IPSW – International Passive Sampling Workshop - Development of adapted versions of ... · 2014-07-18 · Development of adapted versions of Polar Organic Chemical Integrative Samplers

Development of adapted versions of Polar Organic Chemical Integrative

Samplers (POCIS) for alkylphenols and their derivatives

C. Soulier1, N. Abou Mrad1, A. Belles1, V. Loustalot2, K. Cailleaud2, H. Budzinski1

1 Univ. Bordeaux, EPOC‐LPTC, UMR 5805, 351 Cours de la Libération, F‐33400 Talence (France)2 TOTAL, Pôle d’étude et de Recherche de Lacq (PERL), BP47, 64170 Lacq (France)

6th International Passive Sampling Workshop and Symposium, Bordeaux, 26‐29 June 2013

Interest of passive sampling


Time

Con

cent

ratio

n

Spot sampling is a snapshot of contamination at the time of sampling

Real concentration

• Spatial and temporal variability

• Low concentration

• Complex mixture

• Matrice effects

Interest of passive sampling


Time

Con

cent

ratio

n

Real concentration

Passive sampling allow accessing to Time Weighted Average (TWA) concentration on sampling period

• Integrative tools

• Simplification of sampling

• Preconcentrator tools (allow detecting water concentration above LOD)

Theory of passive sampling


TempsTemps

Concentration factor

Time

Kinetic phase Equilibrium phase

Linear phase

Cs: concentration in sorbent(ng/g)Cw: concentration in water (ng/L)ku: uptake rate constant (L/g/d)ke: elimination rate constant( d‐1)

The accumulation of compounds follows a first order kinetic

The water concentration is assessed from the sorbent concentration

Curvilinear phase

Theory of passive sampling


TempsTempsTime

Kinetic regime Equilibrium Regime

Linear regime

Cs: concentration in sorbent(ng/g)Cw: concentration in water (ng/L)ku: uptake rate constant (L/g/d)

Determined by laboratory calibrations

To plot concentration factor (Cf) in function of time, Uptake rate constant were determined by linear regression

Accumulated quantity increases linearly with the time

Concentration factor

ku

Range of application of principal passive samplers


SPMD

POCIS

CHEMCATCHER

MESCO

PDB

Céramic Dosimeter

Apolar compounds

Polar compounds

Polyether Sulfone 0.1 µm membrane

HLB® sorbent

Stainlesssteel ring

Pharmaceutical configuration of POCIS

Stainless steel ring

Polyether Sulfone 0.1 µm membrane

Easy, sensitive and modular tool

EE2: 4.12Gemfibrozil: 4.77Amitriptyline: 4.92

APs

APs, class of interest: regulatory

perspectives Environmentaly

Alkylphénols (APs)


• Listed on Water Framework Directive• The 4‐NP is a mixture of isomers:

Branched alkyl group 3 to 6% in ortho position, 90 to 93% in para

• The 4‐t‐OP isomer is the most widely used• Formed by biodegradation of APEOs• Used in industries such as additives or antioxydants in the production of plastic

(80% 4‐NP and 20% 4‐t‐OP)

4‐nonylphenol(4‐NP)CAS: 84852‐15‐3Log KOW:5.99a

4‐t‐octylphenol (4‐t‐OP)CAS: 140‐66‐9Log KOW:5.50a

a: calculed by KOWWIN

Alkylphénols derivatives


Nonylphenol monoethoxylate (NP1EO)CAS: 26027‐38‐3Log KOW: 5.58a

Nonylphenol diethoxylate (NP2EO)CAS: 26027‐38‐2Log KOW: 5.30a

Nonylphenoxy acetic acid(NP1EC)CAS: 3115‐49‐9Log KOW: 5.80a

a: calculed by KOWWIN

• Anthropogenic origin• NPEOs are amphiphilic compounds and non ionic surfactants• NPEOs represent 80 to 85% of APEOs

Laboratory calibrations


Stock of contamination solutionPeristaltic pumpStock of water

Exposure tank

Stock of waste water

Determination of kinetic exchanges and parameters

Exposure under controlled conditions : Contamination with flow through

system (conc : 5‐ 10 g/L)Constant flowConstant temperature (20°C)

Analysis of water every two days (Cw)

Analysis of POCIS (Cs)

Kinetic accumulation in POCIS


Equation of model: Cf = 1.20 t (R² = 0.92)

ku = 1.20 L/g/dRs = 0.24 L/d

Equation of model: Cf = 1.33 t (R² = 0.89)

ku = 1.33 L/g/dRs = 0.27 L/d

First type of accumulation: Linear trends

0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)

NP1EC

Literature values:Rs = 0.12 L/d 1Rs = 0.06 L/d 2

1‐Arditsoglou. A., and D. Voutsa (2008). Environmental Pollution 156 (2): 316‐3242‐Harman. C., K.E. Tollefsen. O. Boyum. K. Thomas. and M. Grung. 2008. Chemosphere 72 (10): 1510‐1516



• Accumulation with lag effect*

• Integrated uptake is not achieved

• Sampling rates variable over exposure time

Cf = 0.33 e0.20t (R² = 0.94)

012345678

0 5 10 15

Cf(L/g)

Time (d)

4‐NP

02468

10121416

0 5 10 15

Cf(L/g)

Time (d)

NP1EO

Cf = 0.78 e0.18t (R² = 0.96)

0

2

4

6

8

10

12

0 5 10 15

Cf(L/g)

Time (d)

NP2EO

Cf = 0.39 e0.22t (R² = 0.98)

Second type of accumulation: exponential trends

*Time required for the compounds cross the water boundary layer and the membrane



Determination of pseudo kinetic parameters

012345678

0 5 10 15

Cf(L/g)

Time (d)

4‐NP

0

2

4

6

8

10

0 5 10 15

Cf(L/g)

Time (d)

4‐NP (extrapolation)

Int. de conf. (Moyenne 95%)

τ0

• Reasoning only on the linear part of exponential trend• Utake rate constant is determined by linear regression• They must be used carefully• The lag time is over 5 days.



Determination of pseudo kinetic parameters

012345678

0 5 10 15

Cf(L/g)

Time (d)

4‐NP

0

2

4

6

8

10

0 5 10 15

Cf(L/g)

Time (d)

4‐NP (extrapolation)

Int. de conf. (Moyenne 95%)

τ0

CompoundsEquation of

modelR² ku (L.g‐1.d‐1) Rs (L.d‐1) τ0 (d)

4‐NP Cf=‐4.94+0.79t 0.94 0.79 0.16 6.22NP1EO Cf=‐7.29+1.29t 0.95 1.29 0.25 5.62NP2EO Cf=‐8.19+1.27t 0.99 1.27 0.25 6.47



Partition between membrane and sorbent

0

5

10

15

20

25

30

35

0 5 10 15

Concen

tration (µg/g)

Time (d)

Phase Membrane

Accumulation of 4‐NP in sorbent and PES membrane

• Sorption in PES membrane during the earlier stage of exposure

• NP1EC and 4‐t‐OP: less than 20% at 5 days and less than 10% at 15 days

• 4‐NP, NP1EO et NP2EO: more than 60% at 5 days and at 50% at 15 days

• The sorbent accumulation start when PES membrane reach a steady state

• The uptake of 4‐NP, NP1EO and NP2EO is controlled by PES membranes

POCIS‐like. choice of membranes


Membrane

Porosity

(Designation)

Polarity Particularity

Nylon 0.1 µm

(POCIS‐Nylon 0.1 µm)Hydrophilic

Nylon 30 µm

(POCIS‐Nylon 30 µm)Hydrophilic

3 types of membrane were tested but only 2 shown conclusive results

• Nylon polymer have low absorbant power

• The third type of tested membrane is polyethylene

Millipore

Millipore


Kinetic accumulation in POCIS‐like

0

5

10

15

20

25

30

0 5 10 15

Cf (L/g)

Time (d)

NP1EC Nylon 0.1 Nylon 30

05

10152025303540

0 5 10 15

Cf (L/g)Time (d)

4‐t‐OP Nylon 0.1 Nylon 30

05

101520253035

0 5 10 15

Cf (L/g)

Time (d)

4‐NP Nylon 0.1 Nylon 30

0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)

NP1EO Nylon 0.1 Nylon 30

0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)




0

5

10

15

20

25

30

0 5 10 15

Cf (L/g)

Time (d)


05

10152025303540

0 5 10 15

Cf (L/g)Time (d)


05

101520253035

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)




0

5

10

15

20

25

30

0 5 10 15

Cf (L/g)

Time (d)


05

10152025303540

0 5 10 15

Cf (L/g)Time (d)


05

101520253035

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)




0

5

10

15

20

25

30

0 5 10 15

Cf (L/g)

Time (d)


05

10152025303540

0 5 10 15

Cf (L/g)Time (d)


05

101520253035

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


Any lag effect



0

5

10

15

20

25

30

0 5 10 15

Cf (L/g)

Time (d)


05

10152025303540

0 5 10 15

Cf (L/g)Time (d)


05

101520253035

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


0

5

10

15

20

25

0 5 10 15

Cf (L/g)

Time (d)


Lag effect is observed with POCIS‐ Nylon 0.1µm

Mesocosm validations


Parameters to know when they are exposed at low concentrations:

• Kinetic exchanges

• Integrative aspect

• TWA concentrations

Mesocosm validations

• Semi‐controlled conditions

• 4‐Nonylphenol, 4‐tert‐octylphenol, diuron• Analysis of water

• Replicates of POCIS and POCIS Nylon 0.1 and 30µm

3 experiments tested:

• Continuous exposure

• Accidental exposure

• Discontinuous exposure

2 concentrations tested:

• EQS level (300 ng/L for 4‐NP)

• 1/3 EQS level (100 ng/L for 4‐NP)

Sampling strategy


0

1

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

Qua

ntity

Time (days)

Continuous exposure

Injected quantity

Passive sampling

Grab sampling

Study the accumulation

Constant water concentrations

Determine kinetic parameters

Continuous exposure: accumulatedquantities


050

100150200250300350400450

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 0.1µm

0

1000

2000

3000

4000

5000

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 30µm

Lag effect

Equilibrium‐release

Linear trend

R² = 0.91ku= 0.14 L/j/g



050

100150200250300350400450

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 0.1µm

0

1000

2000

3000

4000

5000

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 30µm

R² = 0.91ku= 0.14 L/j/g

No lag effect

R² = 0.66ku= 0.61 L/j/g



050

100150200250300350400450

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 0.1µm

0

1000

2000

3000

4000

5000

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 30µm

R² = 0.91ku= 0.14 L/d/g

R² = 0.66ku= 0.61 L/d/g Determination of ku not possible

ku labo is employed (1.61 L/d/g)



0

100

200

300

400

500

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 0.1µm

0

1000

2000

3000

4000

5000

0 5 10 15 20 25

Conc (n

g/g)

Time (d)

POCIS Nylon 30µm

Accumulated quantityincreases in the followingorder:

POCIS > POCIS‐Nylon 0.1µm > POCIS‐Nylon 30µm

Sampling strategy


0

4

0 5 10 15 20 25

Qua

ntity

Time (days)

Accidental exposure

Injected quantity

Passive sampling

Grab sampling

0

1

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

Qua

ntity

Time (days)

Continuous exposure

Assess integrative aspect

Peak of contamination

Estimate TWA concentrations

Accidental exposure: accumulatedquantities


0

1

2

3

0

200

400

600

800

1000

1200

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Time (d)

POCIS4‐NP

Thoeretical Injection

0

1

2

3

0

5000

10000

15000

20000

25000

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Temps (j)

POCIS Nylon 30µm4‐NPThoeretical Injection



0

1

2

3

0

200

400

600

800

1000

1200

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Time (d)

POCIS4‐NP


0

1

2

3

0

5000

10000

15000

20000

25000

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Temps (j)




0

1

2

3

0

200

400

600

800

1000

1200

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Time (d)

POCIS4‐NP


0

1

2

3

0

5000

10000

15000

20000

25000

0 5 10 15 20 25

Concen

tration (µg/L)

Conc (n

g/g)

Temps (j)


Estimated concentration‐accidental exposure


0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS

Injected water concentration

Water concentrations snapshot by spot sampling



0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS


Integrated average dissolved concentration

Average of water concentration at eachinjection and no‐injection periodsobtained by spot sampling



0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS

Mesured conc (ku NQE continuous)





0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS Nylon 0.1µm

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS






0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS Nylon 0.1µm

0

500

1000

1500

2000

2500

0 5 10 15 20 25Co

nc (n

g/L)

Time (d)

4‐NP‐ POCIS Nylon 30µm

0

500

1000

1500

2000

2500

0 5 10 15 20 25

Conc (n

g/L)

Time (d)

4‐NP‐ POCIS




Comparison of accumulated quantities between experiments


0

20

40

60

80

100

120

0 5 10 15 20 25

Qua

ntity

(ng)

Time (d)

4‐NP‐ POCISContinuous

Accidental

01002003004005006007008009001000

0 5 10 15 20 25

Qua

ntity

(ng)

Time (d)

4‐NP‐ POCIS Nylon 0.1µmContinuous

Accidental

0

500

1000

1500

2000

2500

3000

3500

4000

0 5 10 15 20 25

Qua

ntity

(ng)

Time (d)

4‐NP‐ POCIS Nylon 30µmContinuous

Accidental

POCIS and POCIS‐Nylon 0.1µm have an integrative behaviour for 4‐NP


Conclusion

POCIS have the ability to sample APs and their derivatives

PES membranes prevent to have an use in quantitative tool

Nylon membranes allows eliminating the lag phase observed with POCIS

These tools seem to integrate an accidental contamination

TWA concentrations obtained using these tools are reliable (good agreement with order of magnitude)


Perspectives

More investigation on POCIS‐Nylon 30µm

Check sampled fraction by POCIS Nylon 30µm

Apply PRC approach for APs

Field application of these tools

Aknowledgements


ANR PRECODD EMESTOX

Aquitaine Region

European Community

And you for your attention

Documents

IPSW – International Passive Sampling Workshop - Development of adapted versions of ... · 2014-07-18 · Development of adapted versions of Polar Organic Chemical Integrative Samplers