The Swedish experience

Cajsa Wahlberg

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• Background information on some BFR:s- chemical structure and composition- amounts used- effects- levels in environment

• BFR in sludge samples

• PBDE in soil

• Conclusions

Electronics

Electric devices

Building materials

Polymers

Textiles

Fire retarded goods

3%%(polybrominated biphenyls)

• Known production has ceased

• Environmental levels in Sweden are low

X+Y = 1-10

Theoretically 209 congeners

3%'(���(polybrominated diphenyl ethers) Three different technical products:

SH%'( (5 Br)includes tetra-, penta- and hexaBDE

RF%'(�(8 Br)includes from hexa- to nonaBDE

GH%'( (10 Br)consists mainly of decaBDE

X+Y = 1-10

Theoretically 209 congeners

peBDE

• Used in polymers and textiles• Abundant in environmental samples• Bioaccumulates and biomagnifies• No acute toxicity• Neurotoxic effects on neonatal mice• Hormone disruptive effects• Effects on Thyroid system and liver• EU risk assessment finnished• Comission has proposed a stop for peBDE from july 2003

ocBDE

• Used in a variety of plastics and polymers• World production is low • Reproduction toxicity shown and classification will probably lead to decreasing market• EU risk assessment not yet finalized

DeBDE

• Used in many types of synthetic material includingtextiles.

• Quantitatively a large product

• Low uptake and few effects shown

• Hard to test because of low aq. solubility

• Shown to debrominate under UV radiation, to formlower brominated BDEs

• Less persistent, more reactive than peBDE

• EU risk assessment not yet finalized

+%&'(hexabromocyclododecane)

• Additive to expanded and extruded poly- styrene used in building, construction and textile coating•�Present in fish, birds and mammals• Low acute toxicity• High aqatic toxicity• Indicated as a skin sensitiser• Liver is target organ• More data is needed on effects and persistence•�Next version of EU risk assessment report next year

Br

Br

Br

Br

Br

Br

7%%3$(tetrabromobisphenol A)

HO

Br

Br

Br

OH

Br

H3C CH3

• Quantitatively largest BFR• Incorporated covalently into polymers (epoxy)• Rapidly excreted by mammals• Endocrine effects shown in vitro but not in vivo• Very toxic to aquatic organisms• Present in sediments and sludge• Found in human blood samples but little info of uptake in biota• Present on OSPAR priority list• EU risk assessment just started

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(from www.bsef.com)

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America Europe Asia Total

Penta-BDE Octa-BDE

Deca-BDE HBCD

TBBPA

Calculated from Sellström, Thesis 1999

GH%'(�LQ�ULYHU�VHGLPHQWV

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Santillo, Greenpeace 2001

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200

400

600

800

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DecaBDE

HBCD

BB-209

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HospitalCleaners

ComputerClerks

ComputerTechnicians

ElectronicsDismantlers

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BDE-47

BDE-153

BDE-183

BDE-209

Human occupational exposures toHuman occupational exposures to PBDEs PBDEs

Sjödin HW�DO., EHP 107 (1999) 643Jakobsson HW�DO�, Chemosphere In Press

Herring Gull

sPBDE 200-1400 ng /g w.w.

Peregrine Falcon

BDE-47: 15-3800 ng/g l.w.

BDE-153: 270-16000 ng/g l.w.

BDE-209: 30-430 ng/g l.w.

HBCDD: 34-2400 ng/g l.w.

Shorthorn Sculpin

sPBDE 2.1-8.2 ng /g w.w. (47,99,100 and 153)

sPBDE (F): 665 ± 457 ng/g w.w.

sPBDE (M): 466 ± 230 ng/g w.w.

Beluga Whales

Levels in WildlifeLevels in Wildlife

From Bergman, Dioxin 01

Sellström U. Thesis 1999 Stockholm University Luross HW�DO., PHC 47 (2000) 73-76

100

200

300

400

500

81 85 89 93 97

Lake trout from Lake Ontario

Time trends of BDE-47Time trends of BDE-47

200

400

600

800

1000

1200

69 74 79 84 89 94

(µg/

kg l.

w.)

Guillemot egg from the Baltic Sea

BDE-47 and BDE-153 in SwedishBDE-47 and BDE-153 in Swedishhuman milkhuman milk

D.Meironyté HW�DO., -�7R[LFRO�(QYLURQ�+HDOWK�����D. Meironyté Guvenius and K. Norén, BFR 2001

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PBDE and PCB in three WWTP in StockholmJ�NJ�G�Z�

0

50

100

150

200

250

300

350

400

450

Henriksdal Bromma Loudden

sum te-hxBDE -98

decaBDE ´98

tot PCB -00US levels (n=11):te-hxBDE: 1000-2290 J�NJ� G � ZdeBDE: 85-4890 J� N J�G�Z�

HBCD and TBBPA in three WWTP in Stockholm

J�NJ�G�Z�

0

10

20

30

40

50

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Henriksdal Bromma Loudden

HBCD -98

TBBPA -98

From Matscheko, Thesis, 2001

PBDE in sludge amended soil

Application of sludge to a Swedish farm 1978-82 (tot 25 tons/ha)resulted in a 6 000 and 8 000 fold increase in the soil of BDE-47 andBDE-99 respectively. The WWTP had received waste water from textileindustries.

Fields belonging to two research stations in the south of Sweden wheresludge was spread (1-3 tons/ha*year) 1981-97, had slightly increasedPBDE-levels.

Uptake in earthworms was also shown. BSAFs were 2- 4 in the mostpolluted soil. Higher at other sites.

Conclusions

• BFRs are present in sludge from WWTP

• Levels in Sweden are generally lower than PCB-levels

• PBDEs are persistent in soil and accumulates in earthworms

• A risk assessment based on present knowledge of levels and effects showed large human safety margins for PBDEs at a sludge application rate of 1 ton/ha*year*

• PBB-, PeBDE- and OcBDE-levels in sludge will hopefully not increase

• If use of DeBDE, HBCD and TBBPA increases, the sludge levels may increase

• Levels in sludge should be monitored and limit values considered

* Hellström, VAV-report M 113 (2000)

Other measures should also be taken to reduceinflow to WWTPs :

• Put restrictions on the discharges to the WWTPs

• Point sources must be eliminated

• Bring pressure on authorities and producers of BFR and other PBT-substances

• Set standards at public procurement

• Lobby for phase out of PBT-substances

A very good argument is the concernfor our farmlands!

Thanks to:

Assoc. professor�&\QWKLD�GH�:LWInstitute of Applied EnvironmentalResearch (ITM)at Stockholm University

Professor cNH�%HUJPDQDept of Environmental Chemistryat Stockholm University

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Bergman Å and Örn U, Polybrominated Flame Retardants - A threat? Plenary Lecture, Dioxin ´01, Korea (2001)Bergman Å, Dept. Of Environmental Chemistry.Stockholm University. Personal communication (2001)Bromine Science and Environmental Forum, www.bsef.comde Wit C, Brominated Flame Retardants. Swedish Environmental Protection Agency, report 5065 (2000)de Wit C, Institute of Applied Enviuronmental Research, Stockholm University. Personal communication (2001)Hale R C et al, Persistent pollutants in land-applied sludges, 1DWXUH (412) 140-141, 12 July 2001Hellström T, Brominated Flame Retardants (PBDE and PBB) in sludge - a Problem? The Swedish Water and Wastewater Association (VAV), Report No M 113 (eng), April 2000Lund B-O, National Chemicals Inspectorate, Sweden, personal communication (2001)Matscheko N, Accumulation of persistent organic pollutants in earthworm and soil. Ph D thesis, Umeå University, Sweden (2001)Meironyte D, Norén K, Polybrominated diphenyl ethers in Swedish human milk. The follow-up study. Seminar abstracts. Second International Workshop on BFR, May 14-16, 2001 at Stockholm University, Sweden National Chemicals Inspectorate, Sweden. Lägesbeskrivning för avveckling av bly, bromerade flamskyddsmedel, kvicksilver, nonylfenoletoxilater och klorparaffiner, KemI PM 1/01, jan 2001Santillo D et al. The presence of brominated flame retardants and organotin compounds in dust collected from Parliament buildings from eight countries. Greenpeace Research Laboratories. Technical Note 03/2001Second International Workshop on Brominated Flame Retardants, May 14-16, 2001, Stockholm University, Sweden, Seminar abstracts. http://www.kemi.se/Sellström et al. Bromerade flamskyddsmedel (PBDEs) funna i ägg av pilgrimsfalkar��)DOFR�SHUHJULQXV) häckande i Sverige, Report from Swedish Society for Nature Conservation, http://www.snf.se/, (2001)Sellström U et al, Brominated flame retardants in sediments from European estuaries, the Baltic Sea, and in sewage sludge.�2UJDQRKDORJHQ�&RPSRXQGV Vol 40, 383-386. Dioxin ´99, Venice, Italy (1999)Sellström U, Determination of polybrominated flame retardants in biota, sediment and sewage sludge. Ph. D. thesis. Stockholm University, Sweden (1999)Swedish Environmental Protection Agency and The Swedish Water and Wastewater Association (VAV),Results from a study of BFRs in sludges from 50 WWTP in Sweden, Swedish EPA, The Swedish Water and Wastewater Association, personal communication (report under production), (2001)