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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.
PDMS
POCIS
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
Density: 1.14 g cm-3
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)
HSP distance (MPa1/2)
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)
HSP distance (MPa1/2)
Density: 0.92 g cm-3
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)
HSP distance (MPa1/2)
P+H 0‐5
P+H 5‐10
P+H 10‐15
P+H 15‐20
P+H >20
Density: 0.92 g cm-3
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)
HSP Distance (MPa1/2)
Density: 1.14 g cm-3
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)
HSP Distance (MPa1/2)
P+H 0‐5
P+H 5‐10
P+H 10‐15
P+H 15‐20
P+H >20
Density: 1.14 g cm-3
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)
HSP distance (MPa1/2)
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)
HSP Distance (MPa1/2)
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)
HSP Distance (MPa1/2)
Density: 1.41 g cm-3
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)
HSP Distance (MPa1/2)
P+H 0‐5
P+H 5‐10
P+H 10‐15
P+H 15‐20
P+H >20
Density: 1.41 g cm-3
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