# Presentation: 903984

## Brominated Flame Retardants in the Environment PBBs, PBDEs, TBBPA, HBCDD

- Mehran Alaee
- Atmospheric Contaminant Impacts
-  Aquatic Ecosystem Protection Research Branch
- National Water Research Institute

## Outline:

**Outline:**

**Overview of BFRs**
**Recent developments in analytical methods  **
**Levels and trends in abiotic environment**
**Levels and trends in biota**
**Food web studies**
**Metabolites **
**Summary & Conclusions**

## Overview:

## Major Brominated Flame Retardants Volume Estimates

**Total Market Demand By Region in 2001**

| [MT] | Americas | Europe | Asia | Rest of World | Total |
| --- | --- | --- | --- | --- | --- |
| TBBPA | 18,000 | 11,600 | 89,400 | 600 | 119,700 |
| HBCDD | 2,800 | 9,500 | 3,900 | 500 | 16,700 |
| Deca-BDE
(DBDPO) | 24,500 | 7,600 | 23,000 | 1,050 | 56,100 |
| Octa-BDE
(OBDPO) | 1,500 | 610 | 1,500 | 180 | 3,790 |
| Penta-BDE
(PBDPO) | 7,100 | 150 | 150 | 100 | 7,500 |

- Based on 2001 BFR market demand (BSEF 2003)

## BACKGROUND:

- PBBs were introduced in early 1970’s as flame retardants. Between 1970 and 1976, 11 885 m-tonnes of PBBs were produced in the US. Technical DeBB was in production in Europe till 2000.
- In 1981, Anderson and Blomkvist reported the presence of PBDEs in samples collected along Viskan River in Sweden.
- In 1987 Jansson and his colleagues first indicated that PBDEs are global contaminants by demonstrating their  presence  in fish eating birds and marine mammals in samples collected from Baltic Sea, North Sea and Arctic Ocean.
- In 1987 Watanabe and his colleagues detected PBDE congeners in marine fish, shellfish, and sediments from Japan;  and in 1992 they reported the presence of  PBDEs in air particulate from Japan and Taiwan.

## BACKGROUND:

- In 1983, Stafford reported the presence of PBDEs in eggs and tissues of fish eating birds from the Great Lakes Region (6 states and Ontario)
- In 1991, Kuehl and his co-workers at EPA reported 180-220 ng/g of PBDEs in blubber from bottlenose dolphin on the south Atlantic US coast
- In 1995, Kuehl and Haebler reported up to 8000 ng/g PBDEs in bottlenose dolphin from the Gulf of Mexico.
- In 1983, Watanabe and his colleagues reported occurrence of TBBPA in mussel, river and marine sediments.
- In 1998, Sellström and her colleagues reported on occurrence of HBCDD in fish and sediment from Viskan River
- In 1997 Research on PBDEs was started at CCIW and IOS
- In 1999 research was expanded to included PBBs, HBCDD, and TBBPA

## Analytical Methods

- EPA Method 1614, for determination of PBDEs
- Isomer specific /isotope dilution method for determination of HBCDD (LC/MS based)
- Isotope dilution method for determination of TBBPA

## Analytical Procedures for Determination of BFRs in Environmental Matrices (Not Another PCB, or PCDD/PCDF):

- Each BFR has its own analytical requirements
- TBBPA is a phenolic compound, BDE-209 and HBCDD are thermally labile
- Isomer specific analysis for HBCDD can be accomplished using LC/MS methods
- PBDEs are amenable to GC analysis
- 209 possible congeners ( <45 congeners are commercially available)
- co-elution between various congeners
- GC-ECD
- the simplest and least selective detector used in determination of PBDEs
- requires careful sample preparation
- potential interference from PCBs and other organohalogen contaminants (BDE-47 & CB-180)
- CG-ECNI/MS (ISO method)
- monitors bromine anion formed by dissociative capture
- more selective than ECD, but susceptible to interferences from organobromine compounds such as BDE153 and TBBPA
- CG/HRMS
- most selective technique (US-EPA Method 1614)
- Susceptible to interferences from native and 13C enriched PCBs

## % RSD for Selected PBDE Congeners from the First Interlab Study 

- From de Boer  and Cofino 2002

## % RSD for BDE-209 Congener from the Second Interlab Study 

| Matrix | Mean | %CV | n |
| --- | --- | --- | --- |
| Std. Solution | 828 (780) | 40 | 16 |
| Trout | 0.31 | 165 | 8 |
| Mussels | 0.56 | 256 | 6 |
| Human Milk | 0.35 | 65 | 13 |
| Sed. Extr. | 1871 | 27 | 15 |

- From de Boer 2003

## From de Boer 2003

## From de Boer 2003

## EPA Method 1614

- To be released shortly
- Based on 1613 and 1668, without carbon column cleanup
- Based on 8 BDE congeners, 28, 47, 99, 100, 153, 154, 183 and 209
- Based on HRGC/HRMS
- isotope dilution technique
- m/Δm= 5000-8000
- 30m DB5-HT
- Multi level calibration

## Baseline separation of Tri, Tetra, Penta, Hexa, Hepta, and DecaBDE’s congeners in 44 minutes! 

- Baseline separation of Tri, Tetra, Penta, Hexa, Hepta, and DecaBDE’s congeners in 44 minutes!

- From Macpherson et al. 2002

## HBCDD Analysis LC/MS/MS Procedure 

- Separations were performed on C18 analytical column (5.0 cm × 2.1 mm i.d., 4 μm particle size)
- flow-rate of 300 *μ*L/min.
- MS/MS detection in multiple reaction monitoring (MRM) *m/z* 640.6 ([M – H] ̄)  Br ̄ (both isotopes),
- utilizing unit resolution on the first and third quadrupoles
-  200 ms dwell time
- Quantification was based on the ion signal from the *m/z* 640.6  *m/z* 79 MRM transition.
- Collision activated dissociation using Argon
- Collision energy was –50 eV.

## 

**Negative APCI-LC-MS chromatograms showing a comparison of an HBCDD technical mixture at 10 ppm and a suspended sediment sample from the Detroit River**

**From MacInnis et al. 2003**

**HBCDD  Std   10 ppm**

- 4.00

- 4.20

- 4.40

- 4.60

- 4.80

- 5.00

- 5.20

- 5.40

- 5.60

- 5.80

- 6.00

- 6.20

- 6.40

- 6.60

- 6.80

- 7.00

- 7.20

- 7.40

- Time

- 0

- 100

- %

- 0

- 100

- %

- DR2000

- -

- HBCDD

- -

- STD01

- -

- 1

- SIR of 2

-  Channels AP

- -

- TIC

- 6.28e4

- Area

- 6.39

- 9291

- 5.28

- 1978

- 4.98

- 1757

- DR2000

- -

- 1168

- -

- 8

- -

- B

- SIR of 2 Channels AP

- -

- TIC

- 2.57e4

- Area

- 6.43

- 2417

- 5.02

- 649

- 5.33

- 102

- 7.16

- 57

****

****

****

## Lake Trout

***Lake Trout***

***Alewife***

- alpha

- alpha

- gamma

- gamma

**From Tomy et al. 2003**

## MeTBBPA and AcTBBPA NCI SIM Two small peaks are the non-derivatized and mono-acetylated TBBPA 

- MeTBBPA and AcTBBPA NCI SIM Two small peaks are the non-derivatized and mono-acetylated TBBPA

- From Quade 2003

## TBBPA in Biosolids

- From Quade 2003

## PBDEs in A-biotic Environment 

- PBDEs in A-biotic Environment

**0**

**2**

**4**

**6**

**8**

**Western Basin - B**

**Western Basin - A**** **

**Central Basin**

**Eastern Basin - B**

**Eastern Basin - A**

**pg/L (parts per quadrillion)**

**Suspended**

**Solids**

**Dissolved**

- Water results from Luckey *et al*. 2001

## Concentration of  BDE-209 in a Sediment Core from St. Lawrence Estuary 

- 1920

- 1930

- 1940

- 1950

- 1960

- 1970

- 1980

- 1990

- 2000

- 0

- 1

- 2

- 3

- 4

- 5

- 6

- 7

- DeBDE  (ng/g)

- Year

- 1920

- 1930

- 1940

- 1950

- 1960

- 1970

- 1980

- 1990

- 2000

- 0

- 10

- 20

- 30

- 40

- 50

- 

- PCB (ng/g)

- Year

- Concentration of  BDE-209 in a Sediment Core from St. Lawrence Estuary

- From Lebeuf *et al.* 2002

## Concentration of TBBPA (ng/g dry weight) in Sewage Sludge from STP across Canada

- From Lee and Peart 2002

## From Quade et al. 2003

- From Quade *et al.* 2003

## Concentration of PBDEs (ng/g ww) in Biota 

- (from Manchester *et al.* 2001, Asplund *el al.*1999, Lebeuf and Torttier 2000, Luross *et al.* 2000 She *et al.* 2000,Alaee *et al.* 1999)

- 1

## PBDEs in Avian Egg Specimens(from Wakeford and Simon 2000)

- PBDEs in Avian Egg Specimens(from Wakeford and Simon 2000)

- Tetra for Osprey divided by 5

## Temporal Trends of PBDEs in the Great Lakes

- From Norstrom *et al.* 2002, Luross *et al.*  2001, and Chernyak  *et al.* 2002

## Temporal Trends of PBDEs in the Marine Mammalsfrom Ikonomou et al. 2002, Law et al. 2003, She et al. 2002, and Lebeuf et al. 2002

- Temporal Trends of PBDEs in the Marine Mammalsfrom Ikonomou *et al.* 2002, Law *et al.* 2003, She et al. *2002*, and Lebeuf *et al*. 2002

## Temporal Trends of PBDEs in Europe and Japan

- From Sellström *et al.* 1999 and Ohta *et al.* 2001

## Lake Ontario 

- Benthos
- Sediment

**Lake Ontario **
**Pelagic Food Web**

- Lake Trout

- Smelt

- Sculpin

- Alewife

- Mysids

- Diporeia

- Zooplankton

- Phytoplankton

- Herring Gull

## Bio-magnification of PBDEs in Lake Ontario Pelagic Food Web 

## Comparison between PBDEs and PCBs in Lake Ontario Food Web

- PCB data from Metcalfe *et al.* 1995

## From Tomy et al. 2003

- From Tomy *et al.* 2003

## 1

**1**

**A**

**Exposed Fish, Day 60**

**B**

- No BDE 209

**2**

**3,4,5**

**6**

**7**

**8**

- From Stapleton 2003

## From Stapleton 2003

- O

- Br

- Br

- Br

- Br

- Br

- Br

- Br

- O

- Br

- Br

- Br

- Br

- Br

- Br

- O

- Br

- Br

- Br

- Br

- Br

- Br

- O

- Br

- Br

- Br

- Br

- Br

- Br

- Br

**Hepta-1**

**Hexa-3**

**BDE 154**

**BDE 155**

## Slide 35

## Summary :

- PBDEs are ubiquitous global environmental pollutants
- Levels of PBDEs are on the rise in North American Environment
- TBBPA has been observed in suspended sediments from Detroit River and in sewage sludge across Canada
- HBCDD has been observed in fish from Lake Winnipeg, and Lake Ontario food web

## Acknowledgements:

- This presentation was the result of the hard work by many individuals, I would like to thank everyone who contributed to these studies.
- Funding for these studies has been provided by various agencies and is greatly appreciated.
- In particular funding from the Canadian Government through Toxic Chemicals Program, Toxic Substance Research Initiative, Northern Contaminants Program.