nuevas tendencias en el análisis de trazas de ...©2012 waters corporation 1 nuevas tendencias en...
TRANSCRIPT
©2012 Waters Corporation 1
Nuevas Tendencias en el análisis de trazas de contaminantes emergentes : residuos
farmacéuticos, POP’s y PFC
MS Technology Day
Sesión Alimentación y Medio Ambiente
Madrid, 20 de marzo de 2012
Miguel Ángel Cortés
©2012 Waters Corporation 2
Ultra trace analysis What are the challenges?
Challenging matrix/analyte combinations
Low LOQs • Low target
levels
Amount of sample • Mass/volume
possible to extract
Matrix effects • Complex
matrices
Reproducibility • Trace levels can
affect statistics
©2012 Waters Corporation 3
Waters Holistic Solution
©2009 Waters Corporation | COMPANY CONFIDENTIAL ©2011 Waters Corporation
Ultra trace analysis How can Xevo TQ-S help?
Xevo TQ-S performance enables: Enhanced sensitivity
Reduced volumes during sample prep and analysis
Proactively monitor matrix levels during analysis
Improved reproducibility due to increased signal intensity
Better quality results, minimal user intervention
©2012 Waters Corporation 5
PFCs analysis • Natural water samples • Fire fighting foam run off samples • Biological fluids
• Oasis WAX sample preparation • RADAR to investigate matrix effects
©2012 Waters Corporation 6
PFC’s analysis challenges
Liquid chromatography with tandem mass spectrometer is the method of choice for analyzing perfluorinated compounds. However, it is still a challenge to quantify trace levels of perfluorinated compounds unambiguously.
One of the difficult problems is background PFC contamination.
The major sources of contamination are mobile phases and Teflon components of the instrument. Although methanol and water can be further purified to reduce PFC contaminants by filtering through strong anion-exchange, reversed-phase and active carbon cartridges, the steps involved could be time-consuming and costly.
©2012 Waters Corporation 7
PFC’s analysis chalenges
©2012 Waters Corporation 8
PFC Contaminants Interference with Quantification
©2012 Waters Corporation 9
System PFC isolation
PEEK solvent lines
PFC isolator column
Solvent mixer
From pump
to injector
©2012 Waters Corporation 10
MRM Chromatograms of PFOA: Isolator Column In-line
MRM chromatograms of 463>369 channel
Time2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00
%
0
100
2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00
%
0
100
No peaks
Background PFOA contaminant
Background PFOA contaminant
Analyte PFOA
Blank Injection
300 ppt PFOA standard
0.5 min
©2012 Waters Corporation 11
Waters PFC’s analysis system
Acquity Xevo TQ-S with step wave technology and RADAR
o New source Z-Spray compatible with high flow rate.
o Fast scan speed: enough number of points per peak for quantitative and qualitative analysis, compatible with UPLC with the capability to combine different ionization modes in one run.
o Unparallel software, for complete control of the UPLC/MS(MS) and data management: Quanpedia, TargetLynx, Trendplot, Intellistart, QC Monitor
©2012 Waters Corporation 12
PFBuS
PFHxA
PFHpA PFHxS
THPFOS
PFOA
PFOS
PFNA
PFDA
PFUnDA
PFDoDA
ACQUITY UPLC Separation
©2012 Waters Corporation 13
PFCs – 200fg on column
PFBA
PFPeA
PFHpA
PFHxA
PFOA
PFNA
PFDA
PFDoDA
PFUnDA
PFTrDA
PFBuS
PFHxS
PFOS
PFDS
©2012 Waters Corporation 14
Aqueous Sample Quantitation
413 > 369
413 > 219
413 > 169
Tap Water Lake Mariestadssjön River Svartån
Compound name: PFOACorrelation coefficient: r = 0.999898, r^2 = 0.999796Calibration curve: 0.311728 * x + 0.0612933Response type: Internal Std ( Ref 6 ), Area * ( IS Conc. / IS Area )Curve type: Linear, Origin: Exclude, Weighting: Null, Axis trans: None
Conc0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Re
spo
nse
0.00
1.00
2.00
3.00
4.00
5.00
0.42 ng L-1 1.3 ng L-1 1.1 ng L-1
Compound name: PFOSCorrelation coefficient: r = 0.999705, r^2 = 0.999410Calibration curve: 0.558744 * x + 0.0416708Response type: Internal Std ( Ref 11 ), Area * ( IS Conc. / IS Area )Curve type: Linear, Origin: Exclude, Weighting: Null, Axis trans: None
Conc0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0
Re
spo
nse
0.0
2.0
4.0
6.0
8.0
10.0
Tap Water Lake Mariestadssjön River Svartån
1.5 ng L-1 1.30 ng L-1 1.4 ng L-1
499 > 99
499 > 80
©2012 Waters Corporation 15
RADAR-MRM Monitoring Surface Water Background (Lake Mariestadssjön)
PFHx
A
0.41 n
g L-1
PFBu
S
0.23
ng
L-1
PFHp
A
0.69 n
g L-1
PFHx
S 0
.42 n
g L-1
PFOA
1.
30 n
g L-1
PFNA
0.4
2 ng
L-1
PFOS
1.3
0 ng
L-1
©2012 Waters Corporation 16
RADAR-MRM : Observing Matrix Interferents
Laboratory contaminants
©2012 Waters Corporation 17
RADAR-MRM Laboratory Contaminants
C10 LAS
C11 LAS
C12 LAS
C13 LAS
Full Scan TIC
XIC 297 m/z
XIC 311 m/z
XIC 325 m/z
XIC 337 m/z
PFC isolator hold-up
©2012 Waters Corporation 18
Fire Fighting Training - Samples
Seepage water samples from fire training activity after cleaning steps (close to source)
Borehole from lake adjacent to fire training activity at an airport (further from source)
©2012 Waters Corporation 19
PFHxA
x100
x10
x 2
.5
decr
ease
x 1
0.2
d
ecr
ease
802268
318971
31270
Peak Area
Fire Fighting Training – Samples Diluting Matrix Effects
Original Sample (FFF run off) x10 dilution x100 dilution
Expected RT
©2012 Waters Corporation 20
Biotic Material – Salmon Liver
Complex sample — Oasis sample prep
Two major analytical problems
— PFOS interference
— Retention time shift
Causative sample matrix components can be observed using RADAR-MRM
IMAG
E: N
OAA
©2012 Waters Corporation 21
Salmon Liver - Analytical Problems
Sal
mon L
iver
Solv
ent
Sta
ndar
d
PFHx
A
PFBu
S
PFOA
PFNA
PFOS
PFHp
A
PFHx
S
PFDA
PFUn
DA
PFDo
DA
MRM Interference
RT Shift
©2012 Waters Corporation 22
Salmon Liver DS-MRM
a b
Solv
ent
Sta
ndar
d
Sal
mon M
RM
Sal
mon F
S T
IC
©2012 Waters Corporation 23
498
499
Salmon Liver RADAR-MRM Spectra
b
498
a
514
PFOS 499>80
XIC 499 m/z
Isotopic interference on Pre-cursor mass
©2012 Waters Corporation 24
Salmon liver - PFOS DS-MRM
499>99
499>80 a b
PFOS 2.75ng/g
©2012 Waters Corporation 25
Product ion experiments
deoxytaurocholate
taurocholate
a
b 79.9 94.9
106.9 123.9
290.1
©2012 Waters Corporation 26
RT Shift – Bile acids
Taur
ocho
late &
deox
ytaur
ocho
late
ND ND 4.80 PFDoDA
ND 4.55 4.55 PFUnDA
4.27 4.26 4.27 PFDA
3.95 3.87 3.96 13CPFOS
3.94 3.87 3.96 PFOS
3.93 3.86 3.94 13CPFNA
3.94 4.00 3.94 PFNA
3.45 3.52 3.54 13CPFOA
3.44 ND 3.54 PFOA
ND ND 3.52 THPFOS
3.13 3.06 3.13 PFHxS
3.04 3.00 3.04 PFHpA
2.36 2.35 2.36 PFHxA
1.67 1.67 1.67 PFBuS
Salmon Liver dilution Salmon Liver Standard
Retention Time (min)
©2012 Waters Corporation 27
Possible “Clean-up” Strategy
Target amide group for hydrolysis (ideally prior to extraction)
— PFC resistance possible
Could avoid RT shift and interference problem