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Evolution of an Analytical Method for
Brominated Flame Retardants
K.A. MacPherson, T.M. Kolic and
E. J. Reiner
Ministry of the Environment –Toronto, Ontario
2
Overview
• Ontario Ministry of Environment– Dioxin Laboratory
• BFRs• Sample Preparation • GC-HRMS method development (2000 – 2006)• Current status/capability• Future analyses / Method Development
3
MOE - Laboratory Services Branch
LaSB provides analytical support for the ministry's – environmental monitoring – regulatory programs– data supports standard setting– analytical method development (emerging issues)– ensures the data quality of ministry compliance
enforcement and emergency analytical testing– Emergency response
4
MOE – LaSB -Dioxin LaboratoryPolychlorinated Dioxins and Furans (DFPCB - E3418)
Dioxin-Like PCBs (DFPCB - E3418)
Congener Specific PCBs by HRMS (PCBC - E3459)
Brominated Flame Retardants (PBDE - E3430)
Polychlorinated Naphthalenes (PCN - E3431)
Perflourooctane Sulfonate (PFOS – E3457)
Brominated and mixed Br/Cl dioxins and furans (PBDDc/PBDFs)*
Polychlorinated Diphenylethers (PCDE - 3432)*
LSB Method numbers in brackets (*) = Method under development
5
BFRs in the Environment
• Initial estimates by Environment Canada suggest:
– sewage biosolids may be a major contributor of the total PBDE loadings to the environment (excluding landfills)
– Sewage sludge, a product from waste water treatment process, which is organic rich and often applied as fertilizer on agricultural land
6
BFR survey in Biosolids
• NMA – Nutrient Management Act
• 2002 Legislation – The purpose of this Act is to provide for the management of
materials containing nutrients in ways that will enhance protection of the natural environment and provide a sustainable future for agricultural operations and rural development.
• In response to increased tendency for corporate farming, diminishing concern for land stewardship and increased concern for water quality & quantity
7
Sam
ple P
reparatio
n
8
Sample Cleanup Considerations
• Acid/Base/AgNO3 cleanup may be repeated with difficult samples
• Standard dilution for injection on GC-HRMS =1:50
• Difficult samples (& “overloaded”) may require dilutions up
= 1:800 (many co-extractables present)
9
Ideally one injection per sample
• Major & Minor congener consideration
– Some yet un-identified congeners present at minor concentrations
– Some predominant congeners need dilution for accurate quantification
10
The Era Begins….2000
• 4 function - SIM Experiment• HP 6890+ GC, 40m .18mm x .18µm rtx500 column• Ultima NT, running MassLynx (v4.0) software
• Monitor & quantify six congeners;
Br3 – Br7 : BZ# 28,47,99,100,153,154
11
2002 – Search for Deca • 6 function - SIM Experiment
• Monitor & quantify;
Br1 – Br10 (no Br8/ Br9)
• 13C12-BDE analytical standards available in calibration standard:
BZ#: 3, 15, 28, 47, 99, 153, 154, 183, 209
12
2004 - 2006
• Non-bde analytical standards available in CVS– HBB – Hexabromobenzene– PBEB – Pentabromoethylbenzene– BB-153 – Hexabromobiphenyl– BTBPE – 1,2-Bis(2,4,6-Tribromophenoxyethane)– DBDPE - Decabromodiphenylethane
13
Analytical Challenges
• Ensure Deca BDE efficiently introduced to GC
– Injector conditions
– Temperature
– Liner
– Carrier gas flow• Ensure Deca BDE efficiently leaves GC!
– Minimal Film Thickness
– Minimal length
– Appreciable ID
14
2000-2006
• Uniliner emulates on-column injection and reduces discrimination
• Uniliner potentially effective without sealing column and would also increase longevity
• Minimal injections no matter which injection port liner when high concentrations present
15
Injector Maintenance !
• Over time non-volatile sample residues in injector liner provide sites for absorption of critical analytes
• Enhanced Response
With clean injector
(The Reporter On-Line)
16
30m RTX500 .25mm x .15µm– 42 minutes
17
2003
• SEPARATION • extract injected on each of 2 columns: 15m & 30m
• QUANTIFICATION -
• Br3 -Br7
30m x 0.25mm x 0.10µm DB5-HT
• Br10
15m x 0.25mm x 0.10µm DB5-HT
18
GC experiments
15M
• Injector:280C• Split/Splitless• .9mL/min
• 110C• 40C/min 200 C• 10C/min 330 C
hold until deca elutes
30M
• Injector 280C• Split/Splitless• 1.8mL/min
• 110C• 10C/min 140 C• 80C/min 220 C• 5 C/min 330C
hold until deca elutes
19
30m DB-5HT (0.25mm x 0.10µm)
20
15m DB5-HT (0.25mm x 0.10µm)
21
15m DB-5HT (0.25mm x 0.10µm) 2005 CVS
22
Wide Range in Physical Properties
• Mass– 230 amu - mono– 972 amu - deca
• Melting Point– 300 C
• Boiling Point– 420 C
23
Analytical Challenges - HRMS Experiment Calibration
• Perfluorokerosene (PFK) is used as a reference calibrant
• Instrument calibration requires PFK masses which bracket the range of ions in the ion window (SIR experiment).
• Originally, modification of PFK reference file (Ultima-NT) necessary for successful SIR calibration up to ~971 Da. (13C12BDE 209)
Filename=c:\masslynx\ref\pfk.ref
24
Reference Compound Mixture• Perfluorokerosene-H (PFK)
• Boiling Point : 210 - 240C
• Supplier:
1 Industrial Dr., Pelham, NH 03076
• Catalogue No.: 16596
25
Molecular Ion Quantification
WHY
• 13C12BDE 209 AvailableAnalytical Standard
• Greater probability of positive identification
• No interferents in native ion channel
WHY NOT
1. Better response for [M - 2Br] + ion
2. Difficult calibration at this mass range
26
You never know what you’ll find
13C12-BDE 209
DBDPEDecabromodiphenylethane
27
Leading to production of analytical standard
• “Characterization of Mass-Labeled [13C14]-Decabromodiphenylethane and its use as a Surrogate Standard in the Analysis of Sewage Sludge Samples”
A.Konstantinova*, G.Arsenaulta, B.Chittima, K.MacPhersonb, A.McAleesa, R.McCrindlec, D.Pottera, E.Reinerb, C.Tashiroa and B.Yeoa.
Chemosphere 2004
28
2006 : Analysis for BFRs
• 1 Analytical Run GC: 15m DB5-HT (0.25mm x 0.10µm)
HRMS: 6 function SIM Experiment
CONGENERS: 46 Native + 5 non-BDE BFRs
19 13C12- BDEs4 Injection Standards
• ~16 min. for last elutor (BDE 209)• >900 samples reported
29
Future Method Development
• Transfer method to benchtop GC-MS/MS
• Excellent sensitivity 1pg DecaBDE (molecular ion)
• Less cost per analysisSkill level for operation < sector instruments
30
Jan25_05_c122767_0002a
14.80 15.00 15.20 15.40 15.60 15.80 16.00 16.20 16.40 16.60 16.80 17.00 17.20Time0
100
%
0
100
%
Jan25_05_c122767_0002a 6: Voltage SIR 15 Channels EI+ 959.1679
1.08e615.72
Jan25_05_c122767_0002a 6: Voltage SIR 15 Channels EI+ 969.2102
3.38e516.66
15.70
c122767-0002c 1/50
Time15.00 15.20 15.40 15.60 15.80 16.00 16.20 16.40 16.60 16.80
%
0
100
15.00 15.20 15.40 15.60 15.80 16.00 16.20 16.40 16.60 16.80
%
0
100
15.00 15.20 15.40 15.60 15.80 16.00 16.20 16.40 16.60 16.80
%
0
100
15.00 15.20 15.40 15.60 15.80 16.00 16.20 16.40 16.60 16.80
%
0
100
14un06_bfr3 10: MRM of 7 Channels EI+ 959.2 > 799.3
1.23e515.57
14un06_bfr3 10: MRM of 7 Channels EI+ 969.2 > 809.4
1.54e415.55
16.4515.65
14un06_bfr3 10: MRM of 7 Channels EI+ 969.2 > 485.2
1.66e416.45
15.57
14un06_bfr3 10: MRM of 7 Channels EI+ 969.2 > 482.2
2.10e416.45
DBDPE13C12-BDE 209
BDE 209
BDE 209
13C12-BDE 209
DBDPE
DBDPE
M S/
M S
H R M S
31
10pg DecaBDE / 20pg DBDPE
32
Acknowledgements
• Tereza Gobran – Sample Preparation
• Wellington Laboratories – Analytical Stds.