Pentabromodiphenyl ether as a global POP
1 2 Pentabromodiphenyl ether as a global POP
Johanna Peltola Leena Ylä-Mononen Finnish Environment Institute Chemicals Division
TemaNord 2000:XX
3 4 Contents
PREFACE...... 7
SUMMARY ...... 8
SAMMANDRAG ...... 10
YHTEENVETO ...... 12
1 INTRODUCTION...... 14
1.1 INTERNATIONAL LEGALLY BINDING INSTRUMENTS FOCUSING ON POPS ...... 14 1.2 ADDING NEW POPS TO THE INSTRUMENTS ...... 15 1.3 OBJECTIVES AND STRUCTURE OF THE REPORT...... 16 2 CHEMICAL IDENTITY...... 18
3 INFORMATION ON PENTABROMODIPHENYL ETHER IN RELATION TO THE POP SCREENING CRITERIA...... 20
3.1 PERSISTENCE...... 20 3.2 BIOACCUMULATION ...... 21 3.3 POTENTIAL FOR LONG-RANGE ENVIRONMENTAL TRANSPORT...... 22 3.4 ADVERSE EFFECTS...... 24 4 STATEMENT OF THE REASONS FOR CONCERN AND NEED FOR GLOBAL ACTION ...... 25
5 ADDITIONAL INFORMATION ON PENTABROMODIPHENYL ETHER...... 26
5.1 SOURCES ...... 26 5.1.1 Production and market...... 26 5.1.2 Uses...... 27 5.1.3 Releases to the environment...... 27 5.1.4 Aspects concerning recycling of materials containing pentaBDE ...... 30 5.1.5 Brominated dioxins and furans ...... 30 5.2 PHYSICAL AND CHEMICAL PROPERTIES ...... 31 5.3 ENVIRONMENTAL FATE ...... 32 5.3.1 Degradation and transformation ...... 32 5.3.2 Environmental transport...... 32 5.3.3 Bioaccumulation and biomagnification ...... 34 5.4 EFFECTS ...... 36 5.4.1 Environment...... 36 5.4.2 Laboratory mammals –health effects ...... 37 5.4.3 Predicted no effect levels ...... 38 5.5 EXPOSURE ...... 38 5.5.1 Environmental exposure...... 38 5.5.2 Exposure of humans...... 46 5.6 GENERAL INFORMATION ON NATIONAL AND INTERNATIONAL ADMINISTRATIVE ACTIONS ON PENTABDE ...... 47 5.6.1 Classification and labelling ...... 47
5 5.6.2 Available risk evaluations...... 48 5.6.3 Status under international conventions...... 48 6 ALTERNATIVES AND POLLUTION PREVENTION TECHNIQUES ...... 49
6.1 ALTERNATIVE CHEMICALS AND METHODS ...... 49 6.2 POLLUTION PREVENTION TECHNIQUES ...... 49 REFERENCES...... 51
ANNEX 1. EXECUTIVE BODY DECISION 1998/2 ON INFORMATION TO BE SUBMITTED AND THE PROCEDURE FOR ADDING SUBSTANCES TO ANNEXES I, II OR III TO THE POPS PROTOCOL (EB.AIR/WG.5/52, ANNEX II)...... 60
ANNEX 2. ARTICLE 8 AND ANNEXES D-F OF THE UNEP POP CONVENTION...... 63
ANNEX 3. COMPARISON OF PENTABDE AND ITS ALTERNATIVES TCPP AND PBBE.69
ANNEX 4. USES AND MARKET OF BROMINATED FLAME RETARDANTS IN THE WESTERN EUROPE IN 1998...... 70
ANNEX 5. MONITORING DATA FROM REGIONAL BACKGROUND AREAS...... 71
ANNEX 6. RECENT MONITORING DATA FROM POLLUTED AREAS...... 72
6 Preface
The global negotiations on the convention restricting persistent organic pollutants (POPs) were successfully concluded in the end of the year 2000. While these negotiations focussed solely on the 12 chemicals already generally recognised as POPs, the Nordic Chemicals Group decided to further work on identifying new candidates and gathering information on them. Pentabromodiphenyl ether was selected as a pilot chemical for which a background document was to be prepared.
This report has been prepared in the Finnish Environment Institute by Johanna Peltola and Leena Ylä-Mononen under a contract with the Nordic Chemicals Group. The work has been financed by the Nordic Council of Ministers (project number 33.06.24.10) and the Finnish Environment Institute. Bert-Ove Lund from Kemikalieinspektionen, Sweden, has been in charge of the project. He and other members of the project Steering Group, Helgi Jensson (Holstuvernd rikisins), Niklas Johansson (Naturvårdsverket), Vibeke Sømnes (Statens forurensningstilsyn), and Kim Petersen (Miljøstyrelsen) have provided valuable information and guided the work with their comments.
We thank all those various experts who have kindly provided us with information on pentaBDE and those who have commented the text. The authors would also like to thank the Steering Group members for their constructive comments.
The authors would also wish to thank Mr. Joel Pottala for correcting the English.
7 Summary
There are two international instruments for restricting the use and releases of persistent organic pollutants (POPs). These are the global UNEP POP Convention (signed in 2001) and the POP Protocol of the UNECE Convention on Long-Range Transboundary Air Pollution (signed in 1998). Both frameworks restrict the production and use of selected POPs. They also have obligations related to release reduction measures for by-products such as dioxins and furans and related to waste management measures.
Both frameworks have mechanisms and criteria for including new substances within their scope. The screening criteria are approximately the same in both instruments. Firstly, the substance has to have potential for long-range environmental transport (LRET); in the UNEP POP Convention criterion LRET can occur via air, water or migratory species, whereas the UNECE considers only substances susceptible to LRET via air. In addition, there has to be evidence that the substance is persistent in the environment and that it is bioaccumulating. Also evidence of its ability to cause adverse effects is required.
This document reviews the POP properties of a brominated flame retardant, commercial pentabromodiphenyl ether (pentaBDE) in relation to the screening criteria and gives some additional background information for consideration of its possible nomination as a new POP to be included within the two international frameworks.
According to the data gathered, pentaBDE seems to fulfil the screening criteria set for adding new substances into both POP frameworks. There is clear monitoring evidence of contamination from remote regions and air analyses show that the major components of pentaBDE can be transported long-range by air because they have been observed in a significant portion in the vapour phase. In addition, model results indicate that the atmospheric half-life is between 10 and 20 days for the major components of pentaBDE, BDE-47 and BDE-99. Furthermore, according to an available test result, pentaBDE is not readily biodegradable. Quantitative structure-activity relationship model data of the major congeners show that pentaBDE is persistent in water and sediment. This assumption is supported by sediment profile results and results from remote area marine mammal studies.
The bioconcentration of commercial pentaBDE in carp was found to be very high and bioaccumulation has been reported in blue mussels to be even higher than the bioaccumulation of many PCB congeners. In addition, laboratory mammals and pike take up the major congeners efficiently and eliminate them slowly indicating a high potential for bioaccumulation and resistance to biological transformation. Concentration in aquatic biota has been shown to increase as the trophic level increases, which means that pentaBDE biomagnifies in the food web. Recent
8 studies on top predator bird species give further evidence of bioaccumulation and high persistency against biological transformation in the food web.
PentaBDE’s ability to cause adverse effects have been shown in in vivo experiments. The major effects shown in laboratory mammals are liver disturbances and developmental neurotoxicity. Endocrine disrupting and dioxin- like activity have been shown to occur in cells treated with pentaBDE components and their primary metabolites. In addition, adverse effects on growth and reproduction have been observed in aquatic organisms.
There are also other reasons for concern. Most of the recent studies show increased concentrations of pentaBDE in humans, fish and marine mammals. In some regions of North America environmental concentrations of pentaBDE components are even expected to soon reach the levels of PCBs in the environment. In addition, the use of pentaBDE also contributes to the releases of dioxins and furans.
PentaBDE is used mainly in rigid and flexible polyurethane foams and polyurethane elastomers. Most of this polyurethane is used in turn in upholstery and furnishing. Global market demand for pentaBDE has more than doubled in the last decade to the present 8,500 metric tn per year. Simultaneously, the use in Europe has decreased to approximately 210 tn per year. Alternative chemicals and techniques for avoiding the use of pentaBDE are available for most of its uses.
A major part of releases to the environment occurs from articles containing pentaBDE during or after their service life. The largest amount of the releases occur in connection with weathering and wearing (dust), but volatilisation has also been identified as a significant release route in all life cycle phases. The releases are mainly diffuse by nature. The most feasible way to restrict releases of pentaBDE would seem to be to restrict its use. The European Union is in the process of banning both the use of pentaBDE and placing it on the market as a chemical or as an additive in products.
9 Sammandrag
Det finns två internationella avtal som begränsar användning och utsläpp av beständiga organiska föroreningar (persistent organic pollutants = POPs): Den globala UNEP POP konventionen (undertecknad 2001) och UNECEs POP protokoll om fjärrtransporterade gränsöverskridande luftföroreningar (long-range transboundary air pollution = LRTAP; undertecknat 1998). Bägge ramavtalen begränsar produktionen och användningen av vissa utvalda POPs. Avtalen innehåller även åtgärder för begränsning av biprodukter som dioxiner och furaner samt åtgärder inom avfallshanteringen.
Båda ramavtalen innehåller mekanismer och kriterier för hur nya substanser skall inkluderas i avtalen. Urvalskriterierna är snarlika i bägge avtalen. En sådan substans skall kunna transporteras långa sträckor i miljön (Long-range environmental transport = LRET); enligt UNEP POP konventionens kriterium kan transporten ske via luft, vatten eller flyttande djurarter medan UNECE beaktar endast substanser som kan transporteras via luft. Dessutom skall det finnas bevis på att substansen är stabil i miljön och att den kan bioackumuleras. Slutligen krävs bevis även för substansens förmåga att förorsaka icke önskade effekter.
Denna publikation granskar POP-egenskaperna hos ett bromerat flamskyddsmedel, kommersiell pentabromdifenyleter (pentaBDE) i förhållande till urvalskriterierna. Publikationen ger en del ytterligare information att beaktas som bakgrund då man överväger att eventuellt föreslå att substansen skall inkluderas som en ny POP i de två internationella avtalen.
Enligt den information som insamlats tycks pentaBDE uppfylla båda avtalens urvalskriterier för nya substanser. Det finns mätresultat från miljöövervakningen som klart påvisar kontaminering av avlägsna trakter och mätningar i luft visar att de huvudsakliga komponenterna i pentaBDE kan transpoteras långa vägar i luften eftersom betydande mängder har observerats i gasfas. Dessutom tyder resultat från modellberäkningar på att de viktigaste komponenterna av pentaBDE, nämligen BDE-47 och BDE-99 har en halveringstid i luft mellan 10 och 20 dagar. PentaBDE är inte heller lätt biologiskt nedbrytbart, enligt ett tillgängligt testresultat. Resultat från modellberäkningar av det kvantitativa förhållandet mellan de huvudsakliga komponenternas molekylstrukturer och deras aktivitet tyder på att pentaBDE är stabilt i vatten och sediment. Detta antagande stöds av studier av sediment-profiler och resultat från studier av däggdjur från avlägsna marina miljöer.
Biokoncentrationen av kommersiell pentaBDE i karp har befunnits vara mycket hög och bioackumuleringen i blåmusslor har rapporterats vara till och med högre än många PCB-kongeners bioackumulering. Dessutom upptas de huvudsakliga kongenerna effektivt av laboratoriedäggdjur och gädda samtidigt som ämnena elimineras långsamt, vilket tyder på potentiellt hög bioackumulering och motståndskraft mot biologisk transformering. Koncentrationen i vattenlevande organismer tycks vara större på högre nivåer i näringskedjan vilket visar att
10 pentaBDE anrikas i näringskedjan. Färska studier av rovfåglar högst upp i skedjan ger ytterligare bevis på bioackumulering och hög persistens gentemot biologisk transformering i näringskedjan.
PentaBDEs förmåga att förorsaka oönskade effekter har påvisats genom experiment in vivo. De huvudsakliga effekterna som påvisats hos däggdjur i laboratorium är störningar i levern och neurotoxiska utvecklingshämningar. Hormonella störningar och dioxinlika aktiviteter har påvisats hos celler som behandlats med pentaBDE komponenter och deras primära metaboliter.
Det finns även andra skäl till oro. De flesta nyare studierna visar förhöjda koncentrationer av pentaBDE i människor, fiskar och marina däggdjur. I vissa områden i Nordamerika väntar man sig att koncentrationerna av pentaBDE i miljön snart når samma nivå som koncentrationerna av PCB. Dessutom bidrar användningen av pentaBDE till utsläppen av dioxiner och furaner.
PentaBDE används främst i styva och flexibla polyuretanskum och i polyurethan elastomerer. Största delen av detta polyuretan används i stoppningar och möbler. Den globala efterfrågan på pentaBDE har mer än fördubblats under det senaste årtiondet och marknadsvolymen är för närvarande 8 500 ton per år. Samtidigt har användningen i Europa minskat till cirka 210 ton per år. Det finns alternativa kemikalier och tekniker som gör det möjligt att undvika användning av pentaBDE för de flesta användningsändamålen.
En betydande del av utsläppen sker från föremål som innehåller pentaBDE då föremålen används eller då de tagits ur bruk. Största delen av utsläppen sker i samband med slitage (damm) men även avdunstning har identifierats som en betydelsefull utsläppskälla under alla skeden av livscykeln. De huvudsakliga utsläppen är inte lokala punktutsläpp utan allmänna till sin natur. Det mest ändamålsenliga sättet att begränsa utsläppen av pentaBDE vore att begränsa dess användning. I EU pågår arbete med att förbjuda användningen och marknadsföringen av pentaBDE både som kemikalie och som tillsatsmedel i produkter.
11 Yhteenveto
Pysyvien orgaanisten yhdisteiden käyttöä ja päästöjä rajoittaa kaksi kansainvälistä sopimusta, maailmanlaajuinen UNEP:in POP -sopimus (allekirjoitettu 2001) ja UNECE:n Kaukokulkeutumissopimuksen POP –pöytäkirja (allekirjoitettu 1998). Molemmat sopimukset rajoittavat tiettyjen POP –yhdisteiden valmistusta ja käyttöä. Ne sisältävät myös prosesseissa syntyvien aineiden, kuten dioksiinien ja furaanien päästöjen vähennystoimiin liittyviä velvoitteita sekä jätehuoltovelvoitteita.
Molempiin sopimuksiin sisältyy myös mekanismi ja kriteerit uusien aineiden lisäämiselle niiden piiriin. Valintakriteerit ovat molemmissa sopimuksissa pitkälti samat. Aineella on ensinnäkin oltava taipumus kaukokulkeutua ympäristössä. UNEP:in POP –sopimuksessa aine voi olla kaukokulkeutuva ilman, veden tai eliöiden välityksellä, kun taas UNECE tarkastelee ainoastaan aineita, jotka ovat ilman kautta kaukokulkeutuvia. Kaukokulkeutumistaipumuksen lisäksi on oltava näyttöä siitä, että aine on pysyvä, eliöihin kertyvä ja että sillä on mahdollisesti haitallisia vaikutuksia.
Tämä raportti on yhteenveto yhden bromatun palonestoaineen, teknisen pentabromidifenyylieetterin (pentaBDE) POP -ominaisuuksista suhteessa sopimusten valintakriteereihin. Raportti sisältää myös lisätietoja, joita voidaan käyttää harkittaessa aineen mahdollista nimeämistä POP –sopimuksiin sisällytettäväksi yhdisteeksi.
PentaBDE näyttää täyttävän molempien POP –sopimusten uusien aineiden lisäämistä koskevat valintakriteerit. Seurantatiedot osoittavat pentaBDE:n esiintymisen tausta-alueilla, minkä lisäksi sitä löytyy ilmanäytteistä. Nämä mittaustulokset osoittavat, että pentaBDE on kaukokulkeutuva aine. Lisäksi pentaBDE:n pääkomponenttien, BDE-47:n ja BDE-99:n puoliintumisajan on laskennallisesti arvioitu olevan 10-20 päivää ilmassa. Käytettävissä olevan laboratoriotestituloksen mukaan pentaBDE ei ole helposti hajoava aine. Mallintamistulosten mukaan pentaBDE on pysyvä vedessä ja sedimentissä. Tätä oletusta tukevat pitoisuustulokset sedimenttiprofiileista ja tausta-alueiden merinisäkkäistä.
PentaBDE:n on osoitettu olevan erittäin biokertyvä karppiin ja sen kertymisen sinisimpukoihin on todettu olevan jopa voimakkaampaa kuin monien PCB:n kongeneerien. Laboratorionisäkkäiden ja hauen on havaittu keräävän tehokkaasti pentaBDE:n pääkongeneereja ja eliminoivan niitä hitaasti. Tämä osoittaa aineen korkeaa biokertymispotentiaalia ja kykyä vastustaa biologista muuntumista. PentaBDE:n pitoisuuden vesieliöissä on osoitettu olevan sitä suurempi, mitä korkeammalla ravintoverkossa eliö on, eli se rikastuu ravintoverkossa. Uudet löydökset aineen pitoisuuksista petolinnuissa ovat lisätodisteita aineen biokertyvyydestä ja kyvystä vastustaa muuntumista eliöissä ravintoverkon eri tasoilla.
12 PentaBDE:n kyky aiheuttaa haitallisia vaikutuksia on osoitettu in vivo –kokeissa. Merkittävimpiä vaikutuksia laboratorionisäkäskokeiden mukaan ovat maksavauriot ja hermostolliset kehityshäiriöt. Myös hormonitoimintaa häiritseviä vaikutuksia ja dioksiinin tyyppisiä vaikutuksia on todettu solutason testeissä sekä pentaBDE:llä että sen ensisijaisilla muuntumistuotteilla.
Myös muita huolen aiheita on todettu. Viimeaikaisten tutkimusten mukaan pentaBDE:n pitoisuudet ihmisissä, kaloissa ja merinisäkkäissä ovat kohonneet. Muutamilla Pohjois-Amerikan alueilla pentaBDE:n pääkomponenttien pitoisuuksien on arvioitu saavuttavan pian jopa PCB -yhdisteiden pitoisuustason. Lisäksi pentaBDE:n käyttö lisää osaltaan myös dioksiinien ja furaanien päästöjä.
PentaBDE:ä käytetään lähes yksinomaan erityyppisissä polyuretaanivaahdoissa ja polyuretaanielastomeereissä. Suurin osa pentaBDE:llä palonsuojatusta polyuretaanista käytetään vuorostaan pehmusteissa ja huonekaluissa. PentaBDE:n maailmanlaajuinen kysyntä on yli kaksinkertaistunut viimeisen vuosikymmenen aikana nykyiseen 8500 tonniin vuodessa. Samalla sen käyttö on kuitenkin Euroopassa vähentynyt 210 tonniin vuodessa. Vaihtoehtoisia kemikaaleja ja tekniikoita on saatavilla lähes kaikissa pentaBDE:n käyttökohteissa.
Pääosa pentaBDE:n päästöistä ympäristöön tapahtuu sitä sisältävien tuotteiden käytön aikana ja sen jälkeen kun tuote on poistettu käytöstä. Suurin osa päästöistä muodostuu murustumisesta ja kulumisesta (pölynä), mutta haihtuminen on myös tunnistettu merkittäväksi päästöreitiksi kaikissa pentaBDE:n elinkaaren vaiheissa. Päästöt ovat pääasiassa hajapäästöjä, ja tehokkain tapa rajoittaa niitä näyttääkin olevan pentaBDE:n käytön rajoittaminen. Euroopan unionissa käsitellään parhaillaan ehdotusta pentaBDE:n käytön ja markkinoille saattamisen kieltämiseksi sekä kemikaalina että tuotteissa.
13 1 Introduction
1.1 International legally binding instruments focusing on POPs
Persistent organic pollutants (POPs) are described as chemicals which resist degradation, bioaccumulate, may be transported in the environment far from their sources and have the potential to cause adverse effects on human health or the environment. Due to their ability to travel for long distances, national or regional risk reduction measures have in many cases appeared to be insufficient to protect human health and the environment from the adverse effects of POPs.
During the last few years governments and international organisations have worked together in developing international, legally binding instruments with the aim of eliminating the pollution caused by the long-range environmental transport of POPs. The first international agreement focusing on POPs was agreed under the regional United Nations Economic Commission for Europe (UNECE). The UNECE Convention on Long-Range Transboundary Air Pollution (LRTAP) was extended by the Protocol on POPs, signed in Århus in 1998 (called in the following, the UNECE POP Protocol). Currently 36 parties of the LRTAP Convention have signed the Protocol. However, 16 ratifications are needed for the Protocol to enter into force. Until today, six of the signatory states have ratified the Protocol.
Global negotiations on POPs started officially in 1998 and were governed by the United Nations Environmental Program (UNEP). These negotiations were successfully concluded in Johannesburg, South-Africa in December 2000. The Convention was signed by 91 states in Stockholm in May 2001 (called in the following, the UNEP POP Convention). Fifty ratifications are required before the Convention enters into force. The UNEP Governing Council has encouraged countries to ratify the Convention with a view of its entry into force by 2004.
Both of these international instruments aim to protect human health and the environment by eliminating or restricting the production, use and releases of POPs. The UNEP POP Convention contains at the present a list of 12 POP chemicals. These consist of eight pesticides (aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, mirex and toxaphene), two industrial chemicals (hexachlorobenzene, which is also a pesticide and a by-product, and polychlorinated biphenyls) and two unintended by-products (chlorinated dioxins and furans). The UNECE POP Protocol covers a list of 16 substances. In addition to the 12 globally recognised POPs, the Protocol deals with two pesticides, chlordecone and hexachlorocyclohexane (HCH, including lindane), one industrial chemical, hexabromobiphenyl and one additional group of by-products, polyaromatic hydrocarbons, PAHs.
14 An important difference in the scope of these two instruments is that the UNECE Protocol deals only with those POPs which are transported across international boundaries by air. The POP Convention in principle also takes into account other environmental transport mechanisms, such as water and migratory species.
Both instruments oblige the signatory parties to ban or severely restrict the production and use of certain chemicals and to prevent and reduce their releases as well as those of certain by-products. In addition, they include provisions for dealing with the stockpiles and POP wastes.
1.2 Adding new POPs to the instruments
Both the UNECE Protocol and the UNEP Convention on POPs contain also a mechanism for adding new chemicals to these two instruments. A set of screening criteria and information requirements for additional POPs to be listed has been agreed. Any signatory party may propose to add a chemical to the list of banned or restricted chemicals. However, the proposing party is required to submit certain information to support its proposal. The proposal is then reviewed by a body or bodies of experts in order to ensure that the substance fulfils the criteria and warrants action within the framework of the instrument. The final decision on including a chemical within the scope of the instrument is made by the signatory parties.
The numerical screening criteria for additional POPs are in practice the same in both instruments (see Annex 1 and 2). However, there are significant differences in the emphasis and interpretation of the criteria and in the actual information requirements addressed to the proposing party. In addition, the procedures following the proposal differ considerably. In brief, the procedure laid down in the UNEP POP Convention is less demanding for the proposing party than the procedure agreed by the Executive Body of the UNECE POP Protocol. In the former instrument the mandatory data requirements for making a proposal are less exhaustive and thus facilitate initiatives also from countries with fewer capabilities.
In the UNECE POP Protocol procedure the proposing party has to submit not only data related to the screening criteria but also a risk profile and a summary document. This risk profile is to be a comprehensive review of the scientific information relating to the determination of general human health and environmental risks associated with the uses and releases of a substance, and which although it need not explicitly address risks associated with long-range transboundary air pollution, must provide suitable information for the assessment of such risks. The summary document must include information on alternative chemicals and pollution prevention techniques and their availability as well as health, environmental and socio-economic impacts associated with them. In contrast, in the UNEP POP Convention procedure the responsibility for preparing a risk profile and for analysing the socio-economic impacts of any control measures are given to the POP Review Committee. This procedure is clearly
15 stepwise and strictly separates the risk assessment phase from the risk management assessment dealing with socio-economic considerations.
There are also certain other important differences between these two instruments with regard to the handling of the proposals. The UNEP POP Convention calls for a transparent procedure and all parties and observers are invited to submit additional information during the handling of the proposal. The Convention text refers to the precautionary principle on several occasions and stipulates that the lack of full scientific certainty shall not prevent the proposal from proceeding, while the UNECE Protocol procedure stresses the need for a comprehensive risk profile and a summary document already at the proposing phase.
1.3 Objectives and structure of the report
The objective of this report is to present the required background information on pentabromodiphenyl ether (pentaBDE) in order to facilitate its nomination as a new POP to be included within the UNEP POP Convention and the UNECE POP Protocol. There are various reasons for selecting pentaBDE as a pilot substance for testing the set criteria and information requirements. It is an intentionally produced flame retardant used in many type of articles. Due to its wide use and releases to the environment, elevated levels of pentaBDE have been found in environmental and human tissue samples. All Nordic countries have bound themselves to stop using this flame retardant. The European Commission has already made a proposal for banning the use and placing on the market of pentaBDE or products and articles treated with it. The Commission’s proposal was preceded by the preparation of a comprehensive risk assessment report by the United Kingdom within the framework of the EU Regulation on Existing Chemicals. Therefore, most of the data needed has already been collected and reviewed.
With regard to the two different sets of information requirements and review procedures, this report has been structured to mainly follow the requirements of the global UNEP POP Convention. Chapters 2, 3 and 4 contain the information listed in the Annex D of the POP Convention required for the screening phase of a proposal. Chapter 5 presents additional information, as outlined in Annex E of the UNEP POP Convention, to support the review of the proposal. In addition, Chapter 6 gives an overview of alternatives and pollution prevention techniques for pentaBDE. This data is meant solely to support a possible proposal on pentaBDE in terms of the UNECE POP Protocol, not in terms of the UNEP POP Convention. With regard to the UNECE POP Protocol requirements, Chapters 2 and 3 are intended to form the risk profile for pentaBDE whereas Chapters 5 and 6 are meant to form the summary document.
The ecotoxicological and physical-chemical property data presented in this report are to large extent compiled from two comprehensive, high-quality review reports: the “Risk Assessment Report of Diphenyl Ether, Pentabromo Derivative (Pentabromodiphenyl ether), Final Report of August 2000” (COM 2000) and the “Environmental Health Criteria” no. 162 on “Brominated Diphenyl Ethers”
16 (WHO IPCS 1994). Although the test data from industry summarised in these two documents have not been reviewed from the original reports, the most recent results focussing on the environmental and human exposure in addition to the long-range environmental transport of pentaBDE have, however, been exhaustively researched and reviewed in this report. An abstract book of the “Dioxin 2000” conference (Organohalogen Compounds 2000) and “The Second International Workshop on Brominated Flame Retardants” (The Swedish Chemical Society 2001) also include other valuable new data outside that cited in this document. A recent review of brominated flame retardants in general with emphasis on PBDEs has been written by de Wit (2000).
17 2 Chemical identity
Commercial pentabromodiphenyl ether (pentaBDE) is a highly viscous liquid mixture of tri-, tetra- and pentabromodiphenyl ethers, hexabromodiphenyl ethers and heptabromodiphenyl ethers. The major components of pentaBDE products are 2,2’,4,4’ –tetrabromodiphenyl ether (BDE-47) and 2,2’,4,4’,5 – pentabromodiphenyl ether (BDE-99). The structural formula of BDE-99 is shown in Figure 1.
PentaBDE is one of the three present commercial polybrominated diphenyl ethers (PBDEs). The other commercial mixtures are octabromodiphenyl ether and decabromodiphenyl ether. There are altogether 209 isomers (congeners) in the group of PBDEs. The number of bromine atoms in the group varies between one and ten. Congeners with bromine amounts from three to ten are present in commercial products. Commercial pentaBDE products have been identified by the CAS number 32534-81-9, the CAS number of pentabromodiphenyl ethers. CAS numbers, IUPAC names and shares of the components of commercial pentaBDE are indicated in Table 1.
Br Br
O
Br Br Br
Figure 1. Structural formula of 2,2’,4,4’,5 –pentabromodiphenyl ether (BDE-99), main component of commercial pentaBDE.
Table 1. Chemical identity of the components of commercial pentaBDE.
IUPAC name CAS Number; Components of “a Components of molecular typical” commercial Bromkal 70 5DE formula pentaBDE (COM (Sjödin 1998); % 2000) ; % w/w w/w Tribromodiphenyl ether (TriBDE) 49690-94-0; 0-1 0.11 (BDE-28 C12H7Br3O 0.022 (BDE-17) Tetrabromodiphenyl ether 40088-47-9; 24-28 37 (BDE-47) (TetraBDE) C12H6Br4O Pentabromodiphenyl ether; 32534-81-9; 50-62 35 (BDE-99) diphenyl ether, pentabromo C12H5Br5O 6.8 (BDE-100) derivative (PentaBDE) 1.6 (BDE-85) Hexabromodiphenyl ether 36483-60-0; 4-12 3.9 (BDE-153) (HexaBDE) C12H4Br6O 2.5 (BDE-154 0.41 (BDE-138) Heptabromodiphenyl ether 68928-80-3; Trace (HeptaBDE) C12H3Br7O
18 The trade names of pentaBDE according to WHO IPCS (1994) and COM (2000) are:
• Bromkal 70 • Bromkal 70 DE • Bromkal 70 5DE • Bromkal G1 • Great Lakes DE 71 • Great Lakes DE-60 F (85 % PeBDE) • FR 1205/1215 • Pentabromprop • Saytex 115 • Tardex 50
Other common abbreviations for pentabromodiphenyl ether are: PeBDPE and PentaBDPE.
Synonyms used for pentabromodiphenyl ether are:
• Benzene, 1,1’-oxybis-, pentabromo derivative • Pentabromophenoxybenzene • Pentabromobi(s)phenyl ether; biphenyl ether, pentabromo derivative = PeBBE • Pentabromobi(s)phenyl oxide = PeBBO • Pentabromodiphenyl oxide = PeBDPO = PentaBDPO
In this report, the term pentabromodiphenyl ether and the abbreviation pentaBDE refer to the commercial product if not otherwise stated.
19 3 Information on pentabromodi- phenyl ether in relation to the POP screening criteria
3.1 Persistence
Test and SAR data
According to a standard OECD 301B ready biodegradability test with aerobic activated sludge sewage treatment plant organisms (Schaefer and Haberlein 1997 as cited in COM 2000), pentaBDE is not readily biodegradable.
No experimental studies have been reported on the abiotic degradation of pentaBDE. Nevertheless, according to the results from a decabromodiphenyl ether study (Sellström et al. 1998), photolysis resulting in reductive debromination may be a possible pathway for abiotic degradation. Moreover, based on experiences with brominated biphenyls and other organohalogens it seems that it may be that reductive degradation by photolysis or in anaerobic conditions may also occur, but its significance is unknown (COM 2000).
Abiotic and biotic degradation of pentaBDE in sediment, water and soil have not been reported in experimental studies but the half-lives for these compartments have been estimated for BDE-47 and BDE-99 with the Syracuse Research Corporation’s EPIWIN program based on structure-activity relationship (SAR) - modelling (see Table 2).
Table 2. Estimated total (biotic and abiotic) half-lives of the compounds of pentaBDE in soil, sediment and water. This estimation was carried out by Palm (2001) with the Syracuse Corporation’s EPIWIN program.
Half-life (d) Component Aerobic sediment 600 BDE-47 Soil 150 BDE-47 Water 150 BDE-47 Aerobic sediment 600 BDE-99 Soil 150 BDE-99 Water 150 BDE-99
Evidence from environmental data
PentaBDE congeners deposited in marine sediments a few decades ago are still present in clearly quantifiable amounts (Nylund et al. 1992; Zegers et al. 2000) indicating high persistency in sediment. Also data from remote regions presented in later chapters indicate high persistency to degradation in the environment.
20 3.2 Bioaccumulation
Test data
All components of pentaBDE as well as of commercial pentaBDE have a logKow greater than 5 (e.g., Watanabe and Tatsukawa 1990), suggesting that they have potential to bioaccumulate. All the components of commercial pentaBDE bioconcentrated in carp (Cyprinus carpio). The bioconcentration factor (BCF) for commercial pentaBDE in carp was estimated to be ca. 27 400 (COM 2000).
BDE-47 is taken up more efficiently in pike (Esox lucius) than CB-153, the PCB congener with the highest concentrations in biota. Both BDE-99 uptake and BDE- 153 uptake in pike are similar to those of the other PCBs studied (-31, -52, -77 and -118) (Burreau et al. 1997). BDE-47, BDE-99 and pentaBDE are taken up efficiently and excreted slowly by rats and mice. Excretion is mainly fecal. Uptake efficiency and elimination time correlates negatively with the degree of bromination (von Meyernick et al. 1990; Örn and Klasson-Wehler 1998; Hakk et al. 1999).
The bioaccumulation potentials of the congeners BDE-47 and BDE-99 in blue mussels (Mytilus edulis) have been shown to be one order of magnitude higher than the bioaccumulation potential of the PCB congeners studied (CB-31, CB-52, CB-77, CB-118 and CB-153) (Gustafsson et al. 1999).
Evidence from environmental data
Concentrations of the major pentaBDE congeners increase as the trophic level rises in the biota of the same region, showing that pentaBDE is biomagnified (results from Baltic Sea sprat, herring and salmon by Burreau et al. 1999 and from Atlantic biota by Burreau et al. 2000). Tetrabrominated and pentabrominated diphenyl ethers show the highest biomagnification potential of all PBDEs studied. Increasing levels of pentaBDE congeners with rising trophic position can be observed for the data in biota from around the world.
According to results from pooled Baltic Sea herring samples (Haglund et al. 1997) and sprat samples (Strandman et al. 1999; see Figure 2), concentrations of pentaBDE congeners increase with the age of marine fish, indicating bioaccumulation and high resistence to metabolic transformation.
21 140
120
100
80
60
40
and BDE-153 (ng/g lipid) 20
Sum concentration of BDE-47, BDE-99 0 2468101214 Age (years)
Figure 2. Dependency of the sum BDE-47, BDE-99 and BDE-153 concentration on the age of Baltic sprat (Sprattus sprattus) (Strandman et al. 1999) .
3.3 Potential for long-range environmental transport
PentaBDE components have very low volatility (vapour pressure between ca. 9.6 × 10-8 – 4.7 × 10-5 as measured by Tittlemier and Tomy 2000) and water solubility (between ca. 2 – 13 µg/l, summarised in COM 2000). The estimated Henry’s Law constants (COM 2000) nevertheless suggest that at least the lower brominated components can also be volatilised in significant amounts from aqueous solutions. Vapour pressure and water solubility decreases with increasing bromination.
According to the atmospheric half-life estimates from SAR modelling (see Table 3), pentaBDE has long-range transport potential in the atmosphere.
Table 3. Estimated atmospheric half-lives (reaction with hydroxyl radicals) for pentaBDE components.
Component Half-life (d) Reference BDE-47 11 Palm (2001) BDE-99 13 COM (2000) BDE-99 20 Palm (2001) BDE-99 10 Danish EPA (2001)
Evidence from environmental data
BDE-47 especially has been observed in the vapour phase in air samples indoors and outdoors (Bergander et al. 1995; Sjödin et al. 1999; Alaee et al. 2000; Dodder et al. 2000; Bidleman et al. 2001), which indicates the potential for long-range transport. Also a major share of BDE-99 has been measured in the vapour phase in the same studies. The difference in the PBDE congener profiles from fish samples at a possible point source and a background area suggest that BDE-47 especially is susceptible to long-range transport via air (Dodder et al. 2000).
22 BDE-47, BDE-99 and BDE-100 have been found in the Arctic air at the remote sites of Canada, Alert and Russia, Dunai. Total concentrations were <1-28 pg/m3 and BDE-47 and BDE-99 were the most abundant congeners in samples collected in 1994 (Alaee et al. 2000). At another remote Arctic area in Pallas, Finland, BDE-47 and BDE-99 concentrations were measured between 0.3-2 pg/m3 (Peltola 2001). The same congeners were also observed at two Swedish sites, Ammarnäs and Hoburgen, remote from point sources (Bergander et al. 1995). The sumPBDE concentration in the air varied in this study generally between ca. 1 and 10 pg/m3.
Data from remote areas are still scarce but indicate clearly increasing contamination by pentaBDE. Concentrations of the two major congeners in whales have been reported in the range of ca. 66 to 864 ng/g lipid (BDE-47) and 24 to 169 ng/g lipid (BDE-99) (e.g., de Boer et al. 1998; van Bavel et al. 1999; Alaee et al. 2000; Stern and Ikonomou 2000). BDE-47 concentrations measured in Arctic marine mammals have been found to even exceed the concentrations of CB-153 (Alaee et al. 2000). Figure 3 based on Stern and Ikonomou (2000) shows an increasing temporal trend of PBDE concentrations in Arctic beluga whales (Delphinapterus leucas).
7
6
5
4
3
2
1 Relative increase of the sumBDE concentration 1982 1986 1992 1997
Figure 3. The relative temporal increase of total PBDE concentration in Arctic beluga whales (Delphinapterus leucas) (Stern and Ikonomou 2000). The total concentration consists of tri- to hexaBDEs.
23 3.4 Adverse effects
In vivo rat studies indicate that the liver is the main target organ affected by pentaBDE (summarised in COM 2000) with a NOAEL of 1 mg/kg/d. Other in vivo studies have found i.a., developmental neurotoxicity (Eriksson et al. 1998; Branchi et al. 2001, Eriksson et al. 2001). Eriksson et al. (1998) found behavioral effects already after a single dose of 0.8 mg/kg BDE-99 to 10 days old mouse pups.
BDE-47 was shown to be acutely toxic for a copepod Acartia tonsa in a standard 48 h study by Breitholz et al. (2001). Moreover, BDE-47 caused disturbances in larval development in much lower levels. The EC50 in a 5 day study was determined as 13 µg/l.
Tjärnlund et al. (1998) observed significant inhibition of EROD activity in the liver of rainbow trout (Oncorhynchus mykiss) when fed with food containing BDE-47. Also other metabolic alterations were observed. Effects on rainbow trout fry sack growth were found at the level of 16 µg/l in the study by Wildlife International (2000).
In vitro studies have shown i.a., the thyroxin competing potential of hydroxylated metabolites and other metabolites (Meerts et al. 1998; Brouwer et al. 2001), an ability to activate the Ah-receptor (e.g., Meerts et al. 1998; Bunce et al. 2001) and possible genotoxicity (intragenic recombination) (Helleday et al. 1999). Immunotoxicity for the major pentaBDE congeners has been shown in mice but not in rats (Darnerud and Thuvander 1998). Also antiestrogenic response has been shown in vitro to be caused by several pentaBDE congeners (Brouwer et al. 2001).
24 4 Statement of the reasons for concern and need for global action
According to the available data, pentaBDE resists abiotic and biotic degradation and thus persists in the environment for long times. It has a great potential for bioaccumulation and in addition there is monitoring evidence of its biomagnification. Due to its physical and chemical properties and considerably long atmospheric half-life it can be assumed that pentaBDE can be transported long distances in air. There is a solid data base on the toxic and ecotoxic properties of pentaBDE showing that it or its metabolites cause, inter alia, adverse developmental effects in offspring, liver effects, growth disturbance, dioxin-like effects and endocrine disruption depending on the target organism studied.
This data on the harmful properties of pentaBDE are supported by data from the environment. The available data from remote areas show clearly contamination of biota and air by pentaBDE. A few observations of temporally increasing contamination are also available from remote areas. It must be underscored that biological effects in remote area marine mammals cannot be excluded. An upward trend has been observed also in the general human population in blood and milk.
PentaBDE is widely used as a flame retardant in different articles throughout the world, for the most part in connection with polyurethane applications. The releases of pentaBDE are coming mainly from diffuse sources. The ability of pentaBDE to move in the atmosphere far from its sources further widens the area contaminated by it. No single country nor groups of countries alone can abate the pollution caused by the production, use and releases of pentaBDE. Therefore regional and global actions are needed to eliminate this pollution.
25 5 Additional information on pentabromodiphenyl ether
In addition to reviews and studies cited in this report, further information on pentaBDE can be found i.a., in the conference proceedings of DIOXIN 2000 (Organohalogen Compounds 2000) and “The Second International Workshop on Brominated Flame Retardants (2001).
5.1 Sources
5.1.1 Production and market PentaBDE belongs to the group of organic brominated flame retardants, which in 1997 comprised over 20 % of the world flame retardant market volume by base element content (Roskill Information Services 1997). Brominated flame retardants constitute the major use of the 470 thousand tonnes of annual bromine production (BSEF 2000). Other flame retardants consist mainly of different (mainly organic) chlorine, aluminium, phosphorus, nitrogen and antimony compounds (OECD 1994; WHO IPCS 1997).
At present, due to research efforts on the part of industry and independent research organisations in the last two decades, more is known about the use, fate, adverse properties and exposure of brominated flame retardants than is the case with other flame retardants. The most well known brominated flame retardant is pentaBDE.
Fourty-seven different commercial brominated flame retardants have been listed in Lassen et al. (1999) and in the WHO IPCS (1997). Approximately 30 of them are in wide use (OECD 1994). Global annual market demand for major brominated flame retardants has been reported by the industry for 1999 (see Table 4). The most used flame retardants in the Western European market and their uses are listed in Annex 4.
Table 4. Total market demand for major brominated flame retardants (tn) by region in 1999 according to BSEF (2000). * Used mainly in North America. ** Calculated taken that the use in Asia is 0 tn. TBBPA = tetrabromo-bis-phenol A; HBCD = hexabrmocyclododecane. Europe Americas Asia Total Share of these products TBBPA 13,800 21,600 85,900 121,300 59 % HBCD 8,900 3,100 3,900 15,900 8 % Deca-BDE 7,500 24,300 23,000 54,800 27 % Octa-BDE 450 1,375 2,000 3,825 2 % Penta-BDE 210 8,290* -- 8,500 4 %** (13 % of all PBDEs) Sum of products 30,860 58,665 114,800 204,325 above 15.1 % 28.7 % 56.2 % 100 %
26 PentaBDE is at the present produced in the U.S., Israel and Japan. PentaBDE’s share of the world’s consumption of 40 000 tn/a PBDEs was reported in the 1990’s to be ca. 10 % (WHO IPCS 1994). Based on the market information in the report of BSEF (2000) it would seem that the share of pentaBDE of global PBDE consumption has grown slightly. In 2000, the total consumption of pentaBDE in Europe was according to DETR (2000) approximately 250 tn, of which 125 tn was in the form of chemical products and the rest imported in pentaBDE -treated articles.
According to data from Japan and Europe (WHO IPCS 1994), the consumption of PBDEs increased until the early 1990’s. In Europe, the consumption remained stable at the beginning of the 1990’s (Frost & Sullivan 1997) and decreased subsequently significantly by 1998.
PentaBDE is on the High Production Volume list of the U.S.Environmental Protection Agency (initial list from 1990; voluntarily updated by the end of 1999), meaning that an amount of more than 1 million pounds (ca. 500 tn) of pentaBDE was being produced in or imported to the U.S. annually.
5.1.2 Uses The producers of pentaBDE have provided information to the effect that pentaBDE is used today solely in different polyurethane (PUR) applications. According to DETR (2000), this PUR is in turn used mainly as PUR foam for furniture and upholstery in automotive industry and domestic furnishing. Other possible minor uses are in rigid polyurethane elastomers (e.g., in instrument casings), in epoxy resins and phenol resins (electric and electronic appliances). The current use (as of year 1999/2000) of pentaBDE in flexible PUR covers ca. 95 % of the total consumption of pentaBDE in Europe (DETR 2000).
PentaBDE was used in the past in minor amounts also in textiles, in mining industry rubber belts and in oil drilling fluids (WHO IPCS 1994; COM 2000).
5.1.3 Releases to the environment Emissions from production of pentaBDE
PentaBDE is synthesised from diphenyl ether by brominating it with B2 in the presence of a powdered iron/Friedell-Crafts catalyst (WHO IPCS 1994; COM 2000). The producers of pentaBDE have reported that the major routes of pentaBDE to the environment are filter waste and rejected material, both of which are disposed of in landfills. Waste water releases of pentaBDE may also occur from spent scrubber solutions (COM 2000). No measured data on releases from production sites are available at the moment.
27 Emissions from PUR production
According to the EU risk assessment of pentaBDE (COM 2000), the emissions in polyurethane production are assumed to occur prior to the foaming process when handling the additives (discharges to water) and during the curing (emissions to air). In the phase prior to foaming, releases to waste water are estimated at 0.1 kg/tonne handled pentaBDE. Releases to air may occur during the curing phase of the foam, when the temperature of the foam stays elevated for many hours depending on the production block size. Emission to air at this phase is estimated at 1 kg/tonne pentaBDE, but it is assumed that some of the volatilised pentaBDE condenses in the production room ending up in the waste water. The EU risk assessment concludes that 0.6 kg of pentaBDE is released into waste water and 0.5 kg into air for each ton of pentaBDE used. The worst-case PUR production site releases to waste water and air are estimated at 44.6 kg/year and 37.2 kg/year, respectively.
For the whole EU region the annual releases are estimated at 180 kg to waste water and 150 kg to air assuming that 300 tn/a of pentaBDE is used solely in PUR production in the EU.
Releases during the life-cycle of articles containing PUR with pentaBDE as an additive (releases after the manufacture of PUR)
Losses of pentaBDE to the environment during the life-cycle after manufacturing may occur:
• Through volatilisation during the service life: 3.9 % of the pentaBDE present in articles was estimated to be released through volatilisation during their approximated service life of 10 years in the EU risk assessment (COM 2000). PentaBDE is used solely as an additive chemical. Thus it can volatilise from the products during their whole life-cycle. • From products due to weathering and wearing during their service life. There is no calculated release estimate for this life-cycle phase available (except for a rough estimate as a part of the EU risk assessment). Monitoring data from municipal waste water treatment plant (WWTP) sludge indicate that pentaBDE is released in large quantities to municipal waste water. Concentrations in WWTP sludge from different WWTPs within a region are very similar (Hale et al. 2001; see also Annex 6). This indicates that the source of pentaBDE in the municipal waste water is diffuse by nature. • From products due to weathering, wearing, leaching and volatilisaton at the end of their service life during disposal or recycling operations (dismantling, grinding or other handling of waste, transport, storage, etc.).
The annual releases in the EU region from the product life-cycle of PUR products were estimated to be distributed among the different compartments as follows: 75 % to soil, 1 % to air and 24 % to surface water (COM 2000).
28 Releases from landfills by leaching and emissions from incineration are considered negligible. There is no information on possible releases of pentaBDE from products other than articles with PUR.
To conclude, available information on releases of pentaBDE from products during the whole of their life cycle is not exhaustive, but it can be stated that most of the pentaBDE is released as diffuse pollution during and after the service life of articles treated with pentaBDE and as small-scale point source pollution from the waste management chain of the end-products.
Other sources of pentaBDE in the environment
There are traces of congeners appearing in pentaBDE in the other two PBDE products. The traces of tri- to pentabrominated congeners are, however, so small in these two products that their contribution to the exposure is negligible (COM 2000). The composition of the PBDEs on the market according to the EU suppliers is denoted in Figure 4.
97,4 60
50
40
30 % w/w 20
10 0,23 0,04 0 triBDE pentaBDE heptaBDE nonaBDE
Commercial pentaBDE Commercial octaBDE Commercial decaBDE
Figure 4. The composition of present three commercial PBDEs as reported by the EU market suppliers (compiled from COM 2000).
According to photodegradation studies by Sellström et al. (1998), Eriksson et al. (2001) and Tysklind et al. (2001), reductive debromination of photochemical degradation of commercial octa- and decaBDE products may also be a source of congeners present in pentaBDE products. However, in relation to the direct emissions and releases of pentaBDE, the contribution of the degradadation of octaBDE and decaBDE to the environmental levels of pentaBDE’s components is presently considered insignificant (COM 2000).
29 5.1.4 Aspects concerning recycling of materials containing pentaBDE Most of the pentaBDE which is still present in articles after their service life can be expected to end up mainly in landfills but some of it may also end up in incinerators. However, products such as cars or other products with metal parts undergo a recycling process, mainly in shredders, where the metal parts are separated from other parts. Shredding can cause significant releases of dust from products depending on the shredding technique. Releases of pentaBDE occur most likely with dust releases. However, no air or dust analyses have been performed so far in metal recycling plants except in electronics dismantling plants, where pentaBDE releases can be expected to be low.
According to several studies (summarised in WHO IPCS 1998; COM 2000), if plastics waste containing brominated flame retardants is incinerated, polybrominated dioxins and polybrominated furans (PBDD/Fs) will be formed if the combustion process is not complete. On the other hand, in a well functioning incineration process PBDD/Fs are not formed. Moreover, according to Tange (2001) bromine can be recovered from incineration as HBr.
5.1.5 Brominated dioxins and furans The properties, formation, occurrence, fate and adverse effects of PBDD/Fs have been reviewed in the WHO IPCS (1998) and health effects lately by Birnbaum (2001). PBDD/Fs have low water solubility and they are more susceptible to photodegradation than polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs).
PBDD/Fs may be present in pentaBDE as an impurity. They have also been observed to be formed from PBDEs due to exposure to light. PBDFs have been formed from pentaBDE in thermal exposure, especially in temperatures of 700- 800 ºC. PBDDs are also formed in thermolysis from brominated flame retardants. PBDD/Fs have been consequently observed in PUR (exothermal production process) with pentaBDE. However, accidental fires have been assumed to be the major source of PBDD/F releases, but no estimate of the significance of different sources has been presented.
PBDD/Fs are thought to bioaccumulate in a manner similar to that of PCDD/Fs. PBDD/Fs have been detected in urban air and dust and indoor air of rooms with electronic equipment. They have also been quantified in sewage sludge, sediment and soil but they were not found in humans. PBDD/Fs cause the same spectrum of adverse effects as PCDD/Fs with varying potency. The potency of most toxic PBDD/Fs is similar to or for a few endpoints even higher than the potency of 2,3,7,8, -tetrachlorodibenzo-p-dioxin, the most toxic halogenated compound.
30 5.2 Physical and chemical properties
The environmentally relevant physical and chemical properties of pentaBDE are presented in Table 5.
Table 5. Physico-chemical properties of pentaBDE. Source: COM (2000) if not otherwise stated.
Molecular weight 564.66 g/mol (commercial product, 70.8 % bromine by weight)
Melting point -7 to -3°C (commercial product)
Boiling point Decomposes at > 200 °C (commercial product)
Relative density 2.25-2.28 (commercial product)
Vapour pressure 4.69×10-5 Pa at 21°C (commercial product) Tittlemier and Tomy 1.43×10-4 Pa at 25°C (BDE-28, i.e. triBDE) (2000) 1.45×10-5 Pa at 25°C (BDE-47, i.e. tetraBDE) -’’- 1.55×10-6 Pa at 25°C (BDE-85, i.e. pentaBDE) -’’- 7.76×10-6 Pa at 25°C (BDE-99, i.e. pentaBDE) -’’- 7.59×10-7 Pa at 25°C (BDE-118, i.e. heptaBDE) -’’- -8 -’’- 9.55×10 Pa at 25°C (BDE-190, i.e. hexaBDE)
Water solubility 13.3 µg/l (measured; commercial product) 2.4 µg/l (measured; BDE-99) 10.9 µg/l (measured; BDE-47)
Henrys’ Law constant 0.86 (TetraBDE) (Pa m3/mol) 0.36 (BDE-99) 0.36 (BDE-100) 0.15 (HexaBDE) 0.06 (HeptaBDE)
Octanol-water 6.57 (measured; commercial product) partition coefficient 7.88 (calculated; commercial product) (logKow) 5.47-5.58 (measured; TriBDE) Watanabe and 5.87-6.16 (measured; TetraBDE) Tatsukawa (1990) 6.46-6.97 (measured; PentaBDE) -“- 6.86-7.92 (measured; HexaBDE) -“-
Sediment-water 28.29 (measured; TetraBDE) Watanabe (1988) partition coefficient 49.17 (measured; PentaBDE) -“- (kpsed l/kg) 62,73 (measured; HexaBDE) -“-
Viscosity Highly viscous at room temperature (ca. 2×106 cps at 25°C); commercial product
31 5.3 Environmental fate
5.3.1 Degradation and transformation Methoxylated tetra- and pentabrominated diphenyl ethers (MeO-BDEs) have been detected simultaneously with tetra- and pentabrominated diphenyl ethers in Baltic Sea marine mammals and fish (Haglund et al. 1997; Asplund et al. 1999a). Asplund et al. (1999a) have reported (tetra- to penta-) MeO-BDEs in Baltic Sea salmon in the same concentrations as PBDEs, whereas concentrations of hydroxylated PBDEs (OH-BDEs) have been found at levels 20-30 % smaller. The source of such amounts of methoxylated brominated diphenyl ethers in Baltic Sea biota is so far unknown. Nevertheless, rat metabolism studies with BDE-99 show that MeO-BDEs can be formed as metabolites although in minor amounts (Hakk et al. 1999).
PentaBDE is not readily biodegradable according to a standard OECD test (Schaefer and Haberlein 1997). In addition, BDE-47 and BDE-99 did not show any biotransformation in an in vitro test with harbour seal hepatic microsomes, indicating higher persistency than for CB-26, CB-28 and CB-101 in the same test (de Boer et al. 1998). On the other hand, in vitro biotransformation of major pentaBDE congeners among other PBDE congeners to unknown hydroxylated metabolites was induced in incubations with rat hepatic microsomes (Meerts et al. 1998).
Levels of pentaBDE congeners increase with age according to results from pooled Baltic Sea herring samples (Haglund et al. 1997) and sprat samples (Strandman et al. 1999), indicating persistency to biological elimination. In both studies the concentrations level off in the oldest generations. The increase of concentration may also reflect change in trophic position with age and simultaneous saturation for a steady state concentration, but the question has not been addressed in the available literature.
5.3.2 Environmental transport Once in the environment, pentaBDE is expected to be transported in the environment by being mainly absorbed onto particles due to its low volatility, low solubility and high affinity for carbon compounds. Palm (2001) has presented a model of how, due to their properties, the major pentaBDE congeners partition between the different compartments of the environment (see Figure 5 for BDE- 99).
32 2.08x10-5 kg/year To 3.16 kg/year stratosphere
2.25x10-3 3.18 kg/year Air kg/year 1.73x10-4 kg (0.10%) 6.15 pg/m3 0 kg/year f = 2.22x10-11 Pa 0.010 kg/year
1.47x10-3 kg/year Urban film 5.92 x10-3 kg/year 2.52x10-3 3.87x10-4kg (0.23 %) kg/year 50.1 mg/m3 f=1.25E-11Pa 8.38x10-4 kg/year 4.41x10-3 kg/year Soil 0.59 kg/year Water 0.10 kg (60.4 %) 1.58x10-3 kg/year 9.40x10-4 kg (0.54 0.12 ng/g ar -14 g/ye %) 5.33pg/L f = 2.25x10 Pa .14 k 0 f= 3.84x10-14 Pa 0.025 kg/year 0.17kg/year 0 kg/year 0.42 kg/year 0.12 kg/year
Sediment emission 0.067 kg (38.7 %) 0.50 ng/g -13 Total mass: 0.172 kg f =5.92x10 Pa advection Persistence = 385.74 h = 16.07 days 0.028 kg/year reaction 0.09 kg/year intermedia transport
Figure 5. Environmental distribution and transport of BDE-99 in the urban environment of Stockholm (from Palm 2001). f = fugacity of the chemical in the given media.
The EU risk assessment on pentaBDE concluded that the major part of releases end up in soil. From soil, pentaBDE congeners can be expected to be moved mainly through leaching with water in the suspended solids fraction or through wind erosion where it occurs. A small part of the mass in the soil can be volatilised, especially in the warm season.
Although pentaBDE has low water solubility, it has been found in water (Lake Ontario, 1999). BDE-47 and BDE-99 made up >70 % of the total amount of PBDEs and approximately 90 % of the all PBDEs were in the soluble phase (Luckey et al. 2001). Total PBDE concentrations were between 4 and 3 pg/l. BDE-47, BDE-99 and BDE-100 have been detected in Sweden where water contained them as a total 0.3 ng/l (study summarised by de Wit 2000). BDE-47, BDE-99 and BDE-100 were also found in urban stormwater leachate in level of ca. 10 ng/l as the sum of the three congeners (Peltola 2001). These results indicate that pentaBDE can be transported with water in the soluble and particle phases.
Figures 6a and 6b are examples of the results of air analyses where pentaBDE congeners have been detected in both the vapour and particle phases. The figures present a typical disribution of congeners between the two phases as far as they have been studied.
33 Ammarnäs Hoburgen
5 ) 3 4
3
2
1 Concentration in air (pg/m Concentration in 0 Particulate phase
7 9 Gas phase E-4 -9 D 7 B DE 4 9 B -9 0 DE- 0 BDE-100 B DE B E-1 D B Figure 6a. Sum of mono- to heptaBDEs in Figure 6b. Air concentrations of the major archived air extracts from Tagish, Yukon, Canada pentaBDE congeners at two Swedish 1994-1995. Results from polyurethane filter (PUF) sampling sites far from sources (data from indicate the concentration in the vapor phase and Bergander et al. 1995, C. de Wit, Inst. filter results the concentration in the particulate Appliend Env. Res., Stockholm University, phase. BDE-47 and BDE-99 were the main personal communication). congeners in all samples. 74-98 % of BDE-47 was observed in the vapor phase (Bidleman et al. 2001).
5.3.3 Bioaccumulation and biomagnification Uptake efficiency of BDE-47 (> 90 %) in pike (Esox lucius) as an amount remaining in the body after 9 days of a single dose was clearly higher than the uptake efficiency of CB-153 (< 80 %), the most abundant PCB congener in the environment. The uptake efficiencies of BDE-99 and BDE-153 were similar to those of the other PCBs studied (-31, -52, -77, -118) (Burreau et al. 1997).
The half-lives of the major components of the pentaBDE product Bromkal 70 were shown to be long in an in vivo single dose 10-week test with rats (von Meyernick et al. 1990). The half-lives varied between 19 and 119 days depending on the component and gender. The test results indicate a potential for bioaccumulation for some if not all components.
According to Örn and Klasson-Wehler (1998) and Hakk et al. (1999), BDE-47 and BDE-99, respectively, are poorly metabolised in rats. BDE-47 was metabolised somewhat better in mice in the study by Örn and Klasson-Wehler (1998), where 39 % of the excreted part of the single dose was metabolites. In a single dose study of BDE-47, 86 % and 47 % of the dose remained after 5 days in the tissues of rats and mice, respectively (Örn and Klasson-Wehler 1998). BDE- 99 was reported to be excreted slightly faster in rats by Hakk et al. (1999), but also mainly as the unmetabolised BDE-99. The previously described in vitro study with marine mammal cells also confirms poor metabolisation in higher organisms (de Boer et al. 1998).
The bioaccumulation potential of the congeners BDE-47 and BDE-99 in blue mussels (Mytilus edulis) expressed as bioaccumulation factor (BAF) have been shown to be one order of magnitude higher than the bioaccumulation potential of the PCB congeners studied (CB-31, CB-52, CB-77, CB-118, CB-153) in an in
34 5 5 vivo study (Gustafsson et al. 1999). Bioaccumulation factors were 13î10 , 14î10 5 and 2.2î10 for BDE-47, BDE-99 and BDE-153, respectively. The theoretical depuration half-lives of the three BDEs were all similar (7.7-8.1 d) and also similar to those of CB-31, CB-52, CB-77 but shorter than those of CB-118 and CB-153.
The biomagnification potentials of BDE-17+25, BDE-28, BDE-35, BDE-47, BDE-49, BDE-66, BDE-99, BDE-100 and BDE-154 have been estimated with concentrations in Baltic Sea sprat, herring and salmon. These estimations were based on the stable 14N and 15N isotope shares (Burreau et al. 1999) in fish. Tetra- and pentaBDEs showed the highest biomagnification potential and BDE-154 clearly a smaller potential. Tri- to pentabrominated congeners seemed to biomagnify more effectively than all PCBs studied.
Bioaccumulation can be observed from measured concentrations in top food chain predators. Eggs of peregrine falcons (Falco peregrinus) from Sweden contained 15-3800 ng/g lipid BDE-47, 110-9200 ng/g lipid BDE-99 and similar levels of BDE-100, BDE-153 and BDE-154 (Sellström et al. 2001a). Lepom et al. (2001) detected high levels of congeners of pentaBDE in the blood of nestlings of the peregrine falcon (0.6-6.4 µg/l), white-tailed eagle (Haliaetus albicilla) (1.1-1.6 µg/l), goshawk (Accipiter gentilis) (2.0-7.4 µg/l) and sparrowhawk (Accipiter nisus) (26.6-29.2 µg/l) from Germany. A few of the adults measured had levels 10 to 100 times higher than nestlings. The sum of PCB-138, PBC-153 and PCB-180 concentrations were in same order of magnitude or higher.
Other studies of concentrations at different trophic levels seem to confirm the results of the two biomagnification studies above. E.g., concentrations of pentaBDE congeners in recently sampled Baltic Sea grey seals (Halicoerus crypus) were reported to be between 60-582 ng/g lipid by Roos et al. (2001), which is considerably higher than those seen in Baltic herring and higher than concentrations in Baltic salmon.
35 5.4 Effects
5.4.1 Environment
Aquatic biota
Table 6 shows the major ecotoxicity studies of the aquatic environment and their main results.
Table 6. Major results from ecotoxicological studies in the aquatic environment.
Organism Test type Test result Reference (substance) Rainbow trout Early life stage toxicity Effects on growth 1) (Oncorhynchus test/OECD 210 with NOEC of 8.9 mykiss) (mixture of tri- to µg/l and LOEC of 16 hexaBDEs) µg/l
22 d exposure via EROD inhibition 2) daily feeding (BDE-47)
Calanoid Acartia tonsa 48h acute toxicity test LC50 = 2.37 mg/l 3) (BDE-47)
5 day larval 0.013 mg/l 3) development test (BDE-47)
Cladoceran Daphnia 48 h acute toxicity EC50 = 14 µg/l 4) magna test/based on OECD NOEC = 4.9 µg/l 202 (mixture of tetra- to hexaBDEs)
21 d life-cycle NOEC = 5,3 µg/l 5) study/OECD 202 LOEC = 9,8 µg/l (mixture of tetra- to hexaBDEs) 1) Wildlife International (2000), as cited in COM (2000). 2) Tjärnlund et al. (1998). 3) Breitholz et al. (2001). 4) CITI (1982), as cited in COM (2000). 5) Dottar and Krueger (1998), as cited in COM (2000).
Terrestrial biota
Adverse effects of pentaBDE have been studied with terrestrial plants, and earthworms (summarised in COM 2000). Studies on tomato and soybean showed a small but significant effect to growth. Only for tomato could a NOEC of 125 mg/kg dry weight be quantified.
36 5.4.2 Laboratory mammals –health effects Table 7 shows some of the major toxicity studies and their main results.
Table 7. Most relevant toxicological findings from studies with laboratory mammals.
Animal Test type (substance) Effect LOAEL/NOAEL Ref. Rat Repeated dose study of 90 Liver effects 10 mg/kg/day 1) days (DE-71) (LOAEL)
Rat Several single and repeated Several liver effects 1 mg/kg/day 2) dose studies (NOAEL; identified from a 30 day study with DE-71)
Mouse Single dose study (DE-71) Serum thyroxin 0.8 mg/kg (LOAEL) 3) decreased
Mouse Developmental study, Offspring toxicity; 1 mg/kg/day 4) maternal exposure (DE-71) serum thyroxin (LOAEL) decreased
Mouse Developmental study, single Developmental neuro- 5) dose (BDE-99) toxicity: *Spatial learning 12 mg/kg (LOAEL) *Spontaneous motor 0.8 mg/kg (LOAEL) behavior
Mouse Developmental study, Developmental neuro- 0,6 mg/kg/day 6) perinatal exposure, repeated toxicity (spontaneous (LOAEL) dose (BDE-99) motor behavior)
Mouse Developmental study, single Developmental neuro- 10.5 mg/kg (LOAEL) 5) dose (BDE-47) toxicity 0.7 mg/kg (NOAEL)
1) WHO IPCS (1994). 2) Several studies carried out by the industry, summarised in COM (2000). 3) Fowles et al. (1994) as interpreted in Darnerud et al. (2001). 4) Zhou et al. (2000) as interpreted in Darnerud et al. (2001). 5) Eriksson et al. (1998). 6) Branchi et al. (2001).
37 5.4.3 Predicted no effect levels Table 8 shows the predicted no-effect concentrations (PNECs) and the identified threshold levels for human health from the EU risk assessment of pentaBDE (COM 2000). The method for determining these concentrations is based on the EU Technical Guidance Document for the risk assessment of substances (COM 1996). The PNECs are derived from a safety factor and from e.g., a test result for NOEC for each effect. Thus the values are not necessarily direct results from toxicity tests but further calculated values.
Table 8. The predicted ”no-effect concentrations” (PNECs) and the threshold levels for human health used in the EU risk assessment of pentaBDE (COM 2000).
Target organism Media of exposure PNEC or other effect threshold value for pentaBDE
Aquatic organisms Surface water 0.53 µg/l Sediment 310 µg/kg dry weight
Terrestrial compartment Soil (standard) 320 µg/kg dry weight
Biota generally/secondary Via food chain 1 mg/kg food poisoning
Human health, general Effect population (laboratory mammal studies)
Liver lesions 0.45 mg/kg body weight/day (NOAEL)
Behavioral effects 0.8 mg/kg body weight (single dose; LOEL)
5.5 Exposure
5.5.1 Environmental exposure Remote areas
Data from those remote areas where concentrations are expected to be at the lowest levels globally are collected in Table 9. Also concentrations in pelagic marine mammals studied have been collected to the table because they reflect the concentamination of the deep ocean waters. This data consists of concentrations in the biota and air. The levels in the Arctic air in remote regions have varied generally between ca. 1 and 10 pg/m3, although higher concentrations have been observed occasionally (Alaee et al. 2000; Peltola 2001).
38 Concentrations of BDE-47 and BDE-99 in whales have been reported in a range of ca. 66 to 864 ng/g lipid (BDE-47) and 24 to 169 ng/g lipid (BDE-99) (de Boer et al. 1998; van Bavel et al. 1999; Stern and Ikonomou 2000).
There are also other data available from areas considered as background or remote areas either regionally or nationally. Selected results are collected in Annex 5.
Ikonomou et al. (2001) have reported an increasing trend of pentaBDE congener levels in Arctic Holman Island ringed seals from the Canadian Northwest Territories. The pentaBDE congeners BDE-28/33, BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154 contributed ca. 90 % of the total concentration (see Figure 7). The other temporal trend reported from remote areas is shown in Figure 3.
6 Total 5 47 100 4 99 3 28/33 153 2 154 ng/g lipid (ppb) 1
0
lk 5 4 0 -1 -15 -15 -1 -3 -35 b 6 7 6 7 0 9 c M M M 9 5 9F 3 pro 1 6 1 5F1 8 91 96 8M 9 0 0 0 0 Figure 7. Levels of PBDEs in the blubber of ringed seals from Holman Island, Canada in 1981-2000 (Ikonomou et al. 2001). Data labels denote year, number of individuals, sex and age range.
39 Table 9. Concentrations of pentaBDE in the remote areas and pelagic species. The reported sumBDE concentrations consist to the largest part or completely of pentaBDE congener concentrations. Concentrations in biota given as ng/g lipid and in air as pg/m3, if not otherwise stated. Marine mammal samples are all blubber samples. Year of sampling and sex is indicated, if available. Sample type Site; sampling year Ref. BDE-47 BDE-99 Sample description Beluga whale (Delphinapterus leucas) females Canadian Arctic 1 81 (sumBDE) Average of unknown sample amount Beluga whale males Canadian Arctic 1 160 (sumBDE) Average of unknown sample amount -“- SE Baffin, Canadian Arctic 2 See figure 3 51 animals from -82, -86, -92, -96 and -97 Long-finned pilot whale (Globicephala melas), male Faroe Islands, Northern Atlantic; 1997 3 366 75 -“- -“- 3 271 55 -“- -“- 3 469 93 Long-finned pilot whale, female Faroe Islands, Northern Atlantic; 1997 3 212 51 -“- -“- 3 167 32 -“- -“- 3 66 24 Long-finned pilot whale, juvenile male Faroe Islands, Northern Atlantic;1997 3 332 72 -“- -“- 3 249 67 -“- -“- 3 557 113 Long-finned pilot whale, juvenile female Faroe Islands, Northern Atlantic; 1997 3 864 169 -“- -“- 3 247 67 -“- -“- 3 749 160 Long-finned pilot whale, male Stranded at the British coast; 1997 4 163 51 Given as µg/kg wet weight Sperm whale (Physeter macrocephalus), male Stranded at the Dutch coast 5 95 26 -“- -“- -“- 5 58 15 -“- -“- -“- 5 61 10 -“- Fin whale (Balaenoptera physalus), female Stranded at the British coast; 1992 4 13 12 -“- Minke whale (Balaenoptera acutorostrata), female Stranded at the British coast; 1996 4 47 13 -“- Minke whale Stranded at the Dutch coast 5 88 23 -“- Sowerby's beaked whale (Mesoplodon bidens), male Stranded at the British coast; 1998 4 62 27 -“- Atlantic white-sided dolphin (Lagenorhynchus acutus), male Stranded at the British coast; 1994 4 33 21 -“- White-beaked dolphin (Lagenorhynchus albirostris), female Stranded at the British coast; 1995 4 2480 622 -“- -“- Stranded at the British coast; 1998 4 5780 1480 -“- Whitebeaked dolphin Stranded at the Dutch coast 5 5500 1000 -“- Table 9 continues on the next page.
40 Table 9 continues.
Sample type Site; sampling year Ref. BDE-47 BDE-99 Sample description Striped dolphin (Stenella coeruloealba); male Stranded at the British coast; 1996 4 162 77 -“- Common dolphin (Delphinus delphis); female Stranded at the British coast; 1998 4 121 99 -“- Risso's dolphin (Grampus griseus); male Stranded at the British coast; 1994 4 631 393 -“- Ringed seal (Pusa hispida), female Spitsbergen, Arctic 6 40 as Bromkal 70-5 Ringed seal, male Canadian Arctic 150 (sumBDE) Average of unknown sample amount Ringed seal, female Canadian Arctic 1 26 (sumBDE) Average of unknown sample amount -“- Svalbard, Arctic 7 47 2 Pooled sample of 7 specimen, caught 1981 Ringed seal Holman Island, NWT, Canada 8;9 See figure 7 Alltogether 35 males and 14 females caught 1981, 1991, 1996 and 2000; pentaBDE congeners contribute ca. 90 % of the sumBDE. Air (bulk) Dunai, Russia (Arctic); 1994-1995 10 0-8 (sumBDE) -“- Alert, Canada (Arctic) 1994-1995 10 1-28 (sumBDE) -“- Pallas, Finland (Arctic) 111.2 (BDE-47 + BDE-99) Winter 2001 -“- Pallas, Finland (Arctic) 11 2.6 (BDE-47 + BDE-00) Fall 2000
References: 1) Alaee et al. (1999); 2) Stern and Ikonomou (2000); 3) van Bavel et al. (1999); 4) Law, personal comm. (2001); 5) de Boer et al. (1998); 6) Jansson et al. (1987); 7) Sellström et al. (1993); 8) Ikonomou et al. (2000); 9) Ikonomou et al. (2001); 10) Alaee et al. (2000); 11) Peltola (2001).
41 Global distribution
The first large scale study of concentrations of PBDEs have been reported by Jones et al. (2001). The concentration in butter (see Figure 8) reflects quite well the relative regional exposure levels. It is assumed that the major part of PBDEs in butter originate from atmospheric deposition.
1400
1200 PB DE 4 7 PB DE 9 9 1000 PBDE 153 800
600
400
200
0
K lia ico dia a SA x U pain razil n r e S China B I t Japan U M Zealand S. Africa Aus Germanyw e N
Figure 8. Distribution of major congeners of pentaBDE in world butter samples (Jones et al. 2001).
Preliminary results from air samples from an Atlantic research cruise are presented in Figure 9. They demonstrate that pentaBDE congeners are transported long-range to the open sea and that they have spread also to the southern polar region, where local releases are not assumed to occur.
10000 900 9000 800 8000 700 47 7000 600 6000 99 153 500 5000 400 4000 (fg/ m3) 300 3000 2000 200 Air Concentration (fg/m3) Concentration Air BDE153 AiConce r ntra ti on 1000 100 0 0 -80 -60 -40 -20 0 20 40 60 Latitude
Figure 9. Distribution of major congeners of pentaBDE in air from an Atlantic cruise (Jones et al. 2001, oral presentation, preliminary results).
42 PentaBDE has been detected also i.a., in waste water treatment plant sludge, storm water and terrestrial animals in polluted areas. Recent results are collected in Annex 6.
A large number of results from levels in the environment have been reviewed e.g., in COM (2000), de Wit (2000) and WHO IPCS (1994).
Temporal trends
Time trends have not been studied intensively and the only remote area time trends have been reported by Stern and Ikonomou (2000) for beluga whales and Ikonomou et al. (2001) for ringed seals (see Figure 3 and Figure 7).
A sediment sample from the southern part of the Baltic Sea Proper shows an increasing trend of the sum of BDE-47, BDE-99 and BDE-100 from 1939 to 1986 (Nylund et al. 1992; see Figure 10). The laminates analysed were dated by assuming that each lamina represents one year’s sediment deposition. A downward trend in Europe can be expected to be observed in the near future due to the reduced use of pentaBDE by the end of 1990’s and the forthcoming restrictions.
1990
1980
1970
1960
1950
1940
1930 00,511,522,53 Sum concentration of BDE-47, -99 and -100 (ng/g IG)
Figure 10. Concentration of sum of BDE-47, BDE-99 and BDE-100 in the sediment from the Bornholm Deep, the Baltic Sea Proper (Nylund et al. 1992).
Temporal trends have been analysed also from Drammenfjord in Norway, the western Wadden Sea in the Netherlands (both coastal areas receiving diffuse and point source pollution) and from Lake Woserin in northern Germany by Zegers et al. (2000). The results show that concentrations of pentaBDE congeners have levelled off in the Wadden Sea and Lake Woserin but levels in Drammenfjord are still increasing (see Figure 11).
43 10 9 8 7 6 5 4 3 2 1 0 1946±3 1966±2 1975±1 1981±1 1985±1 1988±1 1994±1 1998±1 Concentration of BDE-47 and BDE-99 (ng/g TOC)
BDE47 BDE99
Figure 11. Temporal trends of BDE-47 and BDE-99 concentrations found in a sediment core from Drammenfjord, Norway (Zegers et al. 2000).
Swedish Lake Bolmen pike and Lake Krankensjö roach time trends of BDE-47 show an increase in concentrations until the mid-late eighties but after that the concentrations seem to have levelled off (Kierkegaard et al. 1999). However, concentrations vary considerably between years, and thus more studies are needed to confirm the development of concentrations in time. Concentrations of BDE-47 and BDE-99 in guillemot eggs in the Baltic Sea, Sweden, showed an increase until the late eighties and then clearly decreased thereafter (Sellström et al. 1993).
In contrast to the available European trend data, temporal trends from North America show increase. Luross et al. (2000) reported an over 100 fold increasing concentration of i.a., BDE-47 and BDE-99 and total PBDE in Lake Ontario lake trout whole fish homogenates in 1978-1998, and Moisey et al. (2001) observed a similar trend in herring gull eggs from the Great Lakes in 1981-2000 (see Figure 12).
44 1600 1400
1200 1000 800 600
400 200
SumBDE concentration (ng/g wwt) 0 1980 1985 1990 1995 2000
Shelter Island, Lake Huron Gull Island, Lake Michigan Snake Island, Lake Ontario
Figure 12. Tetra- to hexaBDE concentrations as a sumBDE in Great Lakes herring gull eggs (Moisey et al. 2001).
Congener profiles
Comparison of congener profiles of concentrations in biota, air and sediment near urban areas or other sources of intensive pollution with the congener profiles of the same matrices further from pollution sources indicate that especially BDE-47 and BDE-99 are more easily transported than higher brominated BDEs. Nevertheless, this does not exclude the possibility that other PBDEs could arrive later into the areas away from pollution sources. Figure 13 demonstrates what is probably a typical congener pattern of PBDEs in remote area biota. The pattern indicates both the better long-range transport potential of BDE-47 and BDE-99 and also the preferential uptake of these congeners when compared to those of other congeners present in pentaBDE or other PBDE products (see Figure 4).
80
70
60
50
40 30
measured PBDEs 20
10
0 Congener composition (%) of the sum triBDE tetraBDE pentaBDE hexaBDE
Congener composition in 1982 Congener composition in 1997
Figure 13. Congener pattern of Arctic beluga whale (Stern and Ikonomou 2000).
45 5.5.2 Exposure of humans
Levels in humans
BDE-47 has been detected in the general human population in i.a., milk, adipose tissue and blood in levels of a few ng/g lipid (i.a., Darnerud et al. 1998; Strandman et al. 1999; Norén and Meironyté 2000; Schröter-Kermani et al. 2000; Lind et al. 2001; Nagayama et al. 2001; Ryan and Patry 2001). Levels in humans have been reviewed by Darnerud et al. (2001) and specifically for Europe by Hagmar and Bergman (2001). Figures 14a and b show time trends of pentaBDE levels in Europeans. The levels in Europe can be expected to level off or decrease due to the reduced consumption of pentaBDE in recent years.
According to the results of Sjödin et al. (1999a and b) major pentaBDE congeners have accumulated in the whole general human population regardless of occupation. In contrast, according to some recent Swedish results (Sjödin et al. 1999a; Hagmar et al. 2000), computer technicians and electronics dismantling plant workers are occupationally exposed to BDE-153, BDE-183 and BDE-209. Also computer clerks are shown to be exposed to some BDE congeners. However, any occupation-specific exposure could not be shown in these studies for the BDE-47, but it was found in similar levels as in the control groups (BDE-99 was not measured).
In studies of the general human population in Sweden the BDE-47 congener is generally found in higher concentrations than other congeners in adipose tissue, human blood serum and mother milk followed by the BDE-99 (Klasson-Wehler et al. 1998; Meironyté Guvenius 1999; Sjödin et al. 1999; Norén 2000). This pattern for PBDEs has also been reported in Europe and North America (Strandman et al. 1999; Schröter-Kermani et al. 2000; She et al. 2000; Strandman et al. 2000; Ryan and Patry 2001).
Exposure via the food web
The main exposure route of pentaBDE to humans is food. Several available studies show (see table 9 and Annexes 5 and 6) that fish species consumed by humans are contaminated with pentaBDE. A Finnish study by Strandman et al. (2001) suggests that fish has the highest levels of pentaBDE of food items. The pentaBDE congeners BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154 were present in all the food items studied. The study encompassed cereal products, liquid and solid milk products, meat and egg, fish, potato products, vegetables, fruits and berries and fats and oils. Sum concentrations of congeners studied varied from 0.0013 ng/g fresh weight to 0.85 ng/g fresh weight in fish. In fish, potato products and fruit and berries BDE-47 was found in higher concentration than other BDE congeners. BDE-99 was predominant in cereal products, vegetables and fat and oils. These results are supported by a Swedish study where, in addition to measuring PBDEs in food, the total daily intake of 27 ng/day from food (as the sum of BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) was calculated for 87 primiparous women (Lind et al. 2001). The major part of the intake via food came from fish, the second largest source was dairy products,
46 although the group studied exhibited low consumption of fish in relation to the Swedish population in general.
The connection between levels of pentaBDE in humans and the dietary consumption level of fish has been reported by Hagmar and Bergman (2001) and in a Japanese study (Ohta et al. 2000).
1200 6 6
1000 5 5
800 4 4
600 3 3
400 2 2
200 1 Concentration (ng/g lipid) 1 Concentration of PCBs (ng/g lipid)
0 0 Concentration of PBDEs (ng/g lipid) 0 1970 1980 1990 2000 2010 1985 1990 1995 2000
sumPBDE BDE-47 PCBs PBDEs
Figure 14a) Exponentially until 1997 increased Figure 14b) Concentration of PBDEs in occurrence of PBDEs and decreasing occurrence human blood in Germany 1985-1999 of sumPCBs in human milk (Norén and Meironyté (Schröter-Kermani et al. 2000). The 2000). sumPBDE consists of components present in pentaBDE products in both figures.
5.6 General information on national and international administrative actions on pentaBDE
5.6.1 Classification and labelling PentaBDE has been recently classified in the European Union. The same classification and labelling is applied in all EU Member States. The classification and labelling for human health is: “Xn; R 48/21/22 –64”: “Harmful, danger of serious damage to health by prolonged exposure in contact with the skin or if swallowed. May cause harm to breastfed babies.” For the environment the classification and labelling is: N; R50/53: “Harmful for the environment. Very toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.”
According to the available information, a commercial pentaBDE product, Bromkal G 1, is classified in the USA as a Skin/Eye Irritant. It has been given a TSCA Flag T (subject to a Section 4 test rule). There are currently no data available on the classification and labelling of pentaBDE in other countries.
47 5.6.2 Available risk evaluations PentaBDE has, together with other brominated flame retardants, been reviewed in the International Programme on Chemical Safety (IPCS). This review was contained in “The Environmental Health Criteria” (WHO IPCS 1994) published in 1994.
In addition, the Organisation for Economic Cooperation and Development (OECD) has conducted a review of brominated flame retardants in general in 1994 (OECD 1994). This review, however, focused on the production and use of these substances.
The risks of pentaBDE to human health and to the environment have recently been evaluated comprehensively within the framework of the EU Council Regulation (EEC) 793/93 on Existing Substances. This evaluation was performed by the United Kingdom, and the risk assessment report was published in 2000 (COM 2000). On the basis of the risk assessment report, a separate risk reduction strategy (DETR 2000) was also prepared by the UK and published. Following the conclusions agreed upon the risk reduction strategy, the European Commission has made an official proposal for the restriction of the use and placing on the market of pentaBDE (COM 2001).
5.6.3 Status under international conventions PentaBDE has currently not yet been proposed to be listed in the UNECE POP Protocol or in the UNEP POP Convention. For the time being, pentaBDE has also not been listed in the Rotterdam Convention (Convention on the Prior Inform Consent; PIC) Procedure for Certain Hazardous Chemicals and Pesticides in International Trade.
Brominated flame retardants have been included in the list of chemicals for priority action in the recent hazardous substances strategy of the Commission for the Protection of the Marine Environment of the North-East Atlantic (OSPAR Commission).
48 6 Alternatives and pollution prevention techniques
6.1 Alternative chemicals and methods
The following other flame retardants are used today in furniture upholstery foams: chlorinated alkyl phosphor esthers, melamine (not alone), ammonium polyphosphates and reactive phosphorus polyols. Ammonium polyphosphates and red phosphor have been cited as alternatives to applications of rigid PUR. Phosphate esthers may also be alternatives to pentaBDE. Another brominated flame retardant tetrabromobenzoate (TBBE) is also used currently in a similar manner as pentaBDE. Graphite impregnated foams and hydrated alumina have also been reported as possible alternatives to pentaBDE (Lassen, Løkke et al., 1999; DETR 2000). According to Lassen, Løkke et al. (1999), Denmark has succeeded in phasing out the use of all brominated flame retardants made from flexible PURs in the 1990s.
EU risk reduction strategy for pentaBDE (DETR 2000) suggests that only TBBE and chlorinated alkyl phosphate esthers, tri (2-chloroisopropyl) phospate (TCPP) in particular, followed by phosphate esthers, are relevant chemical alternatives to pentaBDE. Annex 3 gives an overview of the suitability of TCPP and TBBE as alternatives. Health and/or environmental toxicity data of a few chemical alternatives have been reviewed in Gustafsson (1994), Berglind (1995), National Research Council (2000) and Miljøstyrelsen (2001).
The simplest technical alternative to pentaBDE in foams is to increase the density of products with mild fire safety requirements (Miljøstyrelsen 2001).
6.2 Pollution prevention techniques
Most of the releases of pentaBDE occur during and after the service life from articles containing polyurethane. Thus pollution prevention techniques at pentaBDE production sites and polyurethane production sites have minor impact on the total exposure. Reduction of point sources at the PUR production sites may be further reduced according to DETR (2000) by making changes in the processing of PUR, improving storage and handling and installing further treatment systems or by altering diposal routes.
Prevention of releases due to the weathering and wearing of articles containing pentaBDE during their service life seems not to be feasible, but on the other hand, this issue has not been thoroughly assessed. Prevention of releases from metal recycling plants may be effectively reduced by abating dust formation and by efficient dust collection. Inasmuch as pentaBDE is resistent to degradation by
49 sludge micro-organisms, prevention of releases in the release routes of municipal sewage sludge disposal and of application on agricultural land does not seem feasible.
Releases of pentaBDE to the air from products during the service life of articles seem to be unavoidable, unless the flame retarded material is sealed airtight. Partial avoidance of releases from landfills may be reached by the management of landfills according to best management practices. Emissions from incineration are highly dependent on e.g., temperature and the application of Best Available Technology.
50 References
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59 Annex 1. EXECUTIVE BODY DECISION 1998/2 ON INFORMATION TO BE SUBMITTED AND THE PROCEDURE FOR ADDING SUBSTANCES TO ANNEXES I, II OR III TO THE POPS PROTOCOL (EB.AIR/WG.5/52, Annex II)
The Executive Body,
Resolved to act as early as possible to develop criteria and procedures for adding substances to the forthcoming protocol on persistent organic pollutants,
Adopts, with reference to article 14, paragraph 6, of the protocol, the requirements for information to be submitted and the procedure for adding substances to annexes I, II or III to the protocol on persistent organic pollutants set out below.
INFORMATION TO BE SUBMITTED AND THE PROCEDURE FOR ADDING SUBSTANCES TO ANNEXES I, II OR III TO THE PROTOCOL ON PERSISTENT ORGANIC POLLUTANTS
1. A Party submitting a proposal to amend annexes I, II or III in accordance with article 14, paragraph 6, shall provide the Executive Body with a risk profile on the substance and information on the characteristics below, following the guidance and indicative numerical values, which demonstrate:
(a) Potential for long-range transboundary atmospheric transport: evidence that the substance has a vapour pressure below 1,000 Pa and an atmospheric half-life greater than two days. Alternatively, monitoring data showing that the substance is found in remote regions; and
(b) Toxicity: potential to adversely affect human health and/or the environment; and
(c) Persistence: evidence that the substance=s half-life in water is greater than two months, or that its half-life in soils is greater than six months, or that its half-life in sediments is greater than six months. Alternatively, evidence that the substance is otherwise sufficiently persistent to be of concern within the scope of the protocol; and
(d) Bio-accumulation:
(i) Evidence that the BCF or BAF for the substance is greater than 5,000 or the log Kow is greater than 5; or
(ii) Alternatively, if the bio-accumulative potential is significantly lower than (i) above, other factors, such as the high toxicity of the substance, that make it of concern within the scope of the protocol.
60 The proposal shall also contain a summary report and include, as available, information on:
(i) Production/uses/emissions, measured environmental levels in areas distant from sources, abiotic and biotic degradation processes and rates, degradation products, bio-availability; and
(ii) Socio-economic factors related to the alternatives and/or the techniques available to reduce the emissions of the proposed substance including:
- Alternatives to the existing uses and their efficacy;
- Any known adverse environmental or human health effects associated with the alternatives;
- Process changes, control technologies, operating practices and other pollution prevention techniques which can be used to reduce the emissions of the substance, and their applicability and effectiveness; and
- The non-monetary costs and benefits as well as the quantifiable costs and benefits associated with the use of these alternatives and/or techniques.
2. Upon receipt of a submission prepared in accordance with paragraph 1 above and if the risk profile is deemed acceptable, the Parties shall, at a meeting of the Executive Body and by consensus, ensure that one or more technical reviews of the proposal are conducted if, on the basis of the submission and any other relevant information submitted to the Executive Body, further consideration of the substance is determined to be warranted. Any such technical reviews shall be in writing and evaluate, inter alia:
(a) The monitoring or equivalent scientific information suggesting long-range transboundary atmospheric transport; and
(b) Whether sufficient information exists to suggest that the substance is likely to have significant adverse human health and/or environmental effects as a result of its long-range transboundary atmospheric transport; and
(c) A list of the sources of the substance in the atmosphere, including the use of products, estimates of the total emissions from these sources and the methodologies used; and
(d) Whether measures exist to reduce the risk of adverse effects on human health and/or the environment as a result of its long-range transboundary atmospheric transport, and whether they are technically feasible, as well as their associated effects and costs.
61 3. The term risk profile mentioned in paragraphs 1 and 2 above refers to a comprehensive review of the scientific information related to the determination of general human health and environmental risks associated with the uses and releases of a substance. Such a review need not explicitly address risks associated with long-range transboundary air pollution, but must provide suitable information for the assessment of such risk.
4. On the basis of the submission specified in paragraph 1 above and any technical review(s) that may have been prepared in accordance with paragraph 2 above, the Parties shall, at a meeting of the Executive Body, complete their evaluation of the proposal taking into account the objective of the protocol set out in article 2.
62 Annex 2. Article 8 and Annexes D-F of the UNEP POP Convention
FINAL ACT OF THE CONFERENCE OF PLENIPOTENTIARIES ON THE STOCKHOLM CONVENTION ON PERSISTENT ORGANIC POLLUTANTS
[…]
Article 8
Listing of chemicals in Annexes A, B and C
1. A Party may submit a proposal to the Secretariat for listing a chemical in Annexes A, B and/or C. The proposal shall contain the information specified in Annex D. In developing a proposal, a Party may be assisted by other Parties and/or by the Secretariat.
2. The Secretariat shall verify whether the proposal contains the information specified in Annex D. If the Secretariat is satisfied that the proposal contains the information so specified, it shall forward the proposal to the Persistent Organic Pollutants Review Committee.
3. The Committee shall examine the proposal and apply the screening criteria specified in Annex D in a flexible and transparent way, taking all information provided into account in an integrative and balanced manner.
4. If the Committee decides that:
(a) It is satisfied that the screening criteria have been fulfilled, it shall, through the Secretariat, make the proposal and the evaluation of the Committee available to all Parties and observers and invite them to submit the information specified in Annex E; or
(b) It is not satisfied that the screening criteria have been fulfilled, it shall, through the Secretariat, inform all Parties and observers and make the proposal and the evaluation of the Committee available to all Parties and the proposal shall be set aside.
5. Any Party may resubmit a proposal to the Committee that has been set aside by the Committee pursuant to paragraph 4. The resubmission may include any concerns of the Party as well as a justification for additional consideration by the Committee. If, following this procedure, the Committee again sets the proposal aside, the Party may challenge the decision of the Committee and the Conference of the Parties shall consider the matter at its next session. The Conference of the Parties may decide, based on the screening criteria in Annex D and taking into account the evaluation of the Committee and any additional information provided by any Party or observer, that the proposal should proceed.
63 6. Where the Committee has decided that the screening criteria have been fulfilled, or the Conference of the Parties has decided that the proposal should proceed, the Committee shall further review the proposal, taking into account any relevant additional information received, and shall prepare a draft risk profile in accordance with Annex E. It shall, through the Secretariat, make that draft available to all Parties and observers, collect technical comments from them and, taking those comments into account, complete the risk profile.
7. If, on the basis of the risk profile conducted in accordance with Annex E, the Committee decides:
(a) That the chemical is likely as a result of its long-range environmental transport to lead to significant adverse human health and/or environmental effects such that global action is warranted, the proposal shall proceed. Lack of full scientific certainty shall not prevent the proposal from proceeding. The Committee shall, through the Secretariat, invite information from all Parties and observers relating to the considerations specified in Annex F. It shall then prepare a risk management evaluation that includes an analysis of possible control measures for the chemical in accordance with that Annex; or
(b) That the proposal should not proceed, it shall, through the Secretariat, make the risk profile available to all Parties and observers and set the proposal aside.
8. For any proposal set aside pursuant to paragraph 7 (b), a Party may request the Conference of the Parties to consider instructing the Committee to invite additional information from the proposing Party and other Parties during a period not to exceed one year. After that period and on the basis of any information received, the Committee shall reconsider the proposal pursuant to paragraph 6 with a priority to be decided by the Conference of the Parties. If, following this procedure, the Committee again sets the proposal aside, the Party may challenge the decision of the Committee and the Conference of the Parties shall consider the matter at its next session. The Conference of the Parties may decide, based on the risk profile prepared in accordance with Annex E and taking into account the evaluation of the Committee and any additional information provided by any Party or observer, that the proposal should proceed. If the Conference of the Parties decides that the proposal shall proceed, the Committee shall then prepare the risk management evaluation.
9. The Committee shall, based on the risk profile referred to in paragraph 6 and the risk management evaluation referred to in paragraph 7 (a) or paragraph 8, recommend whether the chemical should be considered by the Conference of the Parties for listing in Annexes A, B and/or C. The Conference of the Parties, taking due account of the recommendations of the Committee, including any scientific uncertainty, shall decide, in a precautionary manner, whether to list the chemical, and specify its related control measures, in Annexes A, B and/or C.
64 […]
Annex D
INFORMATION REQUIREMENTS AND SCREENING CRITERIA
1. A Party submitting a proposal to list a chemical in Annexes A, B and/or C shall identify the chemical in the manner described in subparagraph (a) and provide the information on the chemical, and its transformation products where relevant, relating to the screening criteria set out in subparagraphs (b) to (e):
(a) Chemical identity:
(i) Names, including trade name or names, commercial name or names and synonyms, Chemical Abstracts Service (CAS) Registry number, International Union of Pure and Applied Chemistry (IUPAC) name; and
(ii) Structure, including specification of isomers, where applicable, and the structure of the chemical class;
(b) Persistence:
(i) Evidence that the half-life of the chemical in water is greater than two months, or that its half-life in soil is greater than six months, or that its half-life in sediment is greater than six months; or
(ii) Evidence that the chemical is otherwise sufficiently persistent to justify its consideration within the scope of this Convention;
(c) Bio-accumulation:
(i) Evidence that the bio-concentration factor or bio-accumulation factor in aquatic species for the chemical is greater than 5,000 or, in the absence of such data, that the log Kow is greater than 5;
(ii) Evidence that a chemical presents other reasons for concern, such as high bio-accumulation in other species, high toxicity or ecotoxicity; or
(iii) Monitoring data in biota indicating that the bio-accumulation potential of the chemical is sufficient to justify its consideration within the scope of this Convention;
(d) Potential for long-range environmental transport:
(i) Measured levels of the chemical in locations distant from the sources of its release that are of potential concern;
65 (ii) Monitoring data showing that long-range environmental transport of the chemical, with the potential for transfer to a receiving environment, may have occurred via air, water or migratory species; or
(iii) Environmental fate properties and/or model results that demonstrate that the chemical has a potential for long-range environmental transport through air, water or migratory species, with the potential for transfer to a receiving environment in locations distant from the sources of its release. For a chemical that migrates significantly through the air, its half-life in air should be greater than two days; and
(e) Adverse effects:
(i) Evidence of adverse effects to human health or to the environment that justifies consideration of the chemical within the scope of this Convention; or
(ii) Toxicity or ecotoxicity data that indicate the potential for damage to human health or to the environment.
2. The proposing Party shall provide a statement of the reasons for concern including, where possible, a comparison of toxicity or ecotoxicity data with detected or predicted levels of a chemical resulting or anticipated from its long- range environmental transport, and a short statement indicating the need for global control.
3. The proposing Party shall, to the extent possible and taking into account its capabilities, provide additional information to support the review of the proposal referred to in paragraph 6 of Article 8. In developing such a proposal, a Party may draw on technical expertise from any source.
Annex E
INFORMATION REQUIREMENTS FOR THE RISK PROFILE
The purpose of the review is to evaluate whether the chemical is likely, as a result of its long-range environmental transport, to lead to significant adverse human health and/or environmental effects, such that global action is warranted. For this purpose, a risk profile shall be developed that further elaborates on, and evaluates, the information referred to in Annex D and includes, as far as possible, the following types of information:
(a) Sources, including as appropriate:
66 (i) Production data, including quantity and location;
(ii) Uses; and
(iii) Releases, such as discharges, losses and emissions;
(b) Hazard assessment for the endpoint or endpoints of concern, including a consideration of toxicological interactions involving multiple chemicals;
(c) Environmental fate, including data and information on the chemical and physical properties of a chemical as well as its persistence and how they are linked to its environmental transport, transfer within and between environmental compartments, degradation and transformation to other chemicals. A determination of the bio-concentration factor or bio-accumulation factor, based on measured values, shall be available, except when monitoring data are judged to meet this need;
(d) Monitoring data;
(e) Exposure in local areas and, in particular, as a result of long-range environmental transport, and including information regarding bio-availability;
(f) National and international risk evaluations, assessments or profiles and labelling information and hazard classifications, as available; and
(g) Status of the chemical under international conventions.
Annex F
INFORMATION ON SOCIO-ECONOMIC CONSIDERATIONS
An evaluation should be undertaken regarding possible control measures for chemicals under consideration for inclusion in this Convention, encompassing the full range of options, including management and elimination. For this purpose, relevant information should be provided relating to socio-economic considerations associated with possible control measures to enable a decision to be taken by the Conference of the Parties. Such information should reflect due regard for the differing capabilities and conditions among the Parties and should include consideration of the following indicative list of items:
(a) Efficacy and efficiency of possible control measures in meeting risk reduction goals:
(i) Technical feasibility; and (ii) Costs, including environmental and health costs;
(b) Alternatives (products and processes):
(i) Technical feasibility; (ii) Costs, including environmental and health costs;
67 (iii) Efficacy; (iv) Risk; (v) Availability; and (vi) Accessibility;
(c) Positive and/or negative impacts on society of implementing possible control measures:
(i) Health, including public, environmental and occupational health; (ii) Agriculture, including aquaculture and forestry; (iii) Biota (biodiversity); (iv) Economic aspects; (v) Movement towards sustainable development; and (vi) Social costs;
(d) Waste and disposal implications (in particular, obsolete stocks of pesticides and clean-up of contaminated sites):
(i) Technical feasibility; and (ii) Cost;
(e) Access to information and public education;
(f) Status of control and monitoring capacity; and
(g) Any national or regional control actions taken, including information on alternatives, and other relevant risk management information.
68 Annex 3. Comparison of pentaBDE and its alternatives TCPP and PBBE
Source: Mainly DETR (2000) PentaBDE TCPP TBBE Technical suitability For automotive applicationsSuitable Suitable for most Suitable applications. For upholstered furniture Suitable (not when Suitable phosphorus-free foam is required) For Non-Foamed PUR Unknown Suitable Environmental hazards Environmental partitioning Low water solubility and Binds to organic carbon in Likely to partition strongly to volatility, binds strongly to soil, sediment and biota but organic carbon in soil, organic carbon in soil, to much lesser extent than sediment and biota but to sediment and biota pentaBDE slightly lesser extent than pentaBDE Acute toxicity Very toxic to aquatic Either toxic or harmful to Very toxic to aquatic organisms aquatic organisms organisms (less than pentaBDE, based upon limited data) Reproductive toxicity Very toxic Harmful Unknown Biodegradation Not readily biodegradable Not readily biodegradable Not readily biodegradable Bioaccumulation High Low/No Unknown but likely to be between TCPP and pentaBDE Classification for danger to N; R50/53 Not classified R50/53 environment and humans Xn; R48/21/22-64
69 Annex 4. Uses and market of brominated flame retardants in the Western Europe in 1998. The table was compiled from IAL Consultants (1999) and OECD (1994). Flame retardant Market volume (tn) % Target material Some end products Reactive retardants (can also be used as an additive) Tetrabromobisphenol A 13,150 21 Epoxy, Printed circuit boards (major), (TBBPA) polycarbonate, encapsulation, electric and electronic unsaturated appliances, funiture, construction material, polyesters TV and computer housing, roofing, sanitary ware, transportation TBBPA polycarbonate 2,150 3 Acrylonitrile Automotive components, electric and oligomer butadiene styrene electronic appliances, TV and computer (ABS), engineering housing, switchgear, relays, motors thermoplastics TBBPA bis(2,3-dibromopropyl 1,500 2 Polyethene, Wire covering, pipes, shields and ether) polypropylene, encapsulation for construction and other polyolefins transport, switchgear, flooring, TV and computer housing, electronic appliances, switchgear Brominated polyols 8,400 13 Rigid polyurethan Insulation panels (cold storage, processing foams rooms, containers, etc.) Brominated epoxy oligomers 1,250 2 Styrens, PBT Insulation, electronics, switchgear, lighting, Dibromoneopentyl glycol 1,150 2 Unsaturated Roofing, transportation, switchgear, polyesters, electronics, sanitary ware polyurethane Other reactive 250 0.4 Subtotal, reactive 28,800 45 Additive retardants Polybrominated diphenyl 7,050 11 ethers (PBDEs) Decabromodiphenyl ether Plastics in general, ”all, (no clothing)” textiles Octabromodiphenyl ether ABS (major), Electronics, switches, relays, motors, polycarbonates, wiring thermoplastics; always in connection with antimony trioxide Pentabromodiphenyl ether Polyurethane, Furnishing, upholstery, insulation panels, epoxy and phenol elastomers for several uses resins (textile) Polybrominated biphenyls 600 1 General (PBBs; mainly deca-) Hexabromocyclododecane 8,950 14 Expanded Insulation panels, construction materials, (HBCD) polystyrene and furniture, foam and stuffing, curtains, extruded carpets, tents, clothing polystyrene foam, polyethylene foam, textile Ethylene 5,250 8 General bis(tetrabromophtalimide) Polybrominated polystyrenes 4,175 7 Polybutylene Relays, motors, switch, electronics terephtalate, polystyrene Polydibromophenylene oxide 3,250 5 General Saytex 8010 proprietary 2,500 4 Computer housing product Polybrominated imides 850 1 Brominated phenyl indane 750 1 Poly(pentabromobenzyl) 500 0.8 Polymers, Relays, switches, electronics acrylate polybutylene terephtalate Other additive 775 1 Subtotal, additive 34,700 55 Total 62,500 10 0
70 Annex 5. Monitoring data from regional background areas.
Concentration in biota given as ng/g lipid, if not otherwise stated; concentration in air as pg/m3. SumBDE is indicated when congener specific concentrations have not been reported. PentaBDE congeners contribute in that case completely or the major share to the sumBDE. Sampling year has been given where it has been available.
Sample type Site; sampling year BDE-47 BDE-99 BDE-100 BDE-153 BDE-154 SumBDE Specific Ref. Air (bulk) Eagle Harbor, Michigan, U.S.; 1999 3.7 2.6 0.33 0.21 0.11 1 Ammarnäs, Sweden; 1991 6.3 1.6 0.4 2 Hoburgen, Sweden; 1990 0.7 0.35 0.07 2 Reindeer (Rangifer tarandus) Ottsjö, Sweden; 1986 0.17 0.26 0.04 Suet 3 Whitefish (Coregonus sp.) Lake Storvindeln, Sweden; 1986 15 7.2 3.9 Muscle 3 Pike (Esox lucius) Lake Hirvilampi, Finland; 1997 30 18 89 Pooled, dorsal axial muscle 4 White crappie (Pomoxis annularis) Lake of Ozarks, Missouri, U.S.; 1999 190 78 59 7.7 8.6 Whole fish homogenates, 1 average of 3 fish samples Bluegill (Lepomis macrochirus) Lake of Ozarks, Missouri, U.S.; 1999 200 91 59 23 14 A whole fish homogenate 1 White fish (Prosopium williamsoni) Slocan River, headwater river of 14 Muscle, average of 2 males, 1 5 Columbia River, BC, Canada; 1996 female, Lake trout (Salmo trutta) Lake Takvatn, northern Norway 5.51 3.07 Dorsal axial muscle 6 Lake Fjellfrøsvatnet, northern Norway 6.82 6.27 Dorsal axial muscle 6 Lake Grunnvatnet, northern Norway 4.92 2.92 Dorsal axial muscle 6 Burbot (Lota lota) Lake Grensefoss, northern Norway 83.5 91.4 Liver 6 scorpius Shorthorn sculpin (Myoxocephalus Greenland, Usuk; 2000 2.1 Ng/g wwt; sampled ; (average 7 ) of pooled female and pooled male samples) 1) Dodder et al. 2000; 2) Bergander et al. 1995; 3) Sellström et al. 1993; 4) Peltola 2001; 5) Ikonomou et al. 2001; 6) Schlabach et al. 2001; 7) Christensen, et al. 2001.
71 Annex 6. Recent monitoring data from polluted areas.
72