-DD

T (p

g/g-

wet

)

o,p' -DDT (Wildlife/Birds)

7.7

1810

0

20

40

60

80

2002 2003 2004

o,p'

-DD

T (p

g/g-

wet

)

55

C. p,p’-DDE

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

56

Figure 1-4-10-3 Detected Frequency and Detection Range of DDTs (p,p’-DDE)

35/35

70/ 70/70

37/37

114/114

34/34

37/37

102/102

18936/36

38/38

70

189/189

186/186

10 10 10B

189/

38/ 30/ 31/

10/ 10/ 10/

38 30 31VA

W S

F 70/70

p,p' -DDE (Air and Precipitation)

2.96.12.87.22.80

20

40

60

80

100

2002 2003(w) 2003(c) 2004(w) 2004(c)

p,p'

-DD

E (p

g/m

3)

p,p' -DDE (Surface Water)

3626240

200

400

600

800

2002 2003 2004

p,p'

-DD

E (p

g/L)

p,p' -DDE (Bottom Sediment)

6307106600

20,000

40,000

60,000

80,000

100,000

2002 2003 2004

p,p'

-DD

E (p

g/g-

dry)

p,p' -DDE (Wildlife/Bivalves)

1,000

1,1001,100

0

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

p,p'

-DD

E (p

g/g-

wet

)

p,p' -DDE (Wildlife/Fish)

2,5002,0002,5000

20,000

40,000

60,000

80,000

100,000

2002 2003 2004

p,p'

-DD

E (p

g/g-

wet

)

p,p' -DDE (Wildlife/Birds)

36,00063,000

34,000

0

50,000

100,000

150,000

200,000

250,000

2002 2003 2004

p,p'

-DD

E (p

g/g-

wet

)

57

D. o,p’-DDE

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in most of the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water and bottom sediment: The substance had been detected in most of the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

58

Figure 1-4-10-4 Detected Frequency and Detection Range of DDTs (o,p’-DDE)

V

B

A

W S

F 70/70

31/

10/ 9/ 5/

38 30 31

188/189

38/ 30/

38/38

70

184/189

186/186

10 10 10

37/37

113/114

34/34

37/37

102/102

35/35

70/ 67/70

36/36

o,p' -DDE (Air and Precipitation)

1.4 1.10.530.500.60

0

2

4

6

8

10

2002 2003(w) 2003(c) 2004(w) 2004(c)

o,p'

-DD

E (p

g/m

3)

o,p' -DDE (Surface Water)

32.22.30

200

400

600

800

2002 2003 2004

o,p'

-DD

E (p

g/L)

o,p' -DDE (Bottom Sediment)

3543460

10,000

20,000

30,000

2002 2003 2004

o,p'

-DD

E (p

g/g-

dry)

o,p' -DDE (Wildlife/Bivalves)

708488

0

500

1,000

1,500

2002 2003 2004

o,p'

-DD

E (p

g/g-

wet

)

o,p' -DDE (Wildlife/Fish)

6848770

5,000

10,000

15,000

2002 2003 2004

o,p'

-DD

E (p

g/g-

wet

)

o,p' -DDE (Wildlife/Birds)

28

1.02.00

10

20

30

40

50

2002 2003 2004

o,p'

-DD

E (p

g/g-

wet

)

59

E. p,p’-DDD

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in almost all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of its persistence in birds because of variance of the sites, in addition to the fact that only two sites had been monitored, its persistence was still recognised. Surface water: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Bottom sediment: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

60

Figure 1-4-10-5 Detected Frequency and Detection Range of DDTs (p,p’-DDD)

F

V

B

34/ 37/ 37/37A

W S

101/ 35/

114 36 38

102 35 34 37

114/ 36/ 189/

70/ 10/ 10/70/ 70/

38/189 186 189

70 70 70 10 10

189/ 186/

31

10

31/

10/

38/ 30/38 30

p,p' -DDD (Air and Precipitation)

0.120.240.130.300.12

0.0

0.5

1.0

1.5

2.0

2002 2003(w) 2003(c) 2004(w) 2004(c)

p,p'

-DD

D (p

g/m

3)

p,p' -DDD (Surface Water)

1919150

200

400

600

800

2002 2003 2004

p,p'

-DD

D (p

g/L)

p,p' -DDD (Bottom Sediment)

5505905400

20,000

40,000

60,000

80,000

2002 2003 2004

p,p'

-DD

D (p

g/g-

dry)

p,p' -DDD (Wildlife/Bivalves)

3003803400

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

p,p'

-DD

D (p

g/g-

wet

)

p,p' -DDD (Wildlife/Fish)

6405006100

4,000

8,000

12,000

16,000

2002 2003 2004

p,p'

-DD

D (p

g/g-

wet

)

p,p' -DDD (Wildlife/Birds)

310590560

0

1,000

2,000

3,000

4,000

2002 2003 2004

p,p'

-DD

D (p

g/g-

wet

)

61

F. o,p’-DDD

Atmospheric air and precipitation: The persistence of the substance has been monitored since FY2002. The persistent concentrations of the substance in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in FY2002 and in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Wildlife: Bivalves: The substance had been detected in all the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Fish: The substance had been detected in most of the samples from all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas. Birds: Although it is difficult to grasp the tendency of their persistence in birds because of variance of the sites, in addition to the fact that only two areas had been monitored, its persistence was still recognised. Surface water and bottom sediment: The substance had been detected in most of the samples from almost all the monitoring sites since FY2002, and its persistence was still recognised in widespread areas.

62

Figure 1-4-10-6 Detected Frequency and Detection Range of DDTs (o,p’-DDD)

F

V

B

34/ 37/ 37/37A

W

97/ 35/102 35 34 37

38/189 186114 36 38

113/ 36/

70/ 10/ 9/66/ 68/

189

70 70 70 10 10

184/ 186/ 189/S

31

10

31/

10/

38/ 30/38 30

o,p' -DDD (Air and Precipitaion)

0.140.31

0.150.370.14

0.0

1.0

2.0

3.0

2002 2003(w) 2003(c) 2004(w) 2004(c)

o,p'

-DD

D (p

g/m

3)

o,p' -DDD (Surface Water)

67.15.50

50

100

150

200

2002 2003 2004

o,p'

-DD

D (p

g/L)

o,p' -DDD (Bottom Sediment)

1201401400

5,000

10,000

15,000

20,000

2002 2003 2004

o,p'

-DD

D (p

g/g-

dry)

o,p' -DDD (Wildlife/Bivalves)

1602001300

1,000

2,000

3,000

2002 2003 2004

o,p'

-DD

D (p

g/g-

wet

)

o,p' -DDD (Wildlife/Fish)

10073830

500

1,000

1,500

2,000

2002 2003 2004

o,p'

-DD

D (p

g/g-

wet

)

o,p' -DDD (Wildlife/Birds)

5.6

1415

0

10

20

30

40

2002 2003 2004

o,p'

-DD

D (p

g/g-

wet

)

63

(11) PCDDs and PCDFs Atmospheric air and precipitation: The monitoring of PCDDs and PCDFs in the environmental air has been conducted in the scheme other than the “Environmental Survey and Monitoring of Chemicals” Programme – Environmental Survey on Dioxins (hereinafter referred to as “Dioxins Survey”). Dioxins Survey was operated under the supervision of other divisions/offices of MOE. In Dioxins Survey, more than nine hundred sites were targeted every year, and 48 sites among them were selected and fixed for continuous monitoring. The present report referrs to the data obtained at the 48 sites. The report of the Dioxins Survey for FY2004 said that the average value – 0.074pg-TEQ/m3 in FY2004 was significantly low comparing to the data in FY1997 (0.54pg-TEQ/m3). Wildlife: The monitoring of PCDDs and PCDFs has been conducted in the scheme other than the “Environmental Survey and Monitoring of Chemicals” Programme, which does not target bivalves, etc. Surface water: Dioxins Survey targeted 1,340 sites for continuously monitoring of PCDDs/PCDFs in surface water in FY2004. The average value in FY2004 – 0.22pg-TEQ/L was lower than those in FY2002 and 2003 (0.27 pg-TEQ/L and 0.24pg-TEQ/L, respectively). Bottom sediment: Dioxins Survey targeted 961 sites for continuously monitoring of PCDDs/PCDFs in bottom sediment in FY2004. The average value in FY2004 – 8.0 pg-TEQ/g was lower than those in FY2002 and 2003 (11 pg-TEQ/g and 8.9 pg-TEQ/g, respectively).

64

Figure 1-4-11 Detected Frequency and Detection Range of PCDDs/PCDFs

S

1,340/1,340A W 1,335/

1,3351,397/1,397

961/961

48/48

48/48

48/48

978/978

1,042/1,042

PCDDs/PCDFs (Air and Precipitation)

0.160.0740.077

0.0

0.1

0.2

0.3

0.4

0.5

2002 2003 2004

PCD

Ds/

PCD

Fs (p

g-TE

Q/m

3)

PCDDs/PCDFs (Surface Water)

0.220.240.270

2

4

6

8

10

2002 2003 2004

PCD

Ds/

PCD

Fs (p

g-TE

Q/L

)

PCDDs/PCDFs (Bottom Sediment)

8.08.9110

200

400

600

800

1,000

2002 2003 2004

PCD

Ds/

PCD

Fs (p

g/m

3)

65

CHAPTER 2

ENVIRONMENTAL SURVEY AND MONITORING OF OTHER POPs IN JAPAN 1. Target substances and areas This Chapter extracts and summerises the emvironmental survey and/or monitoring data on the chemicals relevant to 5 substances that were proposed for listing in Annex A of Stockholm Convention and considered at the firest meeting of the Persistent Organic Pollutants Review Committee (POPRC) held in November 2005, i.e., Pentabromodiphenyl ether, Chlordecone, Hexabromobiphenyl, Lindane and Perfluorooctane sulfonate (PFOS). Although the proposal was made for Lindane, this Chapter includes the obtained data on alpha, beta, gamma as well as delta isomers of HCH. The media covered by the surveys/monitorings for the substances during FY2002-2004 was as shown in Table 2-1-1. Table 2-1-1 Target Substances/Media for Other POPs Survey and Monitoring during FY2002-2004

Media

No. Target Substances Atmospheric Air &

Precipitation Wildlife Surface

Water Bottom

Sediment

1 Chlordecone X

2

HCHs α-HCH β-HCH γ-HCH δ-HCH

X X X X

3 Pentabromodiphenylether X X 4 Hexabromobiphenyl X X X 5 PFOS X X

2. Survey/monitoring results Summary of the detection results of the FY2002-2004 surveys and/or monitorings is shown in Table 2-2-1 to 2-2-4.

66

Table 2-2-1 Results of Other POPs Survey and Monitoring (Air and Precipitation) during FY2002-2004

SubstanceChlordecone <0 .5 <0 .5 <0 .5HCHs

α-HCH w 38 5,000 210 w 24 3,200 160c 13 1,400 49 c 11 680 68

β-HCH w 1 .1 97 9 .6 w 0 .53 110 6 .6c 14 57 2 .1 c 0 .32 78 2 .6

γ-HCH w 8 .8 2,200 63 w 4 .5 860 46c 14 330 14 c 2 .6 230 19

δ-HCH w 0 .48 120 5 .1 w 0 .15 93 2 .2c 0 .11 47 0 .97 c 0 .07(tr) 18 0 .76

Pentabromodiphenylether 0 .35 5 .4Hexabromobiphenyl <0 .25 <0 .25 <0 .25PFOS <0 .09 44

Legend and Note to this TableUnit is pg/m3.tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL), w = warm season (Aug.-Oct.), c = cold season (Nov.-Dec.)mean = geographical mean assuming the data less than MDL as a half of MDL.

- - -

- - -

- - -

MaxMeanFY2003FY2002

MeanMin Max Min Max

- -- - -

- - -

-

- - -

-

- - -- - -

- - -

- - -

-- - -

-- - -

- -

Air & Precipitation

- - - -

FY2004MeanMin

Table 2-2-2 Results of Other POPs Survey and Monitoring (Wildlife) during FY2002-2004 WildlifeSubstanceChlordeconeHCHs

α-HCH v 12 1,100 65 v 9 .9 610 45 v 12 (tr) 1,800 35f 1 .9(tr) 6,500 51 f 2 .6 590 41 f <4 .3 2,900 57b 93 360 160 b 30 230 70 b 58 1,600 120

β-HCH v 32 1,700 89 v 23 1,100 77 v 22 1,800 69f 5 (tr) 1,800 99 f 3 .5(tr) 1,100 78 f 3 .9(tr) 1,100 100b 1,600 7,300 3,000 b 1,800 5,900 3,400 b 1,100 4,800 2,200

γ-HCH v <1,000 <1,000 <1,000 v 5 .2 130 19 v <10 230 19 (tr)f <1,000 <1,000 <1,000 f 1 .7(tr) 130 16 f <10 660 27 (tr)b <1,000 <1,000 <1,000 b 3 .7 40 14 b 11 (tr) 1,200 34

δ-HCH v <1,000 <1,000 <1,000 v <1 .3 1,300 7 .2 v <1 .5 1,500 3 .0(tr)f <1,000 <1,000 <1,000 f <1 .3 16 3 .5(tr) f <1 .5 270 4 .1(tr)b <1,000 <1,000 <1,000 b 12 31 18 b 6 .4 260 16

PentabromodiphenyletherHexabromobiphenylPFOS

Legend and Note to this TableUnit is pg/g-wet.tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).v = bivalves (Mytilus edulis, Septifer virgatus or Mytilus coruscus).f = fish (Hexagrammos otakii, H. lagocephalus, Cololabis saira, Lateolabrax japonicus, Acanthopagrus sivicolus or Tribolodon hakonensis ).b = birds (Strunus cineraceus or Larus crassirostris ).mean = geographical mean assuming the data less than MDL as a half of MDL.

-

- -

-

-

-- - -

- -

- - -

- - - -

- - -- - - - - -- - -

- -- - - -Max

FY2002Mean

FY2003 FY2004Min Max Mean Min Max Mean Min

Table 2-2-3 Results of Other POPs Survey and Monitoring (Surface Water) during FY2002-2004

SubstanceChlordeconeHCHs

α-HCH 1 .9 6,500 84 13 970 120 13 5,700 150β-HCH 24 1,600 210 14 1,700 250 31 3,400 260γ-HCH 32 370 92 21 8,200 91δ-HCH 1 .1(tr) 200 14 1 .4(tr) 670 24

PentabromodiphenyletherHexabromobiphenyl <15 <15 <15PFOS 70 24,000 1,400

Legend and Note to this TableUnit is pg/L.tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).mean = geographical mean assuming the data less than MDL as a half of MDL.

- -

- -- -- --

- - -- - -- - - -

- - -

--

Surface Water

- -

- -

Max Mean

- -

- - - -

--

FY2002 FY2003 FY2004Min Max Mean Min Max Mean Min

67

Table 2-2-4 Results of Other POPs Survey and Monitoring (Bottom Sediment) during FY2002-2004

SubstanceChlordeconeHCHs

α-HCH 2 .0 8,200 130 2 9,500 140 1 .5(tr) 5,700 140β-HCH 3 .9 11,000 200 5 39,000 220 4 53,000 220γ-HCH 1 .4(tr) 4,000 45 0 .8(tr) 4,100 46δ-HCH <0 .7 5,400 37 0 .5(tr) 5,500 48

Pentabromodiphenylether 50 50 50Hexabromobiphenyl <8 .7 <8 .7 <8 .7PFOS

Legend and Note to this TableUnit is pg/g-dry.tr = value less than Method Quantification Limit (MQL) but over than Method Detection Limit (MDL).mean = geographical mean assuming the data less than MDL as a half of MDL.

FY2003 FY2004Min Max Mean Min Max Mean Min Mean

- - -

- - - - -

- - -

MaxBottom Sediment

- - -

FY2002

-

- - -

- -- - -

- - - -- -- - - - - - -

3. Assessment of survey and/or monitoring results The “Environmental Survey and Monitoring of Chemicals” Programme covered in its surveys and/or monitorings the 5 substances proposed for listing in Annex A of Stockholm Convention and considered at the firest meeting of the POPRC – Pentabromodiphenyl ether, Chlordecone, Hexabromobiphenyl, HCHs and Perfluorooctane sulfonate (PFOS). Results and assessment of the environment survey and/or monitoring for each substance (group) are described below. (1) Chlordecone

A survey of chlordecone in the environmental air was conducted in FY2003 for the first time in Japan. The detection limit was 0.5pg/m3. The sampling was done at 1 site, and the substance was not detected. No surveys and/or monitoring has been done for chlordane for other matrices – wildlife, surface water nor bottom sediment – in the Programme.

68

(2) HCHs

α-HCH β-HCH γ-HCH δ-HCH

Atmospheric air and precipitation: The persistence of the substances has been monitored since FY2003. The persistent concentrations of the substances in the warm season of FY2004 were comparable to those in the warm season of FY2003, while the values in the cold season of FY2004 were comparable to those in the cold season of FY2003. In FY2004, the values were higher in warm season than in cold season, as also seen in FY2003, showing differences in persistent concentrations depending on monitoring seasons and meteorological conditions. Each of α-HCH, β-HCH, γ-HCH and δ-HCH had been detected in all the samples from all the monitoring sites, and their persistence was recognised in widespread areas. Wildlife Bivalves and fish: The substances had been detected in more than a half of the samples from most of the monitoring sites since FY2003, and their persistence was still recognised in widespread areas. Till FY2002, ideal detection limits for γ-HCH and δ-HCH were not achieved, thus both substances were not detected in FY2002. Birds: α-HCH and β-HCH were detected in all the samples from all the monitoring sites in FY2002-FY2004, and their persistence was still recognised. No monitorings were conducted on γ-HCH and δ-HCH in FY2002 for the same reason as described in “Bivalves and fish” above. γ-HCH and δ-HCH were detected in all the samples from all the monitoring sites in FY2004 as well as in FY2003, and their persistence was recognised in widespread areas. Surface water: The substances had been detected in all the samples from all the monitoring sites since FY2002 (since FY2003 for γ-HCH and δ-HCH), and their persistence was still recognised in widespread areas. Bottom sediment: α-HCH and β-HCH had been detected in all the samples from all the monitoring sites since FY2002, and their persistence was still recognised in widespread areas. γ-HCH and δ-HCH were detected in most of the samples from nearly all the monitoring sites in FY2003 and in all the samples from all the monitoring sites in FY2004. Their persistence was recognised in widespread areas.

69

Figure 2-3-2-1 Detected Frequency and Detection Range of HCHs (α-HCH)

34/34 37

37/37

114/

35/35

37/

70/ 70/10

11436/36

38/38

10 10

38/ 30

10/ 10/

38 30 31

10/

A

W

F

S

V

B63/70 70 70

31-

189/189

189/189

186/186

α-HCH (Air and Precipitation)

68160492100

1,000

2,000

3,000

4,000

5,000

2002 2003(w) 2003(c) 2004(w) 2004(c)

α-H

CH

(pg/

m3)

α-HCH (Surface Water)

150120840

2,000

4,000

6,000

8,000

2002 2003 2004

α-H

CH

(pg/

L)

α-HCH (Bottom Sediment)

1401401300

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

α-H

CH

(pg/

g-dr

y)

α-HCH (Wildlife/Bivalves)

3545650

500

1,000

1,500

2,000

2002 2003 2004

α-H

CH

(pg/

g-w

et)

α-HCH (Wildlife/Fish)

5741510

2,000

4,000

6,000

8,000

2002 2003 2004

α-H

CH

(pg/

g-w

et)

α-HCH (Wildlife/Birds)

12070160

0

500

1,000

1,500

2,000

2002 2003 2004

α-H

CH

(pg/

g-w

et)

70

Figure 2-3-2-2 Detected Frequency and Detection Range of HCHs (β-HCH)

S

F

V

B

-A

W

37/ 37/

114 36 38

35/ 34/35 34 37 37

70/

114/ 36/ 38/

70

189/ 186/ 189/

10/ 10/

189 186 189

70/ 70/70 70 10 10

38/ 30/38 30 31

10

31/

10/

β-HCH (Air and Precipitation)

2.66.62.19.60

50

100

150

2002 2003(w) 2003(c) 2004(w) 2004(c)

β-H

CH

(pg/

m3)

β-HCH (Surface Water)

2602502100

1,000

2,000

3,000

4,000

2002 2003 2004

β-H

CH

(pg/

L)

β-HCH (Bottom Sediment)

2202202000

20,000

40,000

60,000

2002 2003 2004

β-H

CH

(pg/

g-dr

y)

β-HCH(Wildlife/Bivalves)

6977890

500

1,000

1,500

2,000

2002 2003 2004

β-H

CH

(pg/

g-w

et)

β-HCH (Wildlife/Fish)

10078990

500

1,000

1,500

2,000

2002 2003 2004

β-H

CH

(pg/

g-w

et)

β-HCH (Wildlife/Birds)

3,400

2,200

3,000

0

2,000

4,000

6,000

8,000

2002 2003 2004

β-H

CH

(pg/

g-w

et)

71

Figure 2-3-2-3 Detected Frequency and Detection Range of HCHs (γ-HCH)

W S

-

--

186 189

3734/ 37/ V

B

-

F

-A 30/30 31

28/

186/ 189/

70/ 55/70 70 10 10

10/ 10/

36 38-

35 34 37

36/ 38/

37/35/

γ-HCH (Air and Precipitation)

194614630

500

1,000

1,500

2,000

2,500

2002 2003(w) 2003(c) 2004(w) 2004(c)

γ-H

CH

(pg/

m3)

γ-HCH (Surface Water)

91920

2,000

4,000

6,000

8,000

10,000

2002 2003 2004

γ-H

CH

(pg/

L)

γ-HCH (Bottom Sediment)

46450

1,000

2,000

3,000

4,000

5,000

2002 2003 2004

γ-H

CH

(pg/

g-dr

y)

γ-HCH (Wildlife/Bivalves)

19190

50

100

150

200

250

2002 2003 2004

γ-H

CH

(pg/

g-w

et)

γ-HCH (Wildlife/Fish)

27160

200

400

600

800

2002 2003 2004

γ-H

CH

(pg/

g-w

et)

γ-HCH (Wildlife/Birds)

34140

500

1,000

1,500

2002 2003 2004

γ-H

CH

(pg/

g-w

et)

72

Figure 2-3-2-4 Detected Frequency and Detection Range of HCHs (δ-HCH)

--

35/

-

B

-VA

W

F

S

37/- 29/

70 70

3437/37

36/

25/30 31

10 10

189/- 189

59/ 10/ 10/

180/18636

38/38

34/35 37

54/

δ-HCH (Air and Precipitation)

0.762.20.975.10

50

100

150

2002 2003(w) 2003(c) 2004(w) 2004(c)

δ-H

CH

(pg/

m3)

δ-HCH (Surface Water)

24140

200

400

600

800

2002 2003 2004

δ-H

CH

(pg/

L)

δ-HCH (Bottom Sediment)

48370

2,000

4,000

6,000

2002 2003 2004

δ-H

CH

(pg/

g-dr

y)

δ-HCH (Wildlife/Bivalves)

3.07.20

500

1,000

1,500

2002 2003 2004

δ-H

CH

(pg/

g-w

et)

δ-HCH (Wildlife/Fish)

4.13.50

100

200

300

2002 2003 2004

δ-H

CH

(pg/

g-w

et)

δ-HCH (Wildlife/Birds)

16180

100

200

300

2002 2003 2004

δ-H

CH

(pg/

g-w

et)

73

(3) Pentabromodiphenyl ether

Atmospheric air and precipitation: A survey was conducted in FY2001 with a detection limit of 0.09 pg/m3, and the substance was detected at all of the surveyed sites (12 sites) with a detection range between 0.10-9.3 pg/m3. The survey conducted in FY2004 with a detection limit of 0.06 pg/m3 detected the substance at all of the surveyed sites (3 sites) with a detection range between 0.35-5.4 pg/m3. The persistence levels of the substance were comparable to the previous data. Bottom sediment: A Survey of the substance in bottom sediment was conducted for the first time in FY2004 with a detection limit of 0.035 ng/g-dry, and the substance was detected at one of the four survey sites with a detection value of 0.050 ng/g-dry. Pentabromodiphenyl ether has not been surveyed nor monitored for other media – wildlife and bottom sediment in the “Environmental Survey and Monitoring of Chemicals” Programme. (4) Hexabromobiphenyl

Atmospheric air and precipitation: A survey of this substance in the environmental air was conducted for the first time in FY2004 with a detection limit of 0.25 pg/m3. The substance was not detected at the surveyed site (1 site only). Surface water: A survey for hexabromobiphenyl in the surface water was conducted in FY2003. The detection limit was15pg/L. The substance was not detected any of the surveyed sites (4sites). Bottom sediment: A Survey of the substance in bottom sediment was conducted in FY2003 with a detection limit of 8,700 pg/g-dry, and the substance was not detected at any of the two surveyed sites. Hexabromobiphenyl has not been surveyed mor monitored for biota in the “Environmental Survey and Monitoring of Chemicals” Programme.

m+ n=5

74

(5) PFOS

Atmospheric air and precipitation: This was the first survey to investigate the substance persisting in atmospheric air. The survey was conducted with a detection limit of 0.09 pg/m3, and the substance was detected in 57 of the 60 samples from all the 20 survey sites, with a maximum detection concentration of 44 pg/m3. Surface water: A survey for PFOS in the surface water, which was the first environmental survey/monitoring for the substance in Japan, was conducted in FY2002. The detection limit was 40 ng/L. The substance was detected at all the surveyed sites (20 sites). Maximum concentration was 24,000pg/L. PFOS has not been surveyed nor monitored for biota and bottom sediment in the “Environmental Survey and Monitoring of Chemicals” Programme.

75

Appendix Analytical Methods for “12 POPs” Monitoring

AirSampled by high-volume air sampler (HV) with quartz-fiber-filter (QFF),polyurethane form (PUF) and active carbon felt (ACF) sorbent media.

RemarksAnalytical Method / Flow ChartSubstance

PCBsDDTsp,p’-DDTp,p’-DDEp,p’-DDDo,p’-DDTo,p’-DDEo,p’-DDD

HCBDrinsAldrinDieldrinEndrin

Chlordanestrans-Chlordanecis-Chlordanetrans-Nonachlorcis-NonachlorOxychlordane

HeptachlorsHeptachlortrans-Heptachlor epoxidecis-Heptachlorepoxide

MirexToxapheneParlar-26Parlar-50Parlar-62

HCHsα-HCHβ-HCHγ-HCHδ-HCH

Other than toxapheneGC/HRMS Column : DB-17HT

Length : 30mI.D. : 0.32mmFilm thickness : 0.15μm

GC/LRMS Column : HT8


ToxapheneGC/NICI-MS Column : HT8-PCB


PCBs GC/HRMSColumn : HT8-PCB


5mL

Dieldrin, Endrin

Hexane redissolution

Florisil column chromatography

Fr.1

Florisil 10g Anhydrous sodium sulfate 2g Washing : 5% Diethylether / hexane Elution : Fr.1 5% Diethylether / hexane 100mLElution : Fr.2 20% Diethylether / hexane 100mL

Fr.2

Concentration

N2gas blow 500μL

Internal standard(syringe spike)

Concentration

Rotary evaporator 30℃, 5mL

GC/HRMSGC/LRMS

PCBs, DDTs, HCB, Aldrin, Chlordanes, Heptachlor, trans-/cis-Heptachlor epoxide, Mirex, Toxaphene, HCHs

Method (B)

Multilayer silica gel column chromatography

Silica gel 0.9g 2%-KOH / silica gel 3g Silica gel 0.9g 44%-H2SO4 / silica gel 4.5g 22%-H2SO4 / silica gel 6g Silica gel 0.9g Anhydrous sodium sulfate 6g Washing : Hexane Elution : Hexane 120mL

Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Method (C)

N2gas blow 500μL



Fr.4

Silica gel column chromatography

Fr.3

PCBs, HCB Aldrin, Mirex

Silica gel 5g Anhydrous sodium sulfate 2g Washing : Hexane Elution : Fr.3 Hexane 30mL Elution : Fr.4 25% Diethylether / hexane 30mL

Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

N2gas blow 500μL


Concentration

GC/HRMSGC/LRMS

DDTs, Chlordanes, Heptachlor, trans-/cis-Heptachlor epoxide*, Toxaphene, HCHs


Fr.1

Florisil 5g Anhydrous sodium sulfate 2g Washing : 5% Diethylether / hexane Elution : Fr.1 20% Dichloromethane / hexane 80mLElution : Fr.2 Dichloromethane 150mL

Fr.2

Dieldrin, Endrin, trans-/cis-Heptachlor epoxide

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS

PCBs, DDTs, HCB, Aldrin, Chlordanes, Heptachlor, Mirex, Toxaphene, HCHs

Method (A)

5mLHexane redissolution

Sample (QFF) Sample (PUF) Sample (ACF)Add surrogate

Soxhlet extraction Soxhlet extractionSoxhlet extraction

Acetone 2～3hrs Toluene 16～24hrs

Acetone 16～24hrs Acetone 2～3hrs Toluene 16～24hrs

Dehydration

Rotary evaporator Hexane 5mL

Concentration / Redissolution

For PCBsFor all target substancesFor all target substances

* in method (B)

Choose from method (A) or (B) or (C)

76

Wildlife (1)
















5mL

Dieldrin, Endrin



Fr.1


Fr.2

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (A-2)



Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Method (A-3)

N2gas blow 500μL



Fr.4


Fr.3



Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

N2gas blow 500μL


Concentration

GC/HRMSGC/LRMS



Fr.1


Fr.2


Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (A-1)


Choose from method (A-1) or (A-2) or (A-3)

Method (A) For all target substances


Anhydrous sodium sulfate Dehydration / grinding

Sample

Add surrogate

Soxhletextraction

Dichloromethane 6hrs

20g (wet base)

Dehydration Anhydrous sodium sulfate

Rotary evaporator Hexane, 5～20mL

* in method (A-2)

77

Wildlife (2)
















Method (B) For all target substances

Shaft of homogenizer

Extract

33% Acetone / hexane 80mL 2min

Homogenizer extraction

Sample

Add surrogate

Washing

20g (wet base)

Shaking

Still standing

Purified water 200mL Slowly

Gel permeation chromatography

BioBeads S-X3 50g 50% Dichloromethane / cyclohexane5mL/min

Centrifugal separation

2500rpm, 5min

33% Acetone / hexane 20mL

Aqueous phase

Rotary evaporator Hexane 5mLConcentration

residual

33% Acetone / hexane 100mL 2min

Homogenizer extraction

Centrifugal separation

2500rpm, 5min

Hexane phase



Shaking

Still standing

Purified water 100mL Slowly

Aqueous phaseHexane phase

Concentration



Concentration

Shaking

Still standing

5min

Acetonitrile phase Hexane phase

Saturated acetonitrile with hexane 50mL 5min

Shaking

Still standing

5min

Saturated acetonitrilewith hexane 50mL 5min

Acetonitrile phase Hexane phase

Shaking

Still standing

5min

2% NaCl 500mL Hexane 50mL 5min

Hexane phase Aqueous phase

Shaking

Still standing

5min

Hexane 50mL 5min

Hexane phase Aqueous phase

Choose from method (B-1) or (B-2)

Method (B-1)

Method (B-2)* * There is a possibility of decreasing HCB recovery rate.

Choose from method (B-3) or (B-4) or (B-5)

78

Wildlife (3)
















5mL

Dieldrin, Endrin



Fr.1


Fr.2

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (B-4)



Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Method (B-5)

N2gas blow 500μL



Fr.4


Fr.3



Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

N2gas blow 500μL


Concentration

GC/HRMSGC/LRMS



Fr.1


Fr.2


Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (B-3)


* in method (B-4)

79

Wildlife (4)
















Residual

Washing50% Ethanol / hexane 20ml Hexane 30mL Hexane 50mL

Method (C) For PCBs

Liquid solution

Sample

Add surrogate

alkaline degradation

1.2mol/L KOH / ethanol 50mL 12hrs at room temperature or 1hr at 80℃

20g (wet base)

Extract


Filtrate

Glass fiber filter Filtration

Transfer 500mL separating funnel

Purified water 100mL 10minShaking

Still standing

Hexane 50mLShaking

Concentrated sulfuric acid 10mLShaking

Still standing

Remove sulfuric acid phase

Repeat until color of hexane phase fade out and sulfuric acid phase become clear

ShakingSaturated NaCl solution Equal amount of hexane

Still standing

Remove aqueous phase

Repeat 3times

Anhydrous sodium sulfate

Dehydration


Concentration

Choose from method (C-1) or (C-2) or (C-3)

80

Wildlife (5)
















5mL

Dieldrin, Endrin



Fr.1


Fr.2

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (C-2)



Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Method (C-3)

N2gas blow 500μL



Fr.4


Fr.3



Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

N2gas blow 500μL


Concentration

GC/HRMSGC/LRMS



Fr.1


Fr.2


Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (C-1)


* in method (C-2)

81

Surface water (1)
















Choose from method (D) or (E) or (F)

Method (E)Method (D) Method (F)

Sample

Add surrogate

Filtration / Solid phase extraction

Filter : GMF150 (Pore size : 2μm) Extraction disc : C18(FF)

Pressurized Fluid Extraction

Acetone, twice Toluene, twice Elution

Methanol 10mL, 3times Acetone 10mL, 3times Toluene 10mL, 3times

Ultrasonic extraction

Acetone 50mL 20min, 3times




Dichloromethane 100mL, twiceWashing

Dehydration / Concentration



Sample containerChoose from method (A) or (B)

Method (A) Method (B)

10L

82

Surface water (2)
















For PCBsFor all target substancesFor all target substances

5mL

Dieldrin, Endrin



Fr.1


Fr.2

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (E)



Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Method (F)

N2gas blow 500μL



Fr.4


Fr.3



Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

N2gas blow 500μL


Concentration

GC/HRMSGC/LRMS

DDTs, Chlordanes, Heptachlor, trans-/cis-Heptachlor epoxide, Toxaphene, HCHs


Fr.1


Fr.2


Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS


Method (D)


* in method (E)

83

Bottom sediment (1)
















Method (A-1) For all target substances

Ultrasonic extraction

Acetone 20min, twice

Soxhletextraction

10% acetone / toluene 18hrs

Sample 20g (dry base)

Add surrogate

Residual

ConcentrationConcentration

Acetone extract


Hexane, 20～30mL

Removeaqueous phase

Concentration 1mL

Transfer 100mL glass bottle Hexane 10mL

ShakingTetrabutylammonium sulfite 10mL 2-propanol 20mL 5min

ShakingAdd sodium sulfite 0.1g at a time until it remains after shaking

Still standing

Add purified water 50mL Over 5minShaking

Over 10min

Hexane 50mL Purified water 50mL 1min

Shaking

Removeaqueous phase

Removeaqueous phase

Purified water 50mL 1min Shaking

Removeaqueous phase

DehydrationAnhydrous sodium sulfate

20～30mL 20～30mL

Extract

100mL


Aqueous phase

Liquid-liquid extraction

Dichloromethane 20mL

Dehydration


Organic phase

Dehydration

Sample

Add surrogate

Soxhletextraction

Acetone 3hrs Toluene 18hrs

separating

20min

20g (wet base)

shaking

centrifugal separator



ConcentrationN2gas blow 1mL

ShakingTetrabutylammonium sulfite 10mL 2-propanol 2mL Over 1min

ShakingAdd sodium sulfite 0.1g at a time until it remains after shaking

Still standing

Add purified water washing by hexane 5mL Over 1min

Shaking

Transfer 50mL glass bottle

Over 5min

Removeaqueous phase

DehydrationAnhydrous sodium sulfate

Extract Rotary evaporator 5mL

Method (B-1) For all target substances

Method (A-2)

Method (B-2)

84

Bottom sediment (2)
















N2gas blow 500μL



Fr.2


Fr.1



Concentration


Concentration

GC/HRMSGC/LRMS

Concentration

DDTs, Dieldrin, Endrin, Chlordanes, Heptachlor, trans-/cis-Heptachlor epoxide, Toxaphene, HCHs

Method (A-2)

Extract

Dieldrin, Endrin


Fr.3


Fr.4

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS

DDTs, Chlordanes, Heptachlor, trans-/cis-Heptachlor epoxide, Toxaphene, HCHs

Concentration

N2gas blow 500μL


Concentration


GC/HRMS GC/LRMS



Fr.3 Fr.4

Concentration

N2gas blow 500μL


Concentration


GC/HRMSGC/LRMS

DDTs, Chlordanes, Heptachlor, Toxaphene, HCHs

Concentration

N2gas blow 500μL


Concentration


GC/HRMS GC/LRMS

Florisil 10g Anhydrous sodium sulfate 2g Washing : 5% Diethylether / hexane Elution : Fr.3 20% Dichloromethane / hexane Elution : Fr.4 Dichloromethane

Choose from method (A-3) or (A-4)

Method (A-4)

Method (A-3)

85

Bottom sediment (3)
















Carbon column chromatography


Silica gel 10g Anhydrous sodium sulfate 2g Washing : Hexane Elution : 5% Diethylether / hexane 100mL

Aliquot of 1/4

Method (B-2)

Extract

500μL


50%-H2SO4 / silica gel 5g Anhydrous sodium sulfate 2g Washing : Hexane Elution : Hexane 200mL

Concentration


Concentration

GC/HRMSGC/LRMS

PCBs, HCB, Mirex, DDTs, Chlordanes, HCHs and the others

Aliquot of 1/2 50mL 25mL


Hexane 1mL

ENVI-carb 250mg Washing : Hexane Elution : Hexane 10mL

Concentration

50μL


Concentration

GC/HRMS GC/LRMS

Aldrin, Dieldrin, Endrin, trans-/cis-Heptachlor epoxideand the others

86

Bottom sediment (4)
















Residual

Washing50% Ethanol / hexane 20ml Hexane 30mL Hexane 50mL

Method (C) For PCBs

Liquid solution

Sample

Add surrogate

alkaline degradation

1.2mol/L KOH / ethanol 50mL 12hrs at room temperature or 1hr at 80℃

20g (wet base)

Extract


Filtrate

Glass fiber filter Filtration

Transfer 500mL separating funnel

Purified water 100mL 10minShaking

Still standing

Hexane 50mLShaking

Concentrated sulfuric acid 30mLShaking

Still standing

Remove sulfuric acid phase

Repeat until color of hexane phase fade out and sulfuric acid phase become clear

ShakingSaturated NaCl solution Equal amount of hexane

Still standing

Remove aqueous phase

Repeat 3times

Anhydrous sodium sulfate Dehydration


Concentration



Concentration

N2gas blow 500μL


Concentration


GC/HRMS

Documents

Environmental Monitoring Report on Persistent Organic ... · 2 Environmental Monitoring Report on Persistent Organic Pollutants (POPs) in Japan 2002-2004 The information contained