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    Sources, Fates, andEnvironmental and Health Effectsof Persistent Toxic Substancesfrom E-waste Recycling

    Nepal August 2006

    MH Wong*

    Croucher Institute for Environmental Sciences,and Department of B iologyHong Kong Baptist University

    *[email protected]

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    Content

    General Introduction

    Objectives of our Group Research Progress of the Project

    Main Findings Conclusion

    Future Work

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    M a p o f Ch in a s h o w in g o u r s a m p lin g s it eM a p o f Ch in a s h o w in g o u r s a m p lin g s it e

    Taizhou City

    Guiyu Village

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    Primitive E-Waste Recycling

    Technologies

    Guiyu, PR China: A Case Study Since 1995, e-waste from US & elsewhere have

    been continuously transported to Guiyu &recycled by villagers

    Recycling operations

    - melting circuit boards over makeshift grills

    - acid stripping of printed circuit boards

    - burning wires to recover metals, etc.

    Works undertaken by men, women, and evenchildren with little or no protection to health

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    Open Burning of E-Waste

    PCDD/Fs

    PBDD/Fs

    PBDEs

    PAHs

    PCBs

    Heavy Metals

    Photos by CIES, 2004

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    Circuit Board Recycling

    Toxic lead-tin fumes

    Heavy metals

    Toxic respirablesuspended particulates

    (RSP)

    Photos by CIES, 2004

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    Acid Stripping of Chips & Printed Circuit Boards

    Photos by CIES, 2004

    HNO3

    HCl

    Cl2

    SO2

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    Daily Life in Guiyu

    Photos by CIES, 2004

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    Recycling transformer oil

    from e-wasteRiver water contaminated by

    transformer oil (with PCB)

    Taizhou City , Zhejiang Province

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    Burning of wire

    insulation to recover CuOpen burning to extract

    valuable metals from e-waste

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    Objectives Conduct environmental contamination evaluation of

    typical e-waste recycling sites

    Study body loading of different toxic chemicals in humanmilk, placenta and hair samples collected from workersand local residents

    Assess toxic effects of different toxic chemicals generatedduring the e-waste recycling processes, by means ofbioassay tests

    Assess fates of toxic chemicals, in different ecologicalcompartments; and uptake & bioaccumulation in workers

    (& local residents) using different models

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    (Infant)

    Wet and dry deposition

    Runoff

    Air Soil Surfacewater

    SedimentDust

    FishDucks

    VegetablesDucks

    Groundwater

    Drinking(Ingestion)

    (Ingestion)

    (Dermal)(Inhalation)

    (Inhalation)

    (Ingestion)(Dermal)

    (Inhalation)

    Food(Ingestion)

    Irrigation

    Plants

    Milk(Ingestion)

    Aquaticplants

    Food(Ingestion)

    Swimming(Dermal)

    Washingclothes(Dermal)Bathing and

    washingclothes(Dermal)

    (Adult) Humans (Child)

    E-waste pollution sources

    Exposure pathways from e-waste pollution sources tohumans

    P t ti l i t ti i t l

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    Potential interactions among source,environmental

    media, exposure media, and exposure routes in a

    multimedia, multiple pathway exposure assessment

    Source: Caltox, Department of Toxic Substances Control, California Environment Protection Agency,1993

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    Progress of Research

    Determined level of pollution in environmentalmedia and in biotia POPs & heavy metals in soil, sediment, air (TSP &

    PM2.5), roadside dust & workshop dust

    Soil maps

    POPs and heavy metals in fish (environmental anddietary exposure

    Human samples to investigate body loading (breastmilk, placenta, hair)

    Toxicological assessments (will not be reported)

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    Distribution of E-waste Recycling Activities

    AcidLeaching

    Printed CircuitBoards Baking

    PlasticRecycling

    Computer

    Dismantling

    Open Burning

    Beilin

    Longgang

    Yaocouwei

    Nanyang River

    Nanyang

    Ximei

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    I. Soil Pollution

    - Heavy metals

    - PAHs- PCBs

    - PBDEs

    - PCDD/Fs

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    Distributions of Pb and Cu in Soil

    Giyu Soil Survey

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    224

    348

    45.2

    653

    186

    1.66

    Mean

    43.9

    105

    17.9

    64.5

    152

    3.36

    Median Dutch standardGB 15618-1995

    720140500250100Zn

    5308550030035Pb

    210352005040Ni

    1903640010035Cu

    38010040030090Cr

    120.810.60.2Cd

    actionbackground

    Elevated trace metal concentrations in soils

    Some unsuitable for agricultural purposes

    Remedial actions required in some areas

    Heavy metals

    Comparison with regulatory

    standards (mg/kg)

    Giyu Soil Survey

    Guiyu Soil Survey

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    Total PAHs in Guiyu Soils

    Near open burningsites: average PAHs =1400 g/kg (highest 3200g/kg).

    Near circuit board

    heating site: PAHs concwere 1000 g/kg.

    Reservoir & forests:low levels of PAHs - no point

    sources of pollution.

    Guiyu Soil Survey

    Guiyu Soil Survey

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    Comparison with published data - PAHs

    This study58232064549Guiyu, China

    Bucheli et al, 20042256195023Switzerland

    Wilcke et al, 200373347547Brazil

    Nam et al, 2003236283423.3226South Korea

    Wilcke & Amelung,

    20001423216318

    North American

    (20 PAHs)

    Zhang et al, in

    press

    55410753Hong Kong, China

    Hao et al, 2004317125722131Shantou, China

    Chen et al, 2004298616603Hangzhou, China

    Chen et al, 200537630774243Guangzhou, China

    MeanHighestLowest

    References

    Total 16 PAHs concentration(g/kg)No. of

    sampleLocation

    Guiyu Soil Survey

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    Soil guidelines for PCDD/Fs

    Environmental quality

    standard (2003)

    Sweden

    Guideline interim value

    Environmental quality

    guidelines (2003)

    Preliminary remediation goal

    (2000)

    Guideline/Standard AgricultureResidentialCountry

    10 pg I-TEQ/g1500 pg I-TEQ/gNewZealand

    10 pg I-TEQ/g10 pg I-TEQ/gSweden

    1000 pg

    WHO-TEQ/g

    1000 pg WHO-

    TEQ/g

    Japan

    4 pg-TEQ/g4 pg-TEQ/gCanada

    ---1000 pg-TEQ/gUS

    X X

    X

    X

    X

    X

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    Comparison of PCDD/Fs in soils from

    dump sites in Asian countries

    0

    2000

    4000

    6000

    8000

    10000

    12000

    14000

    16000

    Guiyu Philippines Guiyu Cambodia Vietnam

    (Hanoi)

    India Vietnam

    (Ho ChiMinh)

    PCDD/Fconcentratio

    n(pgWHO-TE

    Q/g)

    Minh et al., 2003

    Open burn sites

    Acid leaching site

    28x higher than

    Philippines

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    Deca-BDE (BDE-209) was the most dominant homologue/congener accounting

    for35-82% of total PBDEs

    PBDE Homologue Concentrations (ng/g, dry wt, n=3)

    Soil Combusted residue

    PBDE ReservoirRice

    fieldDuck

    pond

    Printer roller

    dump site

    Acid

    leaching

    Open

    burning site

    Riverbank

    Homologues

    Total Mono-BDE ND 0.116 0.115 0.080 23.1 88 2.64

    Total Di-BDE 0.017 0.367 0.417 0.631 71.8 251 13.4Total Tri-BDE 0.054 0.769 1.00 4.05 167 598 39.4

    Total Tetra-BDE 0.351 1.31 3.99 150 263 1100 55.0

    Total Penta-BDE 0.276 0.665 2.82 411 426 1111 64.4

    Total Hexa-BDE 0.103 1.01 6.35 81.70 378 809 1507

    Total Hepta-BDE 0.086 2.62 20.1 128 357 1473 3060

    Total Octa-BDE 0.090 1.93 17.0 104 332 1010 6359

    Total Nona-BDE 0.102 2.05 18.8 50.9 283 1051 3550

    Total Deca-BDE 2.76 37.3 328 510 1269 16160 48633

    Total PBDEs 3.80 48.2 398.0 1440 3570 23640 63300

    18x

    USEPA standard in residential soil warranting preliminary remediation

    USEPA standard in industrial soil warranting preliminary remediation

    Penta BDE BDE-209

    120,000 610,000

    1,200,000 6,200,000

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    Profiles of PBDE congeners in soil samples

    0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    BDE-47 BDE-49 BDE-66 BDE-99 BDE-100 BDE-153 BDE-154 BDE-183 BDE-197 BDE-203 BDE-207 BDE-209

    PBDE c ongen ers

    %

    PBDE

    congenertototalPBDEs

    ReservoirRice fieldD uck pond

    P rinter roller d ump siteA cid lea chingOp en b urning siteRiverbank

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    Comparison with other PBDE soil studies(ng/g, dry wt.)

    274 - 32746

    Guiyu:

    34.7 - 97400

    76

    Guiyu: 56x

    0.07 - 12

    Guiyu: 2 - 6.2

    Concentration

    Greenpeace China,2005

    HKE-wastestorage site

    Hale et al., 2002USANon e-wastesite: near foam

    manufacturing

    plant

    Hassanin et al., 2004UKBackground

    (grassland/

    woodland)

    ReferenceConcentrationDescription

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    Mass Concentration in Air Samples Collected

    from Guiyu

    47.3

    30.9

    139

    GZ

    Site 2

    51.132.744.950.5PM2.5 (Teflon)

    65

    (USEPA)

    40.231.949.962.1PM2.5 (Quartz)

    260(HK)

    16257.880.1124.1TSP

    GuidelineGZ

    Site 1

    HK

    Site 2

    HK

    Site 1

    Guiyu(g/m3 )

    TSP: Guangzhou (GZ) > Guiyu > Hong Kong (HK)

    PM2.5: Guiyu > Guangzhou > Hong Kong

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    Tianhe ~Hok Tsui

    Liwan > Yuen Long

    (1.3 times)

    Guiyu > Yuen Long

    (2.8 times)

    Guiyu (conc of PCDD/Fs)

    above Japanese standard0.0

    0.1

    0.2

    0.3

    0.4

    0.5

    0.6

    0.7

    Beilin Liwan Tianhe Yuen Long Tsuen Wan Hok Tsui

    ConcentrationofPCDD/Fs

    (pg

    WHO-TEQ/m3)

    China Hong Kong

    Japan: 0.6 pg TEQ/m30.65

    0.35

    0.10

    0.230.14

    0.07

    Guiyu

    Dioxins Levels in Air Particulates from Guiyu

    Compared with Hong Kong & Guangzhou

    Comparison of dioxins levels in S China with air quality standards

    0

    10

    20

    30

    40

    50

    60

    Beilin Liwan Tianhe Yuen Long Tsuen Wan Hok Tsui

    Concentrationof2,3,7,8-TCDD

    (fg/m3)

    China Hong Kong

    USA (Indiana, Kansas and Washington): 30 fg/m3

    54

    Guiyu

    9.84.6

    10.25.3 4.8

    Tianhe ~ Hok Tsui

    ~Tsuen WanLiwan ~ Yuen Long

    Guiyu >>HK

    Guiyu above USA guideline

    September 2004

    September 2004

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    Pb in atmospheric particulates

    0

    100

    200

    300

    400

    500

    600

    700

    800

    900

    TH LW BL YL TW HT

    Pbconcentrations(ng/m3)

    Hong KongGuangzhou

    GuiyuPM2.5

    TSP

    A large frac tion of Pb in the form of PM2.5 a grea ter hea lth risk!

    Summer 2004

    Inhalab le partic ulates!

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    III. Water Bodies- Heavy metals

    - PBDE- PCBs

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    Heavy metals in the sediments collected

    from Lianjiang River

    628590543453574.910.3Max

    31591.3N.A.19790.03.50CCME (PEL)*

    12179.526.012548.6n.d.Min

    156

    165

    181

    Ni

    1208

    512

    1068

    Cu

    28413753.93.94Median

    1431698.973.92Stand dev

    32423057.74.09Mean

    ZnPbCrCdmg/kg

    *Canadian Environmenta l Quality Guidelines, Prob able e ffec t levels

    Total Hg in Sediment of G i

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    Total Hg in Sediment of Guiyu

    0

    0.2

    0.4

    0.6

    0.8

    1

    1.2

    1.4

    1.6

    1.8

    1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

    Sample number

    T

    otalHg(ug/g)

    Lianjiang

    RiverNanyang

    River

    Open

    burn site

    Reservoir

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    0%

    10%

    20%

    30%

    40%

    50%

    60%

    BDE-28 BDE-47 BDE-66 BDE-100 BDE-99 BDE-154 BDE-153 BDE-183

    LJ-Tilapia NY-Crucian NY-BH

    ng/g w. w Bighead Carp-muscles Bighead Carp-abdomen LianJiang-Tilapia

    Medium Largest Lowest Medium Largest Lowest Medium Largest Lowest

    BDE-28 7.64 9.50 5.35 203.72 438.43 48.22 13.41 22.62 8.77

    BDE-47 18.95 21.89 12.97 465.28 955.16 136.27 69.04 110.40 42.94BDE-100 0.65 0.73 0.48 15.66 33.69 3.45 3.58 5.40 2.13

    BDE-99 0.25 0.64 0.07 5.87 11.67 2.37 3.99 8.33 1.73

    BDE-154 0.54 0.62 0.49 6.68 13.08 1.37 8.83 21.05 4.02

    BDE-153 0.56 1.43 0.14 11.75 22.97 2.52 5.27 10.38 2.64

    BDE-183 0.01 0.02 0.00 0.15 0.36 0.00 0.01 0.08 0.00

    Total BDE 34.22 45.01 24.49 802 1628 228 114 196 69.57

    PBDE Congeners in Fish Samples

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    IV. Roadside andWorkshop Dust

    - Heavy metals

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    Intensive study (8 study sites)

    1. Inside workshops 2. Street of workshops

    4. School3. Main trunk road

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    5. Outdoor food market

    6. Longgang

    7. Gurao 8. Shantou University

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    1

    10

    100

    1000

    10000

    100000

    1000000

    PCBR

    W(n

    =12)

    StreetB-

    2-1(

    n=16)

    StreetB-

    2-2(

    n=16)

    Scho

    olya

    rd(n=4

    )

    Near

    scho

    ol(n=4

    )

    Food

    market(

    n=14)

    Long

    gang

    (n=8)

    Gurao(

    n=16)

    Shantou

    Univ

    ersity(

    n=12

    )

    Pbcon

    centration(mg/kg

    Pb in dust

    110000

    632

    530

    530

    85

    de cef

    d

    f

    f

    ab

    f

    Guiyu Outside

    Guiyu

    140

    Exceedenceof New DutchList ActionValue forLead

    >200x!

    New Dutch List ActionValue (The Netherlands)

    New Dutch ListOptimum Value

    Canadian Environmental QualityGuideline Residential/park

    New Dutch List ActionValue (The Netherlands)

    New Dutch ListOptimum Value

    Logarithmic scale

    99x thanPb/Zn mine

    tailings

    Guangdongprovince

    50x Korean

    abandoned

    mines

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    1

    10

    100

    1000

    10000

    100000

    PCBR

    W(n

    =12)

    Stree

    tB-2-1(

    n=16)

    StreetB-

    2-2(n=16)

    Scho

    olyard

    (n=4)

    Near

    scho

    ol(n=

    4)

    Food

    market(

    n=14)

    Longga

    ng(n=8)

    Gurao(

    n=16)

    S

    hanto

    u Univ

    ersity

    (n=12)

    Cuconcentration(mg/kg)

    Cu in dust

    190

    36

    a

    de

    b

    cdde

    dee

    c

    e 63

    ALL exceedsNew Dutch

    List ActionValue forcopper

    CEQG Residential/park(Canada)

    New Dutch List ActionValue (The Netherlands)

    New Dutch ListOptimum Value

    Logarithmic scale

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    Heavy metals in dust:

    Estimation of non-cancer toxic risk (HI)

    Hazard index

    ADDingest ADDdermal ADDinhale RfDoral RfDdermal RfDinhale HQingest HQdermal HQinhale HI

    Cd 4.58E-05 3.65E-07 1.35E-08 0.001 1.00E-05 - 0.046 0.0365 1.350E-05 0.082

    Co 3.82E-05 3.05E-07 1.12E-08 0.02 0.016 5.71E-06 0.002 1.910E-05 0.002 0.004

    Cr 1.40E-04 1.12E-06 4.13E-08 0.003 6.00E-05 2.86E-05 0.047 0.019 0.0014 0.067

    Cu 0.025 1.96E-04 7.21E-06 0.04 0.012 - 0.61 0.016 1.800E-04 0.63Mn 9.90E-04 7.90E-06 2.91E-07 0.046 0.00184 1.43E-05 0.022 0.004 0.02 0.046

    Ni 0.0055 4.35E-05 1.60E-06 0.02 0.0054 - 0.27 0.008 8.020E-05 0.28

    Pb 0.141 1.13E-03 4.15E-05 0.0035 5.25E-04 - 40.3 2.2 0.012 42.5

    Zn 0.0070 5.56E-05 2.05E-06 0.3 0.06 - 0.023 9.260E-04 6.830E-06 0.02

    HI 41.40 2.23 0.036 43.6

    (mg/kg/day)

    Reference doseAverage daily dose

    (mg/kg/day)

    Hazard quotient

    Scenario: Adult worker - printed circuit board workshop

    Pb:

    HQ (dust ingestion) exceeded the safereference dose level by > 40x

    92% of the total HI

    For child, exceeded safe level by 753x !

    19x than for adult scenario.

    Impaired mental &

    physical development

    Neurological Problems

    AutismIQ

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    PCDD/F i h i f T i h

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    PCDD/Fs in hair from Taizhou

    E-waste recycling site sig. higher than control site

    (t-test, P < 0.05, 2-tailed)

    Human hair

    0

    10

    20

    30

    40

    50

    60

    70

    TZ_H_Ave H5 H1

    7H2

    1H2

    2H2

    3

    HZ_H_Ave

    H27

    H28

    H31

    H50

    Hair

    pgWHO-PCDD/F-TEQ/g

    drywt

    Control site (HZ)

    a

    E-waste recycling site (TZ) b

    PBDEs in human specimen

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    PBDEs in human specimen

    collected from Zhejiang

    0

    20000

    40000

    60000

    80000

    100000

    120000

    TZ_Ave #5 #17 #21 #22 #23 HZ_Ave #27 #28 #31 #33 #50

    Samples

    PBDEs(pg/gdw

    )

    Human milk Placenta Hair490,000 pg/g, dw

    E-waste recycling site, i.e. Taizhou

    Sig. correlation (Spearmans) betweenHuman milk & placenta (P < 0.001)

    Human milk & hair (P < 0.001)

    Placenta & hair (P < 0.05)

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    PBDEs in human milk: Comparison

    with other studies (1998-2005)

    0

    10

    20

    30

    40

    50

    60

    70

    80

    USA

    Taizh

    ou,Chi

    na

    Cana

    da

    Japa

    n

    Faro

    eIs

    land UK

    Swed

    en

    Mal

    aysi

    a

    Phili

    ppin

    es

    Kore

    a

    Cambo

    dia

    Indo

    nesia

    H

    angz

    hou,

    Chi

    na

    Viet

    nam

    Indi

    a

    Rus

    sia

    (Bur

    yatia

    )

    Region/country

    PBDEs(n

    g/glipidwt)

    BDE-47 BDE-99 BDE-100 BDE-153

    E-waste recycling site

    Control site

    Comparison on concentration of PCBs in food

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    Comparison on concentration of PCBs in food

    samples from two e-waste sites

    PCB levels in fish and seafood

    0

    20

    40

    60

    80

    100

    loach

    CrucianCarp crab

    Chinesesnakehead

    bloodclam

    yellowcroakerMudsnail

    whiteshrimpPomfretspiralmulletBighead

    CrucianCarpTilapiaMudcarp

    Grasscarp

    SilverCarp

    BlackCarp

    Commoncarp

    bloodclam

    Food items

    PCBconcentrations(ng/gwetwt)

    TZ GY

    Fish and seafood

    In general, TZGY=0

    PCB l l i h l f T i h

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    PCB levels in human samples of Taizhou

    and Lin'an (control site)

    0

    50

    100

    150

    200

    250

    300

    350

    400

    450

    H air P lacenta M ilk

    P

    C

    B

    c

    o

    n

    c

    .

    (n

    g

    /g

    d

    ry

    w

    t)

    TZ

    LA

    PCB levels in human samples of Taizhou

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    Relationship between different human

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    Relationship between different human

    samples (PCBs)

    Good relationship between average pattern of different human samples

    However, total PCB Levels in different persons do not correlate well for tissues

    Relationship of PCB level in human milk and placenta of

    TZ

    R2 = 0.5329

    0

    20

    40

    60

    80

    100

    120

    140

    0 5 10 15

    Placenta (ng/g dry wt)

    Mil

    k

    (ng

    /g

    dry

    wt)

    Relationship of PCB levels in human milk and hair of TZ

    y = 0.2178x - 0.4094

    R2 = 0.9308

    -20

    0

    20

    40

    60

    80

    100

    120

    140

    0 100 200 300 400 500

    Hair (ng/g dry wt)

    Milk

    (ng

    /g

    dry

    wt)

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    Total Hg in hair and placenta (Guiyu)

    Guiyu (34) 0.132-1.47

    Korea 1.1-1.7

    Japan 2.02-2.98Hong Kong 1.57-3.97

    Malaysia 3.38

    Quebec 2.4-3.7

    Columbia 1.33-2.4Sweden 0.9

    Finland 2.1

    Hair

    (g/g)Placenta

    (g/g)

    Guiyu (25) ND 0.0418 g/g

    Ave.= 0.0152 0.0093Ave = 0.492 0.278

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    C l i

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    Conclusions

    PBDE and PCB concentrations in fish and PCDD/Fs in

    human milk suggest bioaccumulation and

    biomagnification

    Bioassay tests using human cell lines demonstrate

    cytotoxic effects due to Guiyu pollution

    The first detailed study on PTS and heavy metals and

    human health risk assessment of an e-waste site

    Research Grant:

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    Team Members:

    Prof MH Wong, CIES/Biol Dept, HKBU (PI)Drs CKC Wong, KC Cheung MS Yang, Prof KKL Yung, RNS

    Wong, NK Mak, CIES/Biol Dept, HKBU

    Dr ZW Cai, Dioxins Lab, HKBU

    Dr CKM Leung (MD), In VitroFertilization Centre, HK

    Dr PKK Louie, Air Services Group, HKEPD

    Dr NS Duzgoren-Aydin, Dept Earth Sci, HKU

    Prof KWK Liu, Dept Anatomy, CUHKProf TW Wong, Dept Community & Family Medicine, CUHK

    Prof J Fu, Guangzhou Inst Geochem, CAS, PRC

    Research staff/students:J Chan, WJ Deng, A Leung, Q Luo, XL Peng, F Wang, C Wong,SC Wu, GH Xing, XZ Yu

    Research Grant:HKBU1/03, Group Research Central Allocation, Research

    Grants Council of Hong KongThe Research Team:

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    Thank You