developments in the measurement of pops: implications for ...€¦ · 2nd seminar meeting of the...
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NERC Knowledge Transfer Network, 7 July 2005Slide 1
2nd seminar meeting of the NERC Knowledge Transfer Network on POPs. Developments in the measurement of POPs: Implications for research progress.
Emerging environmental Emerging environmental contaminantscontaminants –– applications of LCapplications of LC--MSMS
Martin Rose
Central Science LaboratorySand HuttonYORKYO41 1LZ
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NERC Knowledge Transfer Network, 7 July 2005Slide 2
Outline
Analytical approachesAnalytical approachesBrominated Brominated contaminantscontaminantsPCNs PCNs and and ClCl--PAHsPAHsFluorinated compoundsFluorinated compoundsToxapheneToxaphenePharmaceuticalsPharmaceuticalsOthersOthers
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NERC Knowledge Transfer Network, 7 July 2005Slide 3
Analytical approaches
LC-MSHBCDTBBAPFOS and relatedPAHs (LC-FD)Pharmaceuticals
All require careful cleanAll require careful clean--upupprior to instrumental analysisprior to instrumental analysis
GC-MSPXDD/FsPCBsPBDEsDeca-BDEPBBsToxapheneCl-PAHsPAHs
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NERC Knowledge Transfer Network, 7 July 2005Slide 4
Brominated contaminants
6
2
5
3
4
O 2'
6'
3'
5'4'
BrBr
Polybrominated diphenyl ether (PBDE)
Br = 1 to 10
6
2
5
3
4
2'
6'
3'
5'
4'
BrBrBr = 1 to 10
Polybrominated Biphenyl (PBB)
PBDEs and PBBs –emerged
PBDD/Fs / mixed bromo- chloro- dioxins (PXDD/Fs)
TBBA and HBCDD
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NERC Knowledge Transfer Network, 7 July 2005Slide 5
Litten, S., Environmental Science & Technology, 37, 5502-5510, 2003Lioy, P.J., et al., Environ. Health Perspect., 110, 703-714, 2002
World Trade Centre
Tonnes of BFRs burntExceptionally high levels of PBDEs detected in dusts and water run off from ground zero Brominated furans detected in many samplesPBBs > PBDEsPBDD/Fs >> PCDD/Fs
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Blend and Freeze Dry
Alumina
H2SO4
Alumina
H2SO4
HRGC-HRMS
NON-PLANAR FRACTION PLANAR FRACTION
Activated carbon fractionation
Ultra-Turrax (Hexane)
Weigh and add 13C Internal Standards
Multi layer silica column1. DCM/Hexane 2. Toluene
PBDEs & PBBs PBDD/Fs
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Freeze dry, extract, purify and concentrate
250ml Milk
(5-50g solids)25µl Extract
Concentration Factor = 10,000
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Instrumental Analysis
HRGC-HRMS, Triple sector, EISelected Ion MonitoringTwo ions monitored for each analyteMass Resolution 10,000 (4 decimal place)Quantification - Isotope dilution methodology60m DB5-MS, thin film (0.1µm) columnPTV injector - 10 µL injections
16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00 42.00 44.00 46.00Time0
100
%
2
13
10
7
8
11
12/13
15
30 3217
25
28
3537
PCB202
75
49
71
47
66
77 100
119
99
116
118
85
155
126
154153
139138
166
183
181
190
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NERC Knowledge Transfer Network, 7 July 2005Slide 9
Alwyn Fernandes*, Shaun White, Kyle D’Silva and Martin Rose Simultaneous determination of PCDDs, PCDFs, PCBs and PBDEs in food.Talanta 63 (5) 1147-1155 (2004)
Method Performance
0.05 µg/Kg (ppb)50-110%10%PBBs
30–80%
50-110%
Typical Recovery
0.1 - 6.0 ng/Kg (ppt)
0.05 µg/Kg (ppb)
Method LOD (Lipid Weight)
10%PBDD/Fs
11%PBDEs
Method Precision
(RSD)Analyte
Precise, Accurate, RobustPrecise, Accurate, Robust
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NERC Knowledge Transfer Network, 7 July 2005Slide 10
Meironyte, D., Noren, K., and Bergman, A. J. Toxicol. Environ. Health A 58, 329–341, 1999.
PBDEs in Swedish Human Milk
0
500
1000
1500
2000
2500
3000
3500
4000
450019
72
1974
1976
1978
1980
1982
1984
1986
1988
1990
1992
1994
1996
Year
PB
DE
s (p
g/g
fat)
0
20
40
60
80
100
120
TEQ
(pg/
g fa
t)
PBDEsTotal TEQ (PCDD, PCDF, PCB)
Expon. (Total TEQ (PCDD, PCDF, PCB))Expon. (PBDEs)
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NERC Knowledge Transfer Network, 7 July 2005Slide 11
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Rel
ativ
e co
mpo
sitio
n
BD
E-1
5
BD
E-7
BD
E-1
7
BD
E-2
8
BD
E-4
7
BD
E-4
9
BD
E-6
6
BD
E-7
1
BD
E-7
7
BD
E-8
5
BD
E-9
9
BD
E-1
00
BD
E-1
19
BD
E-1
26
BD
E15
3
BD
E13
8
BD
E 1
54
BD
E-1
83
UK Breast Milk Bromkal 70-5DE
PBDE congener profile in UK Human milk
PBDE-153 accumulating?
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NERC Knowledge Transfer Network, 7 July 2005Slide 12
PBDEs in Human Milk
0
1
2
3
4
5
6
7
8
9
10
1970 1975 1980 1985 1990 1995 2000 2005
Sampling Year
Med
ian
valu
e of
Sum
PB
DE
s (n
g/g
lipid
)
Sweden
Germany
Finland
UK
UK (CSL)
Holland
FaroeIslands
Belgium
Japan
UK Breast Milk
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NERC Knowledge Transfer Network, 7 July 2005Slide 13
PBDEs in Herons (1)
Predatory BirdsFeed on Fish, Amphibians, Small Rodents and MammalsSusceptible to bio-accumulating lipophillic environmental pollutants
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NERC Knowledge Transfer Network, 7 July 2005Slide 14
PBDEs in Herons (2)
Birds found dead and deformed – BESTHORPETissue samples taken from Juveniles & Adults at site as well as eggs from nests.Eggs and tissue samples taken from two control sites –HERTFRODSHIRE and CHESHIRE
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NERC Knowledge Transfer Network, 7 July 2005Slide 15
PBDEs in Herons (3)
0
500
1000
1500
2000
ng/g
lipi
d
BD
E-1
7
BD
E-2
8
BD
E-4
7
BD
E-4
9
BD
E-6
6
BD
E-7
1
BD
E-7
7
BD
E-8
5
BD
E-9
9
BD
E-1
00
BD
E-1
19
BD
E-1
26
BD
E15
3
BD
E13
8
BD
E 1
54
BD
E-1
83
Site C (Hertfordshire) Site A (Nottinghamshire) Site B (Cheshire)
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NERC Knowledge Transfer Network, 7 July 2005Slide 16
PBDEs in Herons (4)
0
200
400
600
800
1000
1200
BD
E-1
7
BD
E-2
8
BD
E-4
7
BD
E-4
9
BD
E-6
6
BD
E-7
1
BD
E-7
7
BD
E-8
5
BD
E-9
9
BD
E-10
0
BD
E-11
9
BD
E-12
6
BD
E-15
3
BD
E-13
8
BD
E-15
4
BD
E-18
3
ng/g
lipi
d
Eggs Juvenille Fat Adult FatUp to 1 ppm lipid
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NERC Knowledge Transfer Network, 7 July 2005Slide 17
PBDEs in Herons (5)
0
10
20
30
40
50
60
70
80
BDE-
10BD
E-7
BDE-
11BD
E-8
BDE-
12BD
E-13
BDE-
15BD
E-30
BDE-
32BD
E-17
BDE-
25BD
E-BD
E-35
BDE-
37BD
E-75
BDE-
49BD
E-71
BDE-
47BD
E-66
BDE-
77BD
E-10
0BD
E-11
9BD
E-99
BDE-
116
BDE-
118
BDE-
85BD
E-12
6BD
E-15
5BD
E-15
4BD
E-15
3BD
E-13
8BD
E-16
6BD
E-18
3BD
E-18
1BD
E-19
0BB
-52
BB-4
9BB
-77
BB-8
0BB
-101
BB-1
53BB
-169
ng/g
wet
wei
ght
PBB-153 Banned for >20 years
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NERC Knowledge Transfer Network, 7 July 2005Slide 18
PBDEs and PBBs in Polar Bears (2000)
0
2
4
6
8
10
12
BD
E-1
0B
DE
-7B
DE
-11
BD
E-8
BD
E-1
2/13
BD
E-1
5B
DE
-30
BD
E-3
2B
DE
-17
BD
E-2
5B
DE
-28/
33B
DE
-35
BD
E-3
7B
DE
-75
BD
E-4
9B
DE
-71
BD
E-4
7B
DE
-66
BD
E-7
7B
DE
-100
BD
E-1
19B
DE
-99
BD
E-1
16B
DE
-118
BD
E-8
5B
DE
-126
BD
E-1
55B
DE
-154
BD
E-1
53B
DE
-138
BD
E-1
66B
DE
-183
BD
E-1
81B
DE
-190
BB
-52
BB
-49
BB
-80
BB
-77
BB
-101
BB
-153
BB
-169
Mea
n ng
/g li
pid
(n=
4)
x 10
x 10
PBDE-153 appears
resist metabolism PBB-153 Dominant
to bioaccumulate or
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NERC Knowledge Transfer Network, 7 July 2005Slide 21
Deca-BDE
Occurrence – database poor – high environmental levelsPhoto-degradation to form PBDD/FsDifficult to measure – thermo-labile, adsorption lossesRisk assessments – ongoing (EFSA)
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NERC Knowledge Transfer Network, 7 July 2005Slide 22
Deca-BDEHomogenisation of Sample 50gSample
PreparationInternal Standardisation
with 13C-PBDD/F, Deca-BDE
Hexane/Dichloromethane extraction/elution from
Multilayered modified silica column
Fractionation on activated carbon
PBDD/F fraction – purified on activated alumina
Concentration and Sensitivity Standard addition
Analysis by HRGC-HRMS
Deca-BDE
25µl
Extraction andFractionation
Purification
Measurement
50µl
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2 7 . 0 0 2 8 . 0 0 2 9 . 0 0 3 0 . 0 0 3 1 . 0 0 3 2 . 0 0T i m e0
1 0 0
%
0
1 0 0
%
0
1 0 0
%
p b d e A 0 1 2 2 1 7 2 : V o l t a g e S I R 7 C h a n n e l s E I + 8 1 1 . 3 7 3 6
5 . 0 0 e 53 1 . 2 1
2 7 . 8 5
p b d e A 0 1 2 2 1 7 2 : V o l t a g e S I R 7 C h a n n e l s E I + 7 9 7 . 3 3 5 3
1 . 9 6 e 53 1 . 2 1
3 0 . 9 03 0 . 3 22 9 . 2 42 7 . 8 3 3 2 . 2 43 1 . 8 9
p b d e A 0 1 2 2 1 7 2 : V o l t a g e S I R 7 C h a n n e l s E I + 7 8 3 . 3 3 8 4
3 . 1 5 e 42 9 . 1 3
2 8 . 9 92 8 . 1 7
2 7 . 8 92 6 . 9 6
3 1 . 9 43 1 . 0 3
2 9 . 9 92 9 . 6 6 3 0 . 7 5 3 1 . 1 23 1 . 7 7
3 2 . 0 73 2 . 5 3
13C deca-BDE
deca-BDE
deca-BB
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NERC Knowledge Transfer Network, 7 July 2005Slide 24
Tetrabromobisphenol A: TBBA
CH3
CH3
OH OH
Br
Br
Br
Br
Used to manufacture epoxy resins used in printed circuit boards (up to 34% by weight TBBPA)
High production volume chemical
Reactive flame retardant – bound to matrix
Excess TBBPA can leach out
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NERC Knowledge Transfer Network, 7 July 2005Slide 25
Hexabromocyclododecane: HBCD
Principal flame retardant used in foams (expanded polystyrene) in furniture and building materials
High production volume chemical
Additive flame retardant – can leach from matrix
3 diastereoisomers – α, β, and γ
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NERC Knowledge Transfer Network, 7 July 2005Slide 26
Classification as POPs?
Persistent?Bio-accumulative - YesLong range transport - YesToxic • TBBPA – Endocrine disrupting, estrogenic
activity• HBCD – neuro-developmental, hepatotoxic
Very little toxicological or exposure data!
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NERC Knowledge Transfer Network, 7 July 2005Slide 27
Analytical Methodology - Schematic
Sample homogenisation, Na2SO4 Drying
Internal Standardisation Addition of 13C-HBCD, 13C-TBBPA
Cold Solvent extraction(Hexane:DCM)/acid hydrolysis
Filtration
Sample PreparationSample Preparation
ExtractionExtraction
Solvent exchange Solvent exchange or purificationor purification
MeasurementMeasurement Analysis by HRGC-HRMS (SIM)
Alumina column
Pre-concentration
Solvent exchanged to Methanol:Water
Analysis by HPLC-MS/MS
(MRM)
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NERC Knowledge Transfer Network, 7 July 2005Slide 28
GC-MS
HBCDOptimum temperatures required – all zones
Speciation not possible
Small increases in zone temperature dramatically reduce sensitivity
TBBPANo derivitisation required
Purification requires optimisation – poor recoveries
BOM(s) 156
19.50 20.00 20.50 21.00 21.50 22.00 22.50 23.00Time0
100
%
51
100
%
bfrA000501 Sm (Mn, 1x1) Voltage SIR 9 Channels EI+ 560.7279
2.87e621.32
20.65
bfrA000501 Voltage SIR 9 Channels EI+ 528.7295
6.22e720.66
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NERC Knowledge Transfer Network, 7 July 2005Slide 29
GC-MS Sample Analysis02-Feb-2005, 16:56:25Mackerel (SN: 10704) - Extract 12879
19.25 19.50 19.75 20.00 20.25 20.50 20.75 21.00 21.25 21.50 21.75 22.00Time0
100
%
0
100
%
0
100
%
bfrA001705 Voltage SIR 11 Channels EI+ 572.7687
9.06e521.24
20.6619.66
bfrA001705 Voltage SIR 11 Channels EI+ 560.7279
2.00e621.26
bfrA001705 Voltage SIR 11 Channels EI+ 493.7377
5.13e720.95
13C PBDE-139 (Syringe standard)
13C HBCD
HBCD
Native HBCD in Mackerel
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NERC Knowledge Transfer Network, 7 July 2005Slide 30
HPLC-MS/MS conditions
Column Sunfire C18 150 mm x 2.1 mm, particle size 3.5 µm
Flow rate 0.2 ml/min Mobile phase A = methanol, B = water Gradient t = 0 min, A = 90%; t = 15 min, A = 100%;
t = 16 min, A = 90% Run time 20 min Injection volume 20 µl Column temperature 30 ºC Typical retention time β-HBCD = 6.4 min
γ-HBCD = 7.1 min α-HBCD = 5.5 min TBBPA = 3.0 min
Ionisation mode Electrospray negative ionisation Source temperature 120 ºC De-solvation temperature 300 ºC
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NERC Knowledge Transfer Network, 7 July 2005Slide 31
Limits of detection – HPLC-MS/MSMRM test16-Dec-200419:16:37
Time1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00
%
61
bfr3_161204_2_010 Sm (Mn, 1x2); Sm (Mn, 1x2) 4: MRM of 2 Channels ES- 640.3 > 78.9
1.88e37.12
6.38
5.55
3.001.801.09
0.141.44
2.24 2.79 3.69
5.91
14.66
12.279.228.46 10.24
9.79 11.16 11.73
13.4512.60 13.97
HBCD 0.5 ng/mlα
βγ
Analyte LOD (ng/ml)α-HBCD 0.41β-HBCD 0.49γ -HBCD 0.21
13C α-HBCD 0.33TBBPA 0.77
13C TBBPA 0.40
MRM test16-Dec-200419:16:37
Time1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00
%
63
bfr3_161204_2_010 Sm (Mn, 1x2); Sm (Mn, 1x2) 2: MRM of 2 Channels ES- 554.54 > 430.73
1.77e33.06
2.02
0.48 1.591.17
0.96
2.28
10.63
5.54
5.02
3.41 3.824.29
4.50
8.43
6.63
6.04
7.329.168.59
9.56 10.18
13.84
11.36 11.76
12.49
12.09
13.2012.87
13.54
15.1914.65
14.27
TBBPA 0.5 ng/ml
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NERC Knowledge Transfer Network, 7 July 2005Slide 32
Linearity – 0.5 to 20 ng/ml
Analyte Correlation coefficientα-HBCD 0.9997β-HBCD 0.9988γ -HBCD 0.9996TBBPA 0.9989
0
500
1000
1500
2000
2500
3000
3500
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
co ncentra tio n / ng/ml
β-HBCD
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NERC Knowledge Transfer Network, 7 July 2005Slide 33
Other validation data
Precisionα-HBCD β-HBCD γ -HBCD 13C α-HBCD TBBPA 13C TBBPA
Mean 4803 3308 7990 6516 1868 4561Stdev 461 172 332 448 208 178RSD% 9.6 5.2 4.2 6.7 11.2 3.9
Reference Material dataNo HBCD/TBBPA RM
Bx 1 Bx 2 Bx 338.0 34.1 62.4
α-HBCD concentration (ng/g) mean = 44.8 ng/gRSD = 34 %
published value = 39.6 ng/g
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NERC Knowledge Transfer Network, 7 July 2005Slide 34
Sample chromatograms
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00Time0
100
%
0
100
%
4.63
2.830.11 2.05
1.531.98
2.672.34
2.883.733.21
4.377.356.906.454.89
5.15 5.8614.3514.14
7.68 13.559.018.447.82 11.2310.6110.35
9.60 11.96 12.29 13.14 14.09 14.99
11.95
11.91
11.329.59
11.25
11.15
12.05
α-HBCD 0.49 ng/gβ-HBCD 0.13 ng/gγ -HBCD 0.20 ng/gTBBPA <0.02 ng/g
TDS group 5 - meat products
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NERC Knowledge Transfer Network, 7 July 2005Slide 35
BFRs form brominated dioxins and furans (PBDD/Fs)
PBDD/Fs210 congenersThermal breakdown products of brominated organicsFormed from burning of BFRs in plasticsHighly toxic and persistentMimic hormones – ThyroxineSome congeners more toxic than 2,3,7,8-substituted chlorinated dioxins
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NERC Knowledge Transfer Network, 7 July 2005Slide 36
Brominated dioxins and furans:tri – penta BDFs in food extract
2 4 . 0 0 2 6 . 0 0 2 8 . 0 0 3 0 . 0 0 3 2 . 0 0 3 4 . 0 0 3 6 . 0 0 3 8 . 0 0T i m e3
1 0 0
%
b d x c 0 0 1 7 0 8 3 : V o l t a g e S I R 1 7 C h a n n e l s E I + 5 6 1 . 6 0 5 9
6 . 0 0 e 5
3 4 . 6 3
3 4 . 4 6
3 6 . 0 2
3 6 . 2 2
3 6 . 7 03 8 . 3 9
tri tetra penta
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NERC Knowledge Transfer Network, 7 July 2005Slide 37
Chlorinated napthalenes and Cl-PAHs
PCNsbetter studied, but poor databaseRecognised dioxin-like effects – TEFs ?Documented occurrence – food, environment
Cl-PAHsOccurrence – environmental, food?Toxicity – predicted
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NERC Knowledge Transfer Network, 7 July 2005Slide 38
Fluorinated contaminants
S
F F
F F
F F
F F
F F
F FFF
FF
F
O
ON
O
OH
S
F F
F F
F F
F F
F F
F FFF
FF
F
O
ON
OH
S
F F
F F
F F
F F
F F
F FFF
FF
F
O
OHN
O
OH
N-EtFOSE
PFOSAA
S
F F
F F
F F
F F
F F
F FFF
FF
F
O
ONH2
PFOSA
S
F F
F F
F F
F F
F F
F FFF
FF
F
O
OOH
PFOS
OH
F F
F F
F F
F F
F F
FF
FF
F
PFOA
O
Oxidation
M556
PFOS and related‘Scotchguard’Teflon
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NERC Knowledge Transfer Network, 7 July 2005Slide 39
Summary of LC-MS/MS conditions for PFOS and related compounds
Rt [M-H]- Prod Cone V Prod Cone Vn-C3 Acid PFprA 163 119 10n-C4 Acid PFBA 213 169 8n-C5 Acid PFPeA 10.61 263 219 7n-C6 Acid PFHxA 11.37 313 269 6n-C7 Acid PFHpA 12.17 363 319 6n-C8 Acid PFOA 12.98 413 369 7i -C9 Acid PFTMHxA 463 419 4 219 12n- C9 Acid PFNA 13.79 463 419 7n-C10 Acid PFDeA 14.66 513 469 8n-C11 Acid PFUnA 14 563 519 8n-C12 Acid PFDoA 16.45 613 569 8n-C14 Acid PFTdA 18.24 713 669 8n-C16 Acid PFHdA 20.09 813 769 8n-C18 Acid PFOdA 913 869 9
Tetrahydro THPFHxA 241 221 5 177 8
Labelled-C10 13C2-PFDeA 515 470 6
C4 PFBS 299 99 30 80 30C6 PFHxS 399 99 33 80 33i-C8 i-PFOS 499 169 25 80 35n -C8 n -PFOS 499 99 35 80 35Tetrahydro THPFOS 427 407 20 80 35
i-C8 Amide PFOSA 498 169 25 78 25n-C8 Amide PFOSA 498 169 25 78 25
Primary Secondary
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NERC Knowledge Transfer Network, 7 July 2005Slide 40
Chromatograms
FSQE#2 SunFire C8 2.1x150mm 5 um 20mM AmAcACNgrad
Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES-
813.1 > 769.11.26e5
14.07
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 713.1 > 669.1
6.30e413.74
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 613.1 > 569.1
4.82e413.34
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 563.1 > 519.1
9.36e413.03
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 515.1 > 470.1
1.81e36.725.483.06 3.71 14.8212.5910.228.11 8.31 11.32 16.09
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 513.1 > 469.1
1.94e512.61
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 499.1 > 80.1
3.26e312.92
3.902.15 6.835.79 7.91 11.5210.959.75 16.6214.76
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 498.1 > 78.1
1.09e410.62
6.03
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 463.1 > 419.1
2.41e511.88
FSQE#2 SunFire C8 2.1x150mm 5 um 20mM AmAcACNgrad
Time4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00
%
0
100FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES-
413.1 > 369.18.34e4
10.24
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 399.1 > 80.1
2.20e411.81
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 363.1 > 319.1
7.97e49.35
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 313.1 > 269.1
2.31e48.76
7.14
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 299.1 > 80.1
3.06e49.27
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 263.1 > 219.1
4.78e48.16
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 241.1 > 221.1
3.46e38.82
3.26 7.984.92 5.26 17.4814.2012.2611.37 15.84
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 213.1 > 169.1
2.64e413.256.78
2.04 12.127.74 8.78 9.31 11.39
13.76 16.02 16.57
FSQE003_Data066 Sm (Mn, 3x1) MRM of 20 Channels ES- 163.1 > 119.1
2.57e43.77
13.017.074.41 8.91 10.15 15.5113.74 16.60
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NERC Knowledge Transfer Network, 7 July 2005Slide 41
Total ion current
FSQE#2 SunFire C8 2.1x150mm 5 um 20mM AmAcACNgrad
Time3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00
%
0
100FSQE003_Data066 MRM of 20 Channels ES-
TIC3.32e5
11.86
9.55
9.35
8.16
3.79 6.768.76
10.31
11.52
12.59
14.09
13.03
13.72
14.43
16.0015.5116.77
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NERC Knowledge Transfer Network, 7 July 2005Slide 42
Toxaphene
‘Old’ pesticide; never used in UKPOP and global contaminant1216 congeners
(only a few found)
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NERC Knowledge Transfer Network, 7 July 2005Slide 43
Pharmaceuticals
Veterinary medicinesSulphonamidesTetracyclinesTylosinPenicillins
Dissipation in soilTransport in surface watersDrainflow, sedimentsLeaching
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Reproduced with permission from EMBO Reports, Vol 5(12)
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NERC Knowledge Transfer Network, 7 July 2005Slide 45
Uptake by organisms?
Controlled experimentsControlled experimentsLettuce and carrotsLettuce and carrotsNine veterinary medicinesNine veterinary medicinesExposed for 2 Exposed for 2 –– 4 months4 monthsAnalysis by LCAnalysis by LC--MSMS--MSMS
SoilSoilPlant materialPlant material
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NERC Knowledge Transfer Network, 7 July 2005Slide 46
Other emerging environmental contaminants
PAHs – not POPs (no bioaccumulation), ‘emerged’, recent extension to list of significant PAHs, new interest in exposure from food, MRLs etcTrace elements – esp. speciation studies for As and HgNitro-PAHsPBNsPXDD/FsHexachlorobenzene
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NERC Knowledge Transfer Network, 7 July 2005Slide 47
Dioxin-like toxicity of other compounds
PBDEs? – some early indications but possibly due to PBDD/F contaminationPBDD/Fs? – yes!
[Early studies suggest at least as potent as dioxins]
PXDD/Fs – no tox. data but would seem likelyHexachlorobenzene? Possibly – again possible contamination issuePCNs – very likelyPBNs – very likelyPBBs - very likely
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NERC Knowledge Transfer Network, 7 July 2005Slide 48
WHO-TEF Review: Geneva, 27-30 June 2005
Published revisions to TEFs likely to be in about a yearTransparency and consistencyMechanism for derivation and communication of processConfidential until published
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NERC Knowledge Transfer Network, 7 July 2005Slide 49
Acknowledgements
Alwyn FernandesKyle D’SilvaMalcolm DriffieldDon ClarkeShaun WhiteAlistair Boxall
All the Environmental Contaminants team at CSLAll the Environmental Contaminants team at CSL
Thank you for your attention!Thank you for your attention!