11

Recent results for the Norwegian Research Council funded project ‘PASSIMPACT’ (Use of Passive Sampling Devices in Monitoring of Potential Impact of Offshore Discharges and Accidental Oil Spills)

A holistic passive sampling calibration for alkylated phenols

Chris Harman Olav Bøyum, Knut-Erik Tollefsen, Kevin Thomas and Merete Grung

NIVA, Norwegian Institute for Water Research, Oslo Centre for Interdisciplinary Environmental and Social research (CIENS), Gaustadalléen 21, 0349 OSLO, Norway

22

Norwegian BasinNorwegian Basin(The Norwegian Petroleum Directorate, 2005)

33

Background Background

• Endocrine disrupting effects of octylphenol (OP), nonylphenol (NP) Endocrine disrupting effects of octylphenol (OP), nonylphenol (NP) and some nonylphenol ethoxylates (Aand some nonylphenol ethoxylates (A99PEO)PEO)

• Domestic and industrial cleaning agents but also wide ranging Domestic and industrial cleaning agents but also wide ranging industrial applicationsindustrial applications

• European production of NP is around 4.5 x 10European production of NP is around 4.5 x 1044 tons y tons y-1-1

• Mainly discharged though wastewater treatment plantsMainly discharged though wastewater treatment plants

• Use of APEO in production chemicals offshore phased out in the Use of APEO in production chemicals offshore phased out in the Norwegian sector of the North SeaNorwegian sector of the North Sea

• However AP are naturally occurring in crude oilsHowever AP are naturally occurring in crude oils• Readily found in operational discharges e.g. produced waterReadily found in operational discharges e.g. produced water• Discharge of PW predicted to peak at 2.5 x 108 m3 Discharge of PW predicted to peak at 2.5 x 108 m3 • Low mg LLow mg L-1-1 levels in produced waters, decreasing concentration with levels in produced waters, decreasing concentration with

increasing chain lengthincreasing chain length

44

Alkylphenols – Alkylphenols – documented effects in fishdocumented effects in fish

• Acutely toxicAcutely toxic

• Endocrine disruptorsEndocrine disruptors

• Bind to estrogen receptorsBind to estrogen receptors

• Estrogenic in malesEstrogenic in males

• Interfere with steroid Interfere with steroid production/metabolismproduction/metabolism

• Interfere with steroid Interfere with steroid transporttransport

• Inhibits gonad Inhibits gonad developmentdevelopment

• Cause intersexCause intersex

• Ecological effects uncertainEcological effects uncertain

0

20

40

60

80

100

0

20

40

60

80

100V

tg i

nd

uct

ion

(%

)

Viab

ility (%)

HO

4-t-C4

*

*

0

20

40

60

80

100

0

20

40

60

80

100

HO

2,4-dt-C4

*

Vtg

in

du

ctio

n (

%)

Viab

ility (%)

10 -7 10 -6 10 -5 10 -4 10 -30

20

40

60

80

100

0

20

40

60

80

100

Concentration (mol/L)

Vtg

in

du

ctio

n (

%)

Viab

ility (%)

HO

2,4,6-tt-C4

Tollefsen et al. Submitted to Ecotoxicol. Environ. Saf.

55

Variation in PWVariation in PW

Control

Statfj

ord C

Grane

A

Gullfak

s B

Statfj

ord A

Troll

B

Snorre A

Oseber

g C

Heidru

n

Åsgår

d B

0

2.0×10-9

4.0×10-9

6.0×10-9

8.0×10-9

1.0×10-8

1.2×10-8CYP1A induction

Platform

TC

DD

-EQ

(g T

CD

D/L

PW

)

Control

Snorre A

Statfj

ord C

Statfj

ord A

Heidru

n

Oseber

g C

Åsgår

d B

Gullfak

s B

Grane

A

Troll

B

1.0×10-08

2.0×10-08

3.0×10-08

4.0×10-08

5.0×10-08Estrogenicity

Platform

E2-

EQ

(g E

2/L

PW

)

66

AP calibration as part of PASSIMPACT AP calibration as part of PASSIMPACT

• WP1 : Uptake studies of passive samplers and WP1 : Uptake studies of passive samplers and monitoring organismsmonitoring organisms

• Suite of laboratory exposures using a range of passive Suite of laboratory exposures using a range of passive sampling techniques. Establishment of relevant kinetic sampling techniques. Establishment of relevant kinetic factors under different, controlled conditions, including factors under different, controlled conditions, including membrane fouling.membrane fouling.

• WP2 : WAF experiments WP2 : WAF experiments

• Same exposure systems as WP1, but using the water Same exposure systems as WP1, but using the water accommadated fraction (WAF) of a crude oil with a high accommadated fraction (WAF) of a crude oil with a high content of unresolved complex mixture (UCM). content of unresolved complex mixture (UCM).

• WP3 : Field trialWP3 : Field trial

• Field verification of calibration results by passive Field verification of calibration results by passive sampling the receiving waters of a Norwegian production sampling the receiving waters of a Norwegian production platform.platform.

• WP4 : Data and concept evaluationWP4 : Data and concept evaluation

• Evaluation of the data from the first 3 work packages Evaluation of the data from the first 3 work packages against existing risk assessment models such as against existing risk assessment models such as DREAM.DREAM.

77

Exposure set upExposure set up

• Simple flow through systemSimple flow through system• Both hydrophobic (SPMD) and Both hydrophobic (SPMD) and

hydrophilic (POCIS-Pharms) hydrophilic (POCIS-Pharms) sampling devices exposed to a mix sampling devices exposed to a mix of hydrocarbons commonly found in of hydrocarbons commonly found in PW e.g.PW e.g.

• PAHsPAHs• 30 APs30 APs• CarbazolesCarbazoles

• 100 ng/L for 4 weeks, samplers 100 ng/L for 4 weeks, samplers removed every weekremoved every week

• Biofouling more extensive than Biofouling more extensive than expectedexpected

• losses to biodegradation/ sorptionlosses to biodegradation/ sorption

88

Calibration – analysis and data treatmentCalibration – analysis and data treatment

• Analysis by (underivitised) GC-MSAnalysis by (underivitised) GC-MS• Avoids splitting samplesAvoids splitting samples

• Results corrected for blanks and procedural recoveryResults corrected for blanks and procedural recovery• Quantification by the use of surrogate ISTDQuantification by the use of surrogate ISTD• Curves fitted directly to the data using the overall uptake equationCurves fitted directly to the data using the overall uptake equation

• RRss (L d (L d-1-1) values estimated from the initial linear part of these uptake ) values estimated from the initial linear part of these uptake

curvescurves

oror

tkKCC eSPMDWSPMD exp1

tkKCC eSPMDWSPMD SPMDSWSPMD /VtRCC

99

Results – SPMDs group 1Results – SPMDs group 1

• C0-C2C0-C2• Phenol, o/m/p cresol, Phenol, o/m/p cresol,

2,4/2,5/3,5-dimethyl and 4-2,4/2,5/3,5-dimethyl and 4-ethylethyl

• Log Log KKow ow 1.5-2,61.5-2,6

• At Log At Log KKow ow < ~3< ~3 there is no there is no

quantifiable uptake by quantifiable uptake by SPMDs (as expected)SPMDs (as expected)

• Blank problems and analytical Blank problems and analytical difficulties for some difficulties for some compounds.compounds.

OH

OH

CH3

OHCH3OH

CH3

OH

CH3

CH3

OH

CH3

CH3

OHCH3

CH3

OH

CH3

1010

Results – SPMDs group 2Results – SPMDs group 24-n-Propylphenol

0 7 14 21 280

5

10

15

20

25

Days

ng

/SP

MD

• C3-C4C3-C4

• Log Log KKow ow ~ 3-3.5~ 3-3.5

• Equilibrium attained early Equilibrium attained early tt1/21/2

within a few days – one within a few days – one weekweek

• Time integrative period Time integrative period therefore shorttherefore short

• RRss 20-70mL d 20-70mL d-1-1

• Compounds not well suited Compounds not well suited to sampling with SPMDs?to sampling with SPMDs?

2,4,6-Trimethylphenol

0 7 14 21 2805

101520253035404550556065

Days

ng

/SP

MD

CH3

OH

OH

CH3

CH3 CH3

1111

Results – SPMDs group 3Results – SPMDs group 32,6-Diisopropylphenol

0 7 14 21 280

100

200

300

400

Days

ng

/SP

MD

• C5-C7C5-C7• Log Log KKow ow ~ 3.5-5.0~ 3.5-5.0• Curvlinear - approaching Curvlinear - approaching

equilibrium equilibrium • RRss 100-1000 mL d 100-1000 mL d-1-1 • Typically several hundred Typically several hundred

ng/SPMD after 4 weeksng/SPMD after 4 weeks• Suited to sampling with Suited to sampling with

SPMDsSPMDs• Straight chained APs not Straight chained APs not

includedincluded

2-tert-Butyl-4-methylphenol

0 7 14 21 280

50

100

150

200

Days

ng

/SP

MD

OH

CH3CH3

CH3

CH3

OH

CH3 CH3

CH3

CH3

1212

Results – SPMDs Group 4Results – SPMDs Group 4

2-Methyl-4-tert-octylphenol

0 7 14 21 280

1000

2000

3000

4000

Days

ng

/SP

MD

• C8-C9C8-C9• Log Log KKow ow ~ >5.0~ >5.0• Curvlinear stage but Curvlinear stage but

equilibrium not approachedequilibrium not approached• Time integrative period Time integrative period

longerlonger• RRss 0.5-6 L d 0.5-6 L d-1-1 • Highly suited to sampling Highly suited to sampling

with SPMDswith SPMDs• 4-n-Octyl/Nonyl not included4-n-Octyl/Nonyl not included

OH

CH3

CH3CH3

CH3 CH3

CH3

1313

Results – SPMDs ’group 5’ Results – SPMDs ’group 5’ (straight chained alkylphenols)(straight chained alkylphenols)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

0 7 14 21 28

Days

ng

/SP

MD

4-n-Heptylphenol

4-n-Octylphenol

4-n-Nonylphenol

1414

Group 5Group 5

• Fitting uptake equation to 0-14 day data, overestimated sampling rates.

• Rs estimated from linear 0-7 days curve.

• Pentylphenol – group 2, Heptyl/ Octyl/ Nonyl – group 4

• Increasing relative degradation/ sorption with increasing chain length

4-n-Pentylphenol

0 7 14 21 280

5

10

15

20

25

30

35

40

45

Days

ng

/SP

MD

4-n-Heptylphenol

0 7 14 21 280

500

1000

1500

Daysn

g/S

PM

D

4-n-Octylphenol

0 7 14 21 280

500

1000

1500

2000

2500

3000

3500

Days

ng

/SP

MD

4-n-Nonylphenol

0 7 14 21 280

1000

2000

3000

4000

5000

Days

ng

/SP

MD

CH3

OH

OH

CH3

CH3

OH

CH3

OH

1515

Sampling rates as a function of log Sampling rates as a function of log KKowow

R2 = 0,7812

0,01

0,10

1,00

10,00

0,00 2,00 4,00 6,00 8,00

Log Kow

Sam

pli

ng

rat

e L

d-1

1616

Dissipation of Performance Reference Compounds Dissipation of Performance Reference Compounds (PRCs)(PRCs)

Release of Chrysene D12 Phenanthrene D10 Flourene D10 and Acenaphthene D10

• All SPMDs spiked with PRCs

• Dissipation modelled by

• Allows adjustment of laboratory and field data by, for example

)exp( e0SPMD tkCC

CALe

PRCeCALsfields

k

kRR

0 7 14 21 280

20

40

60

80

100

Days

Re

ten

tion

%

1717

2,3,5-trimethylphenol

7 14 21 28-100

0

100

200

300

400

500

600

Days

ng

/PO

CIS

4-Isopropyl-3-methylphenol

7 14 21 28-100

0

100

200

300

400

500

600

700

Days

ng

/PO

CIS

2,6-Diiosopropylphenol

7 14 21 28

-1000

0

1000

2000

3000

Days

ng

/PO

CIS

4-tert-Butyl-2-methylphenol

7 14 21 28

-500

0

500

1000

1500

Days

ng

/PO

CIS

POCIS results - examplesPOCIS results - examples

OH

CH3

CH3CH3

CH3OH

CH3CH3

CH3

CH3

OHCH3

CH3

CH3

OH

CH3

CH3

CH3

R2 0.99

R2 0.97

R2 0.99

R2 0.99

1818

Results POCISResults POCIS

  RSQ Intercept Rs L d-1

2,4-Dimethylphenol 0,90 39,42 0,16

2,5-dimethylphenol 0,93 19,52 0,10

4-ethylphenol 0,95 18,87 0,11

3,5-Dimethylphenol 0,94 6,63 0,07

2,4,6-Trimethylphenol 0,99 5,05 0,55

2-n-Propylphenol 0,94 3,61 0,18

4-n-Propylphenol 0,96 -6,10 0,09

2,3,5-trimethylphenol 1,00 -0,54 0,20

4-tert-Butylphenol 1,00 -9,10 0,26

4-isopropyl-3-methylphenol 1,00 -11,74 0,22

2-Tert-butyl-4-methylphenol 0,98 -126,65 0,61

4-n-butylphenol 0,93 -23,95 0,05

4-Tert-butyl-2-methylphenol 0,99 -82,68 0,41

2,6-Diiospropylphenol 0,97 -232,44 0,67

6-tertbutyl,2,4dimethylphenol 0,96 -477,59 1,37*

2-Tert-butyl-4-ethylphenol 0,97 -141,73 0,42

2,5-diisopropylphenol 0,95 -36,15 0,16

• Curves fitted by using the linear equation and Rs calculated from the slope

• C0-C1 unfortunately (highest concentration in PW) not quantifiable

• C2-C6 (Log Kow ~ 2-4) sampling rates typically 100-600 mL d-1

• >C6 no quantitative uptake in POCIS

• Intercept - hydrophobicity

• Higher blank values than SPMDs for some compounds (sampling rate for 2,6-Di-tert-butylphenol 34 L d-1!)

*Poor standard response

1919

0 1 2 3 4 5 6 70.01

0.1

1

10SPMD

POCIS

Log Kow

Rs

(L d

-1)

All sampling rates and AP hydrophobicityAll sampling rates and AP hydrophobicity

2020

AP calibration – summary and conclusionsAP calibration – summary and conclusions

• Useful sampling rates for compounds with log kow 2.5-6.0 (C2-C9)Useful sampling rates for compounds with log kow 2.5-6.0 (C2-C9)• Ranging from 0.1-6L dRanging from 0.1-6L d-1-1

• Both POCIS and SPMDs are required to cover the full range of APsBoth POCIS and SPMDs are required to cover the full range of APs• Further modelling will describe the relationship between Further modelling will describe the relationship between

physicochemical properties and uptakephysicochemical properties and uptake• Uptake by SPMDs can be estimated for other APsUptake by SPMDs can be estimated for other APs• More difficult for POCIS as interactions with the sorbent are More difficult for POCIS as interactions with the sorbent are

variedvaried• Also comparison of different PRC correction methodsAlso comparison of different PRC correction methods• Ongoing work will examine the effects of fouling on the uptakeOngoing work will examine the effects of fouling on the uptake• Experiment has been repeated under different conditions – Experiment has been repeated under different conditions –

confirmation of modellingconfirmation of modelling• Allows calculation of time integrated water concentrations for 25 Allows calculation of time integrated water concentrations for 25

alkylphenolsalkylphenols

2121

Acknowledgments Acknowledgments

• FundingFunding• The Norwegian Research Council (NFR)The Norwegian Research Council (NFR)

• Technical assistanceTechnical assistance• Olav Bøyum, NIVAOlav Bøyum, NIVA• Marine research Station – Solbergstrand, NorwayMarine research Station – Solbergstrand, Norway

• Support with PSDsSupport with PSDs• CERC, USGS – Dave Alvarez and Jim HuckinsCERC, USGS – Dave Alvarez and Jim Huckins• University of Portsmouth, UK – Graham MillsUniversity of Portsmouth, UK – Graham Mills