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