study of polymer - lipid partitioning for application in...
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IPSW Bordeaux 2013
Study of polymer - lipid partitioning for application in passive sampling
Foppe Smedes1,2, Tatsiana P. Rusina1 and Henry Beeltje3
1) Recetox, Masaryk University, Brno, Czech Republic2) Deltares, Utrecht, The Netherlands3) TNO, Utrecht, The Netherlands
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Overview
Why lipid sampler partitioning?
What is needed?
Applications
Conclusions
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Environmental compartments
Lipid
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passive sampling in water only can give an equilibrium lipid based concentration that biota would have if they were in equilibriumwith the sampled medium (water)
Can PS predict concentrations in biota?
PS
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What is needed
Sampler-lipid partition coefficients (KP,L or KL,P):• Differ for lipids?
• Differ for polymers?
• Lipid uptake at surface or diffused internal?
• Does absorbed lipid modify properties?
• Temperature effect
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KL,P - lipid sampler partition coefficient of PCBs
PLL,P CCK /
A. Jahnke et al Chemosphere 2008
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Experimental setup
Fig 1. Setup of partitioning experiments
Lipid
Sheet orderImmersedupper middle bottom = Altesil spiked with PRCsSS disc
Variablematerial
Glass jar upside down
Screw cap with SS liner
Polymers• LDPE
• Altesil Silicone rubber
• SSP Silicone rubber
Lipid types• Fish oil
• Triolein
Temperature 4 and 20°C
Exposure times 9 and 40 d
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Lipid uptake
Altesil = 6 mg/g
SSP = 4 mg/g
LDPE = 20 mg/g
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Diffusion of lipids in polymers
Diffusion of lipid in the polymer is slower than for PCB180 by :
0.8 log unit (factor6) for Altesil and SSP (logD= -11.4 m2/s)1.7 log unit (factor 50) for LDPE (logD=-15.25 m2/s
-16
-15
-14
-13
-12
-11
-10
-950 250 450 650 850
M (g mol -1)
log
D (m
2s
-1) Olive oil
Olive oil
Fish oil
Altesil
LDPE
-16
-15
-14
-13
-12
-11
-10
-950 250 450 650 850
M (g mol -1)
log
D (m
2s
-1) Olive oil
Olive oil
Fish oil
Altesil
LDPE
Rusina et al 2011
PCBs
PCBs
PAHs
PAHs
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Lipid in the sampler does not affect KP,L
She
et o
rder
Imm
erse
dup
per
mid
dle
botto
m =
Alte
sil
SS d
isc
SSP PDMSFish oil9 daysat 4OC
Biphenyl d10 (PRC)
Pentachlorobenzene
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0
1
2
3
4
5
6
7
8
Lipid concentration (mg/g)
Pentachlorobenzene
Biphenyl-d10 (PRC)
imm
ersed in lipid
diff 2
facing lipid
diffuision 1
Dosing sheet for PR
Cs
Lipid phase
KP,
L
Lipid content in mg/g
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Lipid profiles by reversedphase HPLC and ELSD(evaporative light scattering detector)
Fish oilTriolein as ISTriolein as IS
Olive oil
C23 as IS
Triolein
8 9 10 11 12 13 14 15 16 17 18
C23 as IS
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Comparing KP,L between lipids KP,L values differ little between lipid types [1,2,3]
[1] Jahnke et al Chemosphere 2008[2] Giesler et al EST 2012[3] Smedes et al 2013 (in prep)
0.20
y = 1.14x - 0.0022R2 = 0.97
0.000.020.040.060.080.100.120.140.160.180.20
0.00 0.05 0.10 0.15
Altesil silicone rubber
K P,L
trio
lein
y = 0.91x + 0.0052R2 = 0.95
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.00 0.05 0.10 0.15 0.20
SSP silicone rubber
KP,L fish oil
y = 1.03x - 0.0049R2 = 0.97
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.00 0.20 0.40 0.60
LDPE
OCPsPRCsPAHs
PCBs
PCBs, OCPs KPL (LDPE)> KP,L (SSP) factor 0.7-5
PAHs KP,L (LDPE)> KP,L (SSP) factor 2-50
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Comparing KP,L for 4 and 20°C
No measurable temperature effect on KP,L
y = 0.95x + 0.0107R2 = 0.94
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.10 0.20 0.30 0.40 0.50 0.60
LDPE
KP,Lfish oil 4°C
y = 1.01x - 0.0018R2 = 0.97
0.000.020.040.060.080.100.120.140.160.180.20
0.05 0.10 0.15 0.20
K P,L
fish
oil 2
0°C
Altesil Silicone rubber
y = 1.05x + 0.0015R2 = 0.97
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.05 0.10 0.15
SSP Silicone rubber
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Applications
• Estimation of SPMD-water partition coefficients
• Lipid-water partition coefficients
• A-biotic (equilibrium) lipid based concentrations compared with
monitoring of biota
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Calculated LogKSPMD-W (L/L) values versus LogKOW
y = 1.2112x ‐ 0.9228R2 = 0.9535
3
4
5
6
7
8
3 4 5 6 7 8LogKow
Log(K S
PMD‐W
L/L)
PAH PRC
PCB HCB
2006Huckins
KSPMD-W=KLDPE-W (mLDPE+mLIP / KLDPE-LIP) x ρSMPD / mSPMD
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logKAL,W
Lipid-water partition coefficients (A-biotic)
logKALT,W logKL,ALTAltesil SRLDPE
0 1 2 3 4 5 6 7 8 9
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Anthracene
Phenanthrene
Pyrene
Fluoranthene
Chrysene
Benz[a]anthracene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Benzo[a]pyrene
Benzo[ghi]perylene
Indeno[1,2,3-cd]pyrene
Dibenz[a,h]anthracene
logKLDPE,W logKL,LDPE
KAL,W=KP,W*KL,P
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A-biotic obtained logKAL,W versus logKOW
naftaleenacenafteenacenaftyleenfluoreenantraceenfenantreen
pyreen
fluoranteenchryseen
benzo(b)fluoranteenbenzo(k)fluoranteenbenzo(a)antraceenbenzo(a)pyreen
benzo(ghi)peryleenindeno(123‐cd)pyreendibenzo(ah)antraceen
y = 1.18x ‐ 0.19R² = 0.97
3
4
5
6
7
8
3 4 5 6 7 8LogKow
PAH PRC
PCB OCP
A-b
iotic
lipi
d-w
ater
par
titio
n co
effic
ient
s
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Measured CLip mussel versus A-Biotic- lipid based concentrations averagedfor all stations and years
PCB153, All years and all stations
1 to 1
y = 0.1366xR2 = 0.2179
0
200
400
600
800
1000
1200
0 2000 4000 6000 8000 10000A‐Biotic lipid based µg/kg
C‐mussel lipid based
µg/kg
AutumnWinter
Pyrene, All years and all stations
y = 0.3384xR2 = 0.8695
0
500
1000
1500
2000
2500
0 1000 2000 3000 4000 5000 6000 7000A‐Biotic lipid based µg/kg
C‐mussel lipid based
µg/kg
Error bars represent the standard deviation over 10 years time
10 year sampling of passive samplers parallel with“cogenetic” deployed mussels
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Ratio of measured CLip in mussels and CAL from PS
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Phe
n
Pyr Flu
Chr
y
BaA BbF BkF
BaP
Bgh
iPe
DB
ahA
InP 28 31 44 49 52 101
105
118
138
153
170
180
187
WinterAutumn
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Ratio of measured CLip and CAL from PS for Eel and Roach
Eel and Roach at 3 freshwater stations
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
HCB 28 52 101 118 153 180
EelRoach
Passive samplers in the vicinity where eeland roach were sampled
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How to obtain the A-biotic lipid based concentration
Passive sampling results• Equilibrium > KP,L - sampler lipid partition coefficient
> Nt amount in sampler after exposure> m mass of samplert
ALP,L
= NCm K
• Linear uptake phase > RS - sampling rate
> t exposure time> KP,W
- sampler water partition coefficient
LP,
P,W
SAL K
KtR
NC t
CP (equilibrium)
CW (free)
ALP,L S
P,W
1
1 exp
tNCm K R t
K m
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Lipid based conc. biota much lower than A-biotic?
No equilibrium?Not all “measured lipid” is adipose lipid (triglycerides)Lipid in biota not pure – differently distributed in tissue
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Conclusions
A-biotic lipid based concentrations can be estimated• KP,L can be measured accurately• Non equilibrium RS and KP,W needed
But CAL not equal to CLip in biota• Lipid present in different configuration?• Metabolism?
No sign of biomagnification
Does it make sense to monitor A-biotic lipid based conc??
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Several ways to lipid based concentrationsClassical
biomonitoring
Select length, age, sex
Homogenise
Analysis
Express conc.on lipid basis
CB / flip
Fishing
1
Bio
tic M
etho
ds
A-b
iotic
Met
hods
Transfer to model lipid basis
eqCP / KP,L
Concentration in the sampler
4
Sample inside the organism
Transfer to model lipid eqCP
/ KP,Ll
Analysis
Equilibrate sampler
with fish tissuePict: U.Berger,Janhke 2009
2
Analysis
Passive sampling in water
Free dissolved conc.in the water phase
Transfer to lipid basis CW х BCF
3
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Availability? Not always GoodAnimal welfare? Not really YesStationary? No guarantees YesImmortal? No YesEqual for species, age, sex, size?
No (No)b Yes
Independent of stress? No YesProxy for exposure?
(chemical activity)More or
less,Yes (Yes) Yes
Includes compounds that metabolize?
No No Yes
Quality standards available?
Yes Yes (biota?) Yes (biota?)
Transfer to model lipid basis
eqCP / Ksr,lip
4
Transfer to model lipid basis
eqCP / Ksr,lip
4
Transfer to model lipid basis
eqCP / Ksr,lil
2
Transfer to model lipid basis
eqCP / Ksr,lil
2
Express conc.on lipid basis
CB / flip
1
Express conc.on lipid basis
CB / flip
1
Transfer to lipid basis
CW х BCF or Cw õ BAF
3
Transfer to lipid basis
CW х BCF or Cw õ BAF
3
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YES, there is a future for a parameter like an A-Biotic exposure level
Required parameters are stable Worldwide comparable Different waters
Fresh and saline water, toxic, anoxic, porewater Relevant for uptake exposure for organisms Exposure is also reflected when metabolization occurs
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Thank you for your attention
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