Exposure of Humans to Persistent pOrganic Pollutants (POPs):

What is the Relevance of Soil?What is the Relevance of Soil? Olaf Paepke

Eurofins Analytik Am Neuländer Gewerbepark 1Eurofins Analytik, Am Neuländer Gewerbepark 1 D-21097 Hamburg, Germany

Email: olafpaepke@eurofins deEmail: olafpaepke@eurofins.de

Outline• General information• Direct intake of soil• Intake via food (milk poultry vegetable• Intake via food (milk-, poultry-, vegetable-

and products R l ti il• Regulations on soil

• Influence of use or origin of soil• Background levels for soil• Examples for elevated levels of soilExamples for elevated levels of soil

What are POPs?What are POPs?

The term POPs refers to 12 chemicals addressed in the Stockholm Conventionaddressed in the Stockholm Convention (SC) on Persistent Organic Pollutants ,

l b l t t ti t d d tha global treaty negotiated under the auspices of the United Nations pEnvironment Program (UNEP) in order to eliminate the production and use or releaseeliminate the production and use or releaseof POPs.

12 Stockholm POPs

Chemical Pesticide Industrial Chemical By-productAldrin +Chlordane +Chlordane +DDT +Dieldrin +Endrin +Heptachlor +Mirex +MirexToxaphene +Hexachlorobenzene + + +PCBPCBs + +

Dioxins +Furans +Furans +

Due to the availability of data, the following will focus on

Dioxins and Dioxin like PCBsDioxins and Dioxin-like PCBs

Components of QuestionComponents of Question• Polychlorinated • Polychlorinatedy

dioxins and furansPCDDs and PCDFs

Polychlorinated biphenylsPCBsC12HxClyO2 (x+y=8; n=75)

C12HxClyO (x+y=8; n=135)

PCBsC12HxCly (x+y=10; n=209)

• Relevant for Humans:• 17 congeners with 2,3,7,8-

chlorine substitution

• Relevant for Humans:• 12 dioxin-like congeners, 4

chlorine substitutiong

non-ortho, 8 mono-ortho

Some General Remarks on PCDDs/PCDFsSome General Remarks on PCDDs/PCDFs

Di i d d i t ti ll th• Dioxins were never produced intentionally, they occur as trace contaminants in a variety of industrial and thermal processesthermal processes

• Due to their chemical, physical and biological stability PCDDs/PCDFs are stable to remain in thePCDDs/PCDFs are stable to remain in the environment for long times. As a consequence dioxins from so called “primary sources” (oncedioxins from so called primary sources (once formed in industrial or combustion processes) can be transferred to other matrices and enter the environment. Such “secondary sources” are e.g. sewage sludge/biosludge, composts, or contaminated soils and sediments

Ch i l & I d t i l SChemical & Industrial Sources for Dioxins

– Waste incineration

– Thermal industrial processes

Metal production– Metal production

– Chlorine industry

– Bleaching of pulp

– TrafficTraffic

– Domestic furnaces

Exposure Pathways of DioxinsE i i FoodE i t

Incineration

Emission FoodBeef, cow

milk/ products

Environment

IncinerationIndustry

milk/-products

Pork/d t

Rain/deposition

ChlorineIndustry

-products

Chicken/-products

Dump Site/Slude

Unwanted

Thermal MetalProcess

products

Fish/-products

Plants, grasby products

CarExhaust

products

VegetablesSoil / Water

Exhaust

HumansHumansHumansHumans

Importance of FoodImportance of FoodC ti f f d t ib t ll ith• Consumption of food contributes normally with

>95 %95 %to the daily total PCDD/PCDF and PCB uptake

• Food rich in fat, especially originating from

i l i t i t tanimals, is most important

• Food originating from plants usually shows a• Food originating from plants usually shows a

lower content of PCDDs/PCDFslower content of PCDDs/PCDFs

Dietary Intake of PCDD/Fs in pg I-TEQ/d from

100Major Food Groups, Adults (≈ 1 pg/day/kg BW)

75Other foods*Fish

50

EggsMeat, poultryDairy products

50

*other foods= cereals,

25 cereal products, vege-tables, fruit, vegetablefats and oils

0Finland France Germany Italy Holland Norway Sweden U.K.

European Commission

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European CommissionSCOOP Task 3.2.5June 7, 2000

Estimated Average Adult Dietary Intakes of Dioxins and dl PCBs in UKDioxins and dl-PCBs in UK

(Upper Bound Calculation)8

678

y

456

O-T

EQ/

eigh

t /da

y

PCBs

234

pg W

HO

g bo

dyw

e CDioxins

UK TDI = 2 pg WHO-TEQ/kg bw/day

12kg

01982 1992 1997 2001

C 02031 FSA Report FD 02/41, 2002

H E t S ilHuman Exposure to Soil

• Direct Intake: IngestionDirect Intake: Ingestion

• Indirect Intake: FoodMilk d ilk d t- Milk and milk products

- Poultry, eggs- Vegetable, fruit

Direct Intake: Ingestion

Soil ingsetion in children and adults in the same family (Davis et al., 2005)

Children: 37 – 207 mg/day *)

Adults: 23 – 625 mg/day *)

*) based on titanium as tracer

Ingestion of Soil, Dependence of Age

0,12

0,14

0 08

0,1

g/da

y)

0,06

0,08

aily

Inta

ke (g

0,02

0,04

Da

0

,

0 to 1 1 to 2 2 to 3 3 to 4 4 to 5 5 to 6 6 to 7Age group (years)Age group (years)

www.epa.gov/superfund/lead/products/ssircolo.pdf

Influences to POP Levels inMilk ProductsInfluences to POP Levels inMilk Products

EnvironmentalEnvironmental air

Emission

Other FEED STUFF

Grass

Soil

Grass

Soil

Influence of Soil Contamination on Dioxin C t ti i GConcentration in Grass

Hembrock-Heger 1990

Effects of Flooding on PCDDs/Fs &Effects of Flooding on PCDDs/Fs & PCBs

• Background: Grazing on milk producing cows on contaminated pastures may result in cont. milk

• During 3 sampling periods (1998-1999) collection of 310 samples (114 milk, 38 feed 79 soil, 79 grass)

• 3 river systems, samples collected from farms with floodplain pastures and nearby control farms

• Results: Milk from flooded prone location show significant higher values for dioxins and PCBs than from control sites Until now data only for milkfrom control sites. Until now, data only for milk available

Reference: Food Standard Agency

Uptake of Soil by Grazing Animals, Overview

Animal Uptake Method ReferenceAnimal Uptake Method ReferenceCow 6-14% of d. m. Titan Healey, 1968

Cow 1.2-18.6 % of d.m. Titan Mayland et al., 1975

Cow 1-18 % of d.m. Titan Thornton & Abrahams, 1983,

Cow 1-2 % of d.m. Cal. via ash Berende, 1990

Sheep 0.4-14 % of d.m. Titan Field & Purves, 1964

Sheep 75 kg/animal and year Air McGrath et al., 1982

Transfer of Dioxins by ConsumptionTransfer of Dioxins by Consumption of Poultry and Products

Influence of Housing on PCDDs/PCDFs in Chicken Eggs n= 285 2005in Chicken Eggs, n= 285, 2005

www.umwelt.nrw.de/verbraucherschutz

G. Schoeters , R. Hoogenboom, 2006

Sources of Dioxins in EggsSources of Dioxins in Eggs(G. Schoeters , R. Hoogenboom, 2006)

Cage hensCage hens• Feed

Free range hensFeed• Feed

• Worms and insects11 %

41 %24 %

FoodWorms

Herbs

• Herbs, grasses,vegetables, leavings

HerbsSoilfrom kitchen gardens

• Soil 24 %24 %

Comparison of “Byker eggs” with levels reported in literature

einf

elde

n

300

350

anta

m P

FHH

ambu

rg Rh e

250

300

g/g

fat

ket

l g t soil

PFH ba

ntam

Wal

es b

a

150

200

DF

I-TEQ

in p

g

e Fa

rm

supe

rmar

ke ow ck an

tam

rura

lny

s du

cken

Pan

teg

uck

rura

len

rura

ldu

ck P

ante

gon

Bac

ott S

tree

ns 4

60 p

pt

orne

rve

r 91

n D

ene

ton

Ath

onys

hen

e Tc

eal

es d

uck

Pra

nxto

n A

b

100

150

PCD

D/P

CD

Haw

thor

neE

U m

inG

erm

any

Cox

lodg

eB

lane

y R

oE

U m

axB

runs

wi c

Wal

es b

aSt

Ant

hoW

ales

he

Wal

es d

uW

ales

hW

ales

dB

ranx

toW

estm

aS

teph

eP

ets

Co

Bol

sov

Den

ton

Bra

nxt

St A

ntH

ulne W

a Br

0

50

0

Pless-Mulloli et al., 2001

Concentration in Eggs by Allotment:I-TEQ (pg/g fat)I-TEQ (pg/g fat)

50

60

g/g

fat

30

40

TEQ

in p

g

20

30

D/P

CD

F I-T

0

10

k A A

PCD

D

awtho

rne Fa

rmCox

lodg

eBlan

ey R

owBrun

swick

St Anth

onys

Branxto

n Btm

acott

Stre

etPets

Corn

erDen

ton D

ene

Branxto

n ASt A

nthon

ysHuln

e Tce

Branxto

n A

Haw

Westm D

Pless-Mulloli et al., 2001

Allotment Coxlodge: gI-TEQ (ash) 4224 pg/g, (egg) 2 pg/g fat

14000

16000

30

35

tash egg

10000

12000

-TE

Q in

pg/

g

20

25

TEQ

in p

g/g

faash egg

6000

8000

ratio

n in

ash

I-

15

20

ion

in e

ggs

I-T

2000

4000

Conc

entr

5

10

Conc

entra

t

0

8- T

CDD

8-Pe

CDD

8 Hx

CDDs

8-Hp

CDD

OCDD

7,8-

TCDF

8 Pe

CDFs

8 Hx

CDFs

8 Hp

CDFs

OCDF

0

2, 3

, 7,

1,2,

3,7,

8

Tota

l 2,3

,7,8

1,2,

3,4,

6,7,

8

2,3,

7

Tota

l 2,3

,7,8

Tota

l 2,3

,7,8

Tota

l 2,3

,7,8

Pless-Mulloli et al., 2001

PCDDs/PCDFs in Exposure MaterialpTotals of ONLY 2.3.7.8-substituted Congeners

100 0

Soil (I-TEQ : 2378 pg/g)

Eggs (I-TEQ : 746 pg/g, lipid)

75,0

100,0Chicken (I-TEQ : 513 pg/g, lipid)

50,0%

0,0

25,0

Tetra-CDD

Penta-CDD

Hexa-CDD

Hepta-CDD

Octa-CDD

Tetra-CDF

Penta-CDF

Hexa-CDF

Hepta-CDF

Octa-CDF

Wuthe et al, 1992

PCDDs/PCDFs in Human BloodResident of contaminated site

5000Background, Germany, mean (I-TEQ : 43)

Resident No.56 (I-TEQ : 175)

3000

4000

id b

ased

1000

2000

pg/g

, lip

i

0

1000

CD

D

CD

D

CD

D

CD

D

CD

D

CD

F

CD

F

CD

F

CD

F

CD

F

Tetra

-C

Pent

a-C

Hex

a-C

Hep

ta-C

Oct

a-C

Tetra

-C

Pent

a-C

Hex

a-C

Hep

ta-C

Oct

a-C

Wuthe et al, 1992

Indirect Intake of Soil Contaminants via F d V t blFood: Vegetable

Increase of PCDD/PCDF in Carrots depending of Soil Concentration Fielddepending of Soil Concentration, Field

Investigation Marsberg

Krause et al., 1993

Comparison of Dioxin Concentrations (ng TEQ/kg DM) in Food Plants Corresponding Soil(ng TEQ/kg DM) in Food Plants, Corresponding Soil

(0-25 cm) and Deposition (TEQ, m2 /d)

Lettuce Endive Kale Soil Deposition

2.4 28.5 65.6 75.1 56

1.5 5.6 20.8 77.6 20

3.1 14.4 53.7 35.9 51

2.8 5.5 20.3 16.4 21

1.8 2.2 4.0 21.3 7.4

2.2 1.7 2.6 21.8 5.7

MURL, 1995

Regulations and Special Influences g pon Soil Contamination

Soil Guideline Concentrations (TEQ, ng/kg d.m.)

• Germany< 5 Target concentration

5 – 40 Control of products if dioxin transfer>100 Soil exchange on children playgrounds>100 Soil exchange on children playgrounds

> 1000 Soil exchange in residential areas> 10,000 Soil exchange independent of the location

• The Netherlands1 Agricultural farming

10 Dairy farming10 Dairy farming• Sweden

10 Sensitive uses250 Non-sensitive uses

• Japan10001000

Example for Contamination of Soil andExample for Contamination of Soil and Vegetation by a Point Source (MSWI)

(Ch P S t l Di i 2003)(Cheng P.S. et al., Dioxin 2003)

Nationwide Distribution of PCDD/F levels in Ambient Air of 19 MSWIs in Taiwan

Correspomding locations

Cheng P.S. et al., 2003

PCDD/Fs Levels in Ambient Air in the Vicinity yof 19 MSWIs in Taiwan. (pg-TEQ/Nm3)

1 60

1,80

2,00

1,20

1,40

1,60

0 60

0,80

1,00

0,20

0,40

0,60

0,00A B C D D E F G H I J K L M N O P Q R S

Cheng P.S. et al., 2003

PCDD/Fs Levels in Vegetation in the Vicinity

35

of 19 MSWIs in Taiwan. (pg-TEQ/g d.m.)

25

30

20

25

10

15

5

10

0A B C D E F *G I J K L N O P Q R *S

Cheng P.S. et al., 2003

PCDD/Fs level in soil in the vicinity of 19

70180,0

MSWIs in Taiwan. (pg-TEQ/g d.m.)

50

60

,

40

50

20

30

10

20

0A B C D E F *G H I J K L *M N O P Q R *S

Cheng P.S. et al., 2003

Nationwide PCDD/Fs Levels in Ambient Air, Vege-tation, and Soil in the Vicinity of 19 MSWIs in Taiwan

12

14

8

10air

vegetation

(* factor 5)

4

6

soil

0

2

4

A B C D E F G H I J K L M N O P Q Rair

soil

0

P Q R S

Cheng P.S. et al., 2003

Influence of Use/Origin on Soil PCDD/F - Contamination, Bavaria/Germany

TEQ (BGA), ng/kg, d.m.

Type of Soil n Med Range

Farmland 41 0.24 ND -18Grassland 27 0.6 ND - 18Forest top layer 32 10 ND - 50Forest, top layer 32 10 ND 50Forest, soil 30 0.8 ND - 17G 30 1 ND 13Green spaces 30 1 ND - 13ND = Not Detected

Fiedler, 1998

Influence of Traffic on Soil PCDD/F - Contamination, Bavaria Germany TEQ (BGA) values ng/kg d mBavaria, Germany, TEQ (BGA) values, ng/kg, d.m.

Distance Distance Remark<5 m >5 m

• City of Munich 10 0.3 C.D.• BAB A3 Nürnberg 16 1 6-0 2BAB A3, Nürnberg 16 1.6 0.2• BAB A8, Dachau 7.6 ND• BAB A8 Nürnberg 5 2 1 0 5• BAB A8, Nürnberg 5 2.1-0.5• Local small road 1-0.6 0.5-ND

C.D. = continuous decline till 70 m Fiedler, 1998

TEQ (PCDD/PCDF only) in Sediment and Soils from EU Member StatesSoils from EU Member States,

ng /kg d. m.S di t S ilSediment Soil

Background, Urban Any Type, Pasture, RuralAustria 1 6 - 14Austria 1.6 - 14Belgium 2.7 - 8.9Finland 0.7 - 100GGermany 1.2 - 73 0.1 - 42Greece 2 - 45Ireland 0.2 - 13Italy 0.1 - 23 0.1 - 43Luxembourg 2.4 - 16 1.4 - 20Netherlands 1 10 2 55Netherlands 1 - 10 2 - 55Spain 0.1 - 8.4Sweden 0.8 - 207 0.1U. Kingdom 2 - 123 0.8 - 87

Fiedler et al., 1999

Typical Congener/Homolog Distribution of Soil Samples

• Incineration pattern:Increase from TCDD to OCDD, decline from TCDF to OCDF,

• Pentachlorophenol pattern:Increase from HxCDD to OCDD, Increase from HxCDF to OCDF

• Agent Orange pattern:Dominated by 2,3,7,8-TCDD, small 1,2,3,7,8-PeCDD

• Chlorine bleaching pattern:Dominated by 2,3,7,8-TCDD/TCDF, small other Tetra + Penta CDDs/Fs

• “Non anthropogenic” pattern:Increase from HxCDD to OCDD, NO PCDFs

Examples for Elevated Soil Levels Values in TEQs, pg/g

• Taiwan PCP Production some 1 000 000Taiwan PCP Production some 1,000,000• Vietnam Agent Orange *) about 1,000,000• Seveso TCP Production some 100,000 **)Seveso TCP Production some 100,000 )• Germany Herbicide Production some 100,000• USA Horse Arena some 100,000,• Germany Metal Reclamation some 10,000• Japan MWI vicinity some 1,000• UK Fly ash pathways some 1,000

*) Former air base **) values given in μg/m2

References for Dietary Intake

• European Commission, SCOOP Task 3.2.5, June 7, 2000• Report FD 02/41, FSA’s Food Survey Information Sheet, 2002

References for Ingestion of SoilReferences for Ingestion of Soil

• Davis S. and Mirik D., Soil ingestion in Children and adults in the same family, J. of Exposure Analysis and Environmental Epidemiology, 1-13, 2005

• http://www.epa.gov/superfund/lead/products/ssircolo.pdfg

• http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6WDM-45M8SWC-2B&_user=10&_rdoc=1&_fmt=&_orig=search&_sort=d&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=9f47f63ea32790c7a2004714d479c0f5

References for Transfer of Dioxins to MilkReferences for Transfer of Dioxins to Milk

• Liem et al., Levels and Patterns of dioxins in cows milk in the vicinity of municipal waste incinerators and metal reclamation plants in the Netherlands, OHC, 1, 567-570, (1990)

• Startin et al., Surveillance of British Foods For PCDDs and PCDFs, Chemosphere, 20, 793- 798, (1990)

• Riss et al., Comparison of PCDD/PCDF Levels in Soil, Cow’s milk, Human Blood and Spruce Needles in an Area of PCDD/PCDF Contamination Trough Emissions from a MetalReclamation Plant, Chemosphere, 21, 1451- 1456, (1990)

•

References for Transfer of Dioxins to EggsReferences for Transfer of Dioxins to Eggs

• http://www.umwelt.nrw.de/verbraucherschutz/pdf/dioxin_eier_bericht.pdf (2005)

• G. Schoeters , R. Hoogenboom ,Contamination of free-range chicken eggs with dioxins and dioxin-like polychlorinated biphenyls, Molekular Nutrition & Food, 50:10, 908 914, 2006p y p y , , , ,

• Pless-Mulloli et al., Transfer of PCDD/F and Heavy Metals from Incinerator Ash onFootpaths in Allotments into Soil and Eggs, OHC, 51, 48-52, (2001)

Fürst et al PCDD/PCDF in Commercial Chicken Eggs Depending on the T pe of• Fürst et al., PCDD/PCDF in Commercial Chicken Eggs – Depending on the Type of Housing, OHC, 13, 31- 34, 1993

• Sagunski et al., Levels and Patterns of PCDD/F in Eggs, Chicken and Human Blood of residents living on a contaminated Area: Investigation of a possible Relationship OHC 13residents living on a contaminated Area: Investigation of a possible Relationship, OHC, 13, 101-104, (1993)

• Wuthe, In Current Views on the impact of dioxins and furans on human health and the environment Berlin Nov 9 11 1992 The Toxicology Forum 252 259 (1992)environment. Berlin Nov. 9-11, 1992. The Toxicology Forum 252-259, (1992)

• Stephens et al., Bioaccumulation of dioxins in food animals II: Controlled exposure studiesChemosphere, 20, 1091- 1096, (1990)

References for Transfer of Dioxins fom Soil to Grass and Vegetables

• Hembrock-Heger A., PCDD/PCDF levels in soil and plants in North Rhine Westphalia, Organohalogen Compounds,1 475- 478, 1990

MURL 1995 Mi i t i fü U lt R d d L d i t h ft L ft i h lt• MURL, 1995, Ministerium für Umwelt, Raumordnung und Landwirtschaft: Luftreinhalte-planung in Nordrhein-Westfalen, Untersuchungsbericht Ostruhrgebiet, Luftüberwachung

• Krause G.H.M, Delschen T., Fürst P., Hein D., Bewertung der Belastung durch PCDD/F aus der ehemaligen K pferge inn ng im Ra m Marsberg NRW Teil 1 PCDD/F n Bödender ehemaligen Kupfergewinnung im Raum Marsberg, NRW, Teil 1, PCDD/F n Böden, Vegetation und Kuhmilch, UWSF Z .Umweltchemie,5,194-203, 1993

• Healey, W.B, The influence of soil type on ingestion of soil by grazing animals, 9th Inter-national Congress of soil sciences transactions 3:437 445 1968national Congress of soil sciences transactions 3:437-445, 1968

• Mayland H., Flore A., Rosenau R., Turner V., Soil ingestion by cattle on semiarid range as reflected by titanium analysis of feces. J Range Managemant 28:448-452, 1975

• Thornton I., Abrahams O., Soil ingestion- a major pathway of heavy metals into livestock grazing contaminated land. Sci. Total Environ. 28:287-294, 1983

• Berende P., Grondobname door melkoeeien, Institut voor veevoedingsonderzoek (IVVO), , , g ( ),Lelstad, NL, Interim Rapport no., 312, 1990

References for Transfer of Dioxins fom Soil to Grass and Vegetables (cont.)

• Riss et al., Comparison of PCDD/PCDF Levels in Soil, Cow’s milk, Human Blood and Spruce Needles in an Area of PCDD/PCDF Contamination Trough Emissions from a MetalReclamation Plant, Chemosphere, 21, 1451- 1456, (1990)

• Field A.C., Purves D., Intake of soil by grazing sheep, Poc. Nutr. Soc. 23: 24-24, 1964

• McGrath D, Pool d., Fleming G., Sinnott J., Soil ingestion by grazing sheep, Irish J. Agr. Res., 21:35, 1990

Thank you for your AttentionThank you for your Attention