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IDENTIFICATION OF ANALYTE SELECTIVE PASSIVE SAMPLING

PHASES USING HANSENSOLUBILITY PARAMETERSMONDAY, JULY 01, 2013

CONTENTS

• Introduction• Hansen Solubility Parameters (HSP)• Literature data• In laboratory experimentation• Field deployment• Future work

INTRODUCTION

• Can an equilibrium passive sampling device be selected that is optimised for a large chemical space, to allow environmental monitoring of a wide range of HPC ingredients?

HISTORICAL APPROACHES

• Most passive samplers are suited either for:-

• Non polar chemicals e.g. PCBs, PAHs .... Traditionally using PDMS/LDPE or SPMD samplers etc.

• Polar chemicals e.g. Pharmaceuticals, polar pesticides Utilising POCIS and recently DGT

CHEMICAL SPACE

CAN A POLYMERIC PHASE BE SELECTED TO COVER A WIDER AREA THAN ANY ONE EXISTING

PASSIVE SAMPLERS?

PROPOSAL

• Using thermodynamics principles to optimise polymeric selection within a chemical space.• In this work we utilise the thermodynamic properties of solubility. • This work uses Hansen solubility parameters (HSP) to assess solubility.

HANSEN SOLUBILITY PARAMETERS

• Provides an indication of dissolution i.e. like dissolves like

• Based on similarity of intermolecular interactions• Hildebrand solubility parameter » The energy from dispersion bonds between molecules. δd

» The energy from dipolar intermolecular forces between molecules. δp

» The energy from hydrogen bonds between molecules. δh

2222HPDhild

ASSUMPTIONS/CHALLENGES

• Thermodynamic equilibrium• HSP is a thermodynamic concept and does not take in to account kinetics.• The 3 parameters adequately define a chemical» The H term includes both Hydrogen donor and acceptor» Abraham solvation may describe better

• Use as a screening tool to assess interaction with a range of chemicals.

COMPARING CHEMICAL’S HSP

• Distance between molecules calculated

• Compared to a radius of interaction (R0) to give relative energy difference (RED)

• If RED< 1 then the two should “mix”

0RR

RED a

HSP SOFTWARE

USING HSP ON LITERATURE DATA

• A literature search of chemicals sampled by commercially available passive samplers was carried out.• The HSP of these chemicals were looked up in the database or predicted from their chemical structure if not present.• Plots of chemicals sampled by the different passive samplers were produced.

CHEMCATCHER

DISCUSSION ON THE LITERATURE DATA

• POCIS and Chemcatcher™ data only shows the materials that were sampled and does not give any information on what was not sampled.• Therefore no data is available on the limitations of these phases making it impossible to define the sphere of interaction, without further data.

POLYMERS SELECTED FOR SCREENING

POLYMER ABREVIATION

Cellulose acetate butyrate CAB

Polyamide nylon 6,6 PA

Polycarbonate PC

polyvinylchloride-unplasticised PVC

polyethylene terephthalate PET

polyethylene-low density LDPE

polytetrafluoroethylene PTFE

polyimide PI

polyoxymethylene-copolymer POM

polypropylene PP

polystyrene-conductive PS

polydimethyl siloxane PDMS

POLYMERS HSP

Cellulose acetate butyrate (12.6)

Polyamide (8)

polycarbonate (8)

polyvinylchloride-unplasticised (8)

polyethylene terephthalate (8)

polyethylene-low density (8)

polytetrafluoroethylene (3.9)

polyimide (21.6)

polyoxymethylene (5.3)

PDMS (5.7)

polypropylene (8)

polystyrene-conductive (10)

0.750.50.250

Dispersive

LABORATORY TEST FOR UPTAKE ONTO POLYMERS

Polymer cut to 10x10x1

mm

Solvent washed in

EtAc , MeOH &

water

Place polymers in

a 5mg/L mixed

solution in 70:30

MeOH:H2O

Shaken for 1 week at 250 rpm and 20oC

Remove polymer

rinse with MilliQ water and extract for 1 week in MeoH

Analyse polymer

extract and loading

solution by GC/MS &

LC-ToF/MS

HSP OF TEST COMPOUNDS

L3 D6 4-C12 LAB 4-C13 LAB D4 D55-C13 LAB Cetrimonium chloride L4 3-C13 LAB 4-C11 LAB 3-C11 LAB4-C10 LAB 3-C12 LAB 7/6 C13 LAB 2-C13 LAB 5-C11 LAB 6-C12 LAB5-C12 LAB 2-C12 LAB 2-C11 LAB 5-C10 LAB 2-C10 LAB 6-C11 LAB3-C10 LAB Benzalkonium chloride DPHHC 2-FBP Phenyl butazone TPAEHMC Octocrylene APE E-methoxy crylene Z-methoxy crylene 4-octylphenolParsol Climbazole Carbazole Mefenamic acid Dodecanol C25H48NO4C25H50NO4 C25H52NO4 C24H50NO4 Proxan Troysan C23H46NO4C23H48NO4 C22H46NO4 UV-4 C21H42NO4 C21H44NO4 Sodium Lauryl SulfateTcS Cinnamic alcohol MIT TCC UV-5 caffeine Brilliant Blue Acetanilide UV-3 UV-2 UV-1

Dispersive

0 0.25 0.5 0.75 1

Polar UV-filter

ColourantNon-Polar UV-

Filters

LAB and VMS

Ester quats

WHAT PROPERTIES ARE DESIRABLE

• A large radius of interaction.» Sample both polar and non-polar.

• Sensible time to equilibrium.» In the field reaches equilibrium in ~2-4 weeks

• Commercially available in a range of film thicknesses at a reasonable cost.

y = ‐0.2006x + 4.7427R² = 0.858

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0.00 5.00 10.00 15.00 20.00 25.00

Log10 concen

tration (ug/L)

HSP distance (MPa1/2)

PDMS CORRELATION PLOT

Density: 1.14 g cm-3

PDMS CORRELATION PLOT

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0.0 5.0 10.0 15.0 20.0 25.0

Log1

0 co

ncen

tratio

n (u

g/L)

HSP Distance (MPa1/2)

L3D64-C12 LAB4-C13 LABD4D55-C13 LABL43-C13 LAB4-C11 LAB3-C11 LAB4-C10 LAB3-C12 LAB7/6 C13 LAB2-C13 LAB5-C11 LAB6-C12 LAB5-C12 LAB2-C12 LAB2-C11 LAB5-C10 LAB2-C10 LAB6-C11 LAB3-C10 LABDPHHC2-FBPTPAEHMCOctocryleneAPEE-methoxy cryleneZ-methoxy cryleneParsolclimbazole?CarbazoleMEFENAMIC ACIDDodecanolC25H48NO4C25H50NO4C25H52NO4C24H50NO4TroysanC23H46NO4C23H48NO4C22H46NO4UV-4C21H42NO4C21H44NO4TCSC19H40NO4UV-5Acetanilide


PDMS CORRELATION PLOTDensity: 1.14 g cm-3

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0.00 5.00 10.00 15.00 20.00 25.00

Log10 c

oncentratio

n (ug/L)


P+H 0‐5

P+H 5‐10

P+H 10‐15

P+H 15‐20

P+H >20

LDPE CORRELATION PLOT

y = ‐0.2263x + 3.9548R² = 0.8866

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.00 5.00 10.00 15.00 20.00 25.00

Log10 conc (u

g/L)



n

LDPE CORRELATION PLOT

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.00 5.00 10.00 15.00 20.00 25.00

Log10 concen

tration (ug/L)


P+H 0‐5

P+H 5‐10

P+H 10‐15

P+H 15‐20

P+H >20


POLYAMIDE CORRELATION PLOT

y = ‐0.0923x + 3.3525R² = 0.4172

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.00 5.00 10.00 15.00 20.00 25.00

Log10 Co

ncen

tration (ug/L)



POLYAMIDE CORRELATION PLOT

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.00 5.00 10.00 15.00 20.00 25.00

Log10 concen

tration (ug/L)


P+H 0‐5

P+H 5‐10

P+H 10‐15

P+H 15‐20

P+H >20


PTFE CORRELATION PLOT

y = 0.008x + 1.3213R² = 0.0051

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0.00 5.00 10.00 15.00 20.00 25.00

Log10 concen

tration (ug/L)


Density: 2.2 g cm-3

CAB CORRELATION PLOTDensity: 1.2 g cm-3

y = ‐0.0863x + 3.8854R² = 0.3376

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.0 5.0 10.0 15.0 20.0 25.0

Log10 conc (u

g/L)

HSP Distance

CAB

O

O

R

O

OR

O

R

n

R=CH3CO,C3H7CO,H

CAB CORRELATION PLOTDensity: 1.2 g cm-3

y = ‐0.0665x + 3.9824R² = 0.5723

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.0 5.0 10.0 15.0 20.0 25.0

Log10 conc (u

g/L)

HSP Distance

CAB

CAB CORRELATION PLOT

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

0.0 5.0 10.0 15.0 20.0 25.0

Log10 Co

ncen

tration (ug/L)


H+P 0‐5

H+P 5‐10

H+P 10‐15

H+P 15‐20

H+P >20

Density: 1.2 g cm-3

POM CORRELATION PLOT

y = 0.038x + 1.1248R² = 0.057

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0.00 5.00 10.00 15.00 20.00 25.00

Log10 cocnen

tration (ug/L)



O

POM CORRELATION PLOT

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0.00 5.00 10.00 15.00 20.00 25.00

Log10 concen

tration (ug/L)


P+H 0‐5

P+H 5‐10

P+H 10‐15

P+H 15‐20

P+H >20


THERMODYNAMICS VS KINETICS

• HSP gives an indication of whether an analyte is thermodynamically favourable to be sampled.• Kinetics are however an important part of passive sampler design.• In polymers the kinetics will be effected by the diffusion of the analyte into the polymer.

SCREENING RESULTS

• PDMS, PA and CAB show large radius’ of interaction.• PA and CAB are potential polymers for more polar chemicals.

SAMPLER DEPLOYMENT

• As well as using lab tests of known chemicals, polymers were also deployed at the effluent point of a local sewage treatment works.• Samplers were deployed for 3 months to ensure equilibrium was reached. • Polymers were then extracted and analysed by GC/MS and LC-ToF/MS.

IDENTIFICATION OF UNKNOWNS IN SAMPLER EXTRACTS

• GC/MS peaks were compared to NIST library, this however proved difficult due to the complexity of some of the extracts.• This will be improved on when we get some of the extracts analysed by GCxGC/MS.

5.00 10.00 15.00 20.00 25.00 30.00 35.00

-14000000

-12000000

-10000000

-8000000

-6000000

-4000000

-2000000

0

2000000

4000000

6000000

8000000

1e+07

1.2e+07

1.4e+07

1.6e+07

1.8e+07

2e+07

2.2e+07

2.4e+07

2.6e+07

Time-->

Abundance

TIC: 130313_007.D\data.ms (*)TIC: 130313_008.D\data.ms (*)

IDENTIFICATION OF UNKNOWNS IN SAMPLER EXTRACTS

SIGNIFICANCE TESTING OF PEAKS

NUMBER OF COMPOUNDS DETECTED IN POLYMER EXTRACTS

NUMBER OF COMPOUNDS DETECTED IN POLYMER EXTRACTS

0

50

100

150

200

250

300

350

400

PS PVC LDPE PET PC PA PP CAB POM PTFE

Numbe

r of che

micals d

etected o

n LC‐ToF/MS

Unique to polymer

Detected on multiple polymers

0

200

400

600

800

1000

1200

1400

1600

1800

PDMS

FUTURE WORK

• Extend the uptake time in the laboratory test to ensure equilibrium is reached in all polymers.• Possible add a kinetic aspect to this test.• Solvent swelling tests to define the HSP of the polymers I have.• Continue to try and identify analytes sampled by the different polymers that were deployed in the field.• Determine Kpolymer-water to allow quantification of analytes in the field.

ACKNOWLEDGEMENTS

Many thanks to:-Todd GoiunRoger van EgmondChris SparhamKevin JonesAndrew Sweetman

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