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Panayot Petrov, John Entwisle, Heidi Goenaga-Infante GC-ICP-MS reference methodology to quantify polybrominatedflame retardants in environmental waters relevant to the European Water Frame Directive.
European Metrology Research
• Traceable measurements for monitoring critical pollutants under the European Water Framework Directive– Duration 10/2011 to 09/2014
– Participants: BAM, BRML, IJS, JRC, LGC, LNE, PTB, SYKE, TUBITAK UME , UBA, ISPRA, REG(HZG)
– Target analytes: TBT, PAH, PBDE
• LGC involvement in ENV08 WFD– WP2 – Development of a validated measurement procedure for PBDE
in whole water samples at a concentration level required by the WFD
– WP4 – Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental aquatic compartments
Metrological aims
• Reference method for determination of PBDE in whole (non-filtered) water– Congeners of interest – PBDE 28, 47, 99, 100, 153, 154– Required LOQs – Σ(6 PBDEs) ≤ 0.15 ng/L in whole water
– Measurement uncertainty (95 % confidence) ≤ 50 % at EQS
• Systematic study of the interaction and partitioning of pollutants by field flow fractionation techniques– Distribution of the pollutants among fractions of different size and type;
– Elucidation of interactions / partitioning– Mass balance data for the size based distribution
Development of a validated measurement procedure for PBDE in whole water samples at a concentration level
required by the WFD
Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental
aquatic compartments
Chromatographic separation of the target PBDEs
• Short program– Species separated in 3.5 min
– Sample throughput – 4 samples per hour– Baseline separation of the target congeners
– Suitable for pre-screening for “above/below EQS”
• Long program– Species separated in 28 min– Sample throughput – 0.5 samples per hour (2h/sample)
– Separation of up to 180 PBDE congeners*
– Suitable for more accurate congener identification in case of PBDE concentrations > EQS level
*J. Chrom. A, 1217, 17, (2010), 2964–2972
Chromatographic separation of the target PBDEs
153154
99
100
47
28
0
20
40
60
80
100
120
140
160
180
200
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Time [sec]
Br S
igna
l [K
cps]
Br79 Br81
153
15499
10047
28
0
5
10
15
20
25
30
35
40
45
50
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000
Time [sec]
Br S
igna
l [K
cps]
Br79 Br81
Long GC separation method
Short GC separation method
Chromatographic separation / detection of the target PBDEs by HPLC-ICP-MS
0
50
100
150
200
250
0 1000 2000 3000 4000 5000 6000 7000
Time [sec]
Br S
igna
l [K
cps]
0
1
2
3
4
5
6
7
124X
e si
gnal
[Mcp
s]
Br79 Br81 124
PBDE 28PBDE 47
PBDE 100 PBDE 99
PBDE 154
PBDE 153
NIST 22571+19 diluted in n-hexane
0
200
400
600
800
1000
1200
1400
1600
0 100 200 300 400 500 600 700 800 900 1000
Time [sec]
Br S
igna
l [K
cps]
Br79 Br81
PBDE 28
PBDE 47
0
100
200
300
400
500
600
700
800
510 530 550 570 590 610
Time [sec]
Br
Sign
al [K
cps]
Br79 Br81
PBDE 100PBDE 99
PBDE 154PBDE 153
NIST 22571+19 diluted in n-hexane
Chromatographic separation / detection of the target PBDEs by HPLC-ICP-MS
Limits of detection for target PBDEs
• Limits of detection with external calibration– Instrumental detection limits – below 1ng/ml Br; calculated as 3 X noise
band width, expressed concentration based on external calibration by peak height
– Similar for both Br isotopes (79Br, 81Br)
– Similar for both Q-ICP-MS and SF-ICP-MS detectors– PBDE based IDLs ~ 1ng/ml
– Current method detection limits – 25 fg/mL as Br
– Current preconcentration factor – 40 000 X
Detection limits of the target PBDEs
• Instrument detection limits – Q-ICP-MS
0
2
4
6
8
10
12
14
16
6.5 7 7.5 8 8.5 9 9.5 10 10.5 11
Time [min]
79B
r Sig
nal [
Kcp
s]
-12
-7
-2
3
8
13
18
81B
r Sig
nal [
Kcp
s]
79Br 81Br
1531549910047
1.56 ng/ml Br
28
Detection limits of the target PBDEs
• Instrument detection limits – SF-ICP-MS
1 .5
2 .5
3 .5
4 .5
5 .5
6 .5
7 .5
8 .5
9 .5
40 0 4 50 50 0 5 50 60 0 6 50
Tim e [s]
Sig
na
l [k
cps]
7 9Br 8 1Br
28
47 100
99154
153
1 ng/ml Br
Preconcentration ProcedureRecoveries
0
20
40
60
80
100
120
PBDE 28 PBDE 47 PBDE 99 PBDE 100 PBDE 153 PBDE 154
Rec
over
y %
at 3
ng/
L
79Br 81Br
•Vary with the congener
•Consistent with relatively large uncertainty
•3 samples, each spiked with ~ 3 ng/L of each congener:
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600 700 800 900
Time [s]
79B
r Sig
nal [
kcps
]
ENV08 spiked ENV08
?
Finnish River Water Analysis
0
50
100
150
200
250
300
0 100 200 300 400 500 600 700 800 900Time [s]
79B
r Sig
nal [
kcps
]
Procedural blank Standards blend
28
47
100
99
154153
?
C= 1.25 ng/LR= 72 to 100%
Thames River Water Analysis
0
20
40
60
80
100
120
4 5 6 7 8 9 10 11
Time [min]
79B
r S
igna
l [K
cps]
PBDE 470.05 ng/L
PBDE 990.2 ng/L
Development of a validated measurement procedure for PBDE in whole water samples at a concentration level
required by the WFD
Advanced analytical platforms for monitoring the interaction and partitioning of pollutants in environmental
aquatic compartments
Fractionation of environmental water samples and NOMs
•Method development samples – Finnish river water, Thames
River water, Suwannee River NOM and Nordic Reservoir
NOM(IHSS), HA and HA-Na (Sigma)
•Size/mass calibrants – 1, 300, 1000 kDa PSS; Spherical S-PS
100, 200 nm; NIST gold nano-particles 10, 30, 60 nm spheres
•Detection:
- Online –> UV-MALS-ICPMS for size and elemental
composition
- Offline –> GC-SF-ICPMS for PBDEs association /
distribution on nano-particles
Fractionation of Finnish Water Sample
0
20
40
60
80
100
120
140
0 10 20 30 40 50 60 70 80Time [min]
Sig
nal [
kcps
]
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
Br s
igna
l [kc
ps]
Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120 Br79 Br81
0
1
2
3
4
5
6
7
8
9
10
0 10 20 30 40 50 60 70 80Time [min]
Sig
nal [
kcps
]
Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120
Fractionation of Thames River Water Samples
0
50
100
150
200
250
0 500 1000 1500 2000 2500 3000 3500 4000
time [s]
Sig
nal [
kcps
]
-2.5
-1.5
-0.5
0.5
1.5
2.5
3.5
4.5
Br s
igna
l [kc
ps]
Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120 Br79 Br81
0
2
4
6
8
10
12
14
16
18
20
0 500 1000 1500 2000 2500 3000 3500 4000
time [s]
Sig
nal [
kcps
]
Al27 Mn55 Fe57 Cu63 Cu65 Zn66 Sn118 Sn119 Sn120
100 ppm 1, 300, 1000 kDa PSS in 0.9% NaCl, 5 mM NH 4NO3 carrier
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0 10 20 30 40 50 60 70 80 90 100
Time [min]
UV
Sig
nal a
t 236
nm [V
]
-0.80
-0.75
-0.70
-0.65
-0.60
-0.55
-0.50
-0.45
-0.40
UV
Sig
nal a
t 254
nm [V
]
1 kDa
300 kDa
1000 kDa
Calibrant Fractograms
Nist Au 10, 30, 60 nm spheres
0
20
40
60
80
100
120
140
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000
Time [s]
Sig
nal [
kcps
]
Field
release
100, 200nm S-PS in 5 mM NH 4NO3 carrier
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0 10 20 30 40 50 60 70 80 90 100Time [min]
UV
Sig
nal a
t 236
nm [
V]
-0.80
-0.60
-0.40
-0.20
0.00
0.20
0.40
0.60
0.80
UV
Sig
nal a
t 254
nm [
V]
236 nm 254 nm
100 nm
200 nm
Field
release
Size Calibrants Fractogramsand MALS Size Estimation
Radius
Time [min]6560555045
Rad
ius
[nm
]
85
80
75
70
65
60
55
50
45
40
35
Detector S
ignal[V]
0.0
- MALS calculated diameters 92 nm and 212 nm
100, 200nm S-PS in 5 mM NH 4NO3 carrier
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0 10 20 30 40 50 60 70 80 90 100Time [min]
UV
Sig
nal a
t 236
nm [
V]
-0.80
-0.60
-0.40
-0.20
0.00
0.20
0.40
0.60
0.80
UV
Sig
nal a
t 254
nm [
V]
236 nm 254 nm
100 nm
200 nm
Field
release
Fractograms of HA -Na and PBDE spiked HA -Na
1 0 0 p p m H A - N a i n 5 m M N H 4 N O 3
0 . 0
0 . 2
0 . 4
0 . 6
0 . 8
1 . 0
1 . 2
1 . 4
1 . 6
1 . 8
2 . 0
0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 7 5 8 0
T i m e [ m i n ]
Sig
nal [
kcp
s]B r 7 9 B r 8 1
1 0 0 p p m H A - N a + 2 5 0 p p b P B D E
0 . 0
0 . 5
1 . 0
1 . 5
2 . 0
2 . 5
3 . 0
3 . 5
4 . 0
4 . 5
5 . 0
0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5 7 0 7 5 8 0
T i m e [ m i n ]
Sig
nal [
kcps
]
B r 7 9 B r 8 1
ASF4 offline GC -SF-ICP-MS analysis of HA -Na
• 2 x 1 ml HA-Na 100ppm, 30 ml fraction, 50µl extract volume
8
18
28
38
48
58
68
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0Time [min]
79B
r sig
nal i
n H
A-N
A s
ampl
e [k
cps]
-10
-5
0
5
10
15
20
79B
r sig
nal i
n a
stan
dard
[kcp
s]
HA-Na PBDEs standard
PBDE-47
PBDE-100
PBDE-99
U1
U2
PBDE-28
PBDE-154
PBDE-153
PBDE-99
PBDE-47
ASF4 offline GC -SF-ICP-MS analysis of HA -Na
• 2 x 1 ml HA-Na 100 mg/L + 500 ng/ml PentaBDE (DE-71)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0
Time [min]
79B
r in
HA
-Na
spi
ked
sam
ple
[Mcp
s]
-10
-5
0
5
10
15
20
79B
r si
gna
l in
a st
anda
rd [k
cps]
PBDE spiked HA-Na sample PBDEs standard
PBDE-47
PBDE-100
PBDE-99PBDE-28
PBDE-154PBDE-153
PBDE-100
PBDE-154 PBDE-153U2U1PBDE-28
Future prospective
• Improve the limits of detection to reach the WFD requirements• Employ 81Br isotopically enriched PBDE species for
quantification of PBDEs in natural water samples • Use FFF in combination with conventional fractionation
techniques to better characterize the interaction and partitioning of PBDEs in water samples, rich in organic and inorganic colloids.
• Validate the methodology and prepare uncertainty budget for quantification of PBDEs in natural waters after LLE, species specific double ID-ICP-MS quantification
Thank you for your attention …
The authors are grateful to EMRP and NMO for sponsoring this research, to Volker Nischwitz, who helped with the method development for WP2 and WP4,to Christopher Hopley for his highly valued advice in GC method development and troubleshooting, and last but not least to all our partners and colleagues, without whom this research wouldn’t be possible.
Acknowledgements: