Document zwZKE8nqea26wOz1EDL2oqGR
AR226-2701
23
AR226-2701
TORONTO WORKSHOP MATERIALS
September 13-14,2004
Measuring
Physical Chemical Propertie & Analytical
Mar/A. Kaiser
DuPont Central Research
September 13,14, 2004
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Why not model, rather than mea
Because these compounds are not well-beh predictable.
The miracles of science"
What is "not well-behaved or predic
EPA OPPT PBT Pro filer (used for chemicals
there is no experimental data)
Should not be used for the following:
9 High Molecular Weight Compounds 9 Mixtures
9 Surfac+an+s
B Highly Fluorina+ed Compounds
9 Chemicals with Unknown or Variable Compositio 9 Inorganic Chemicals 9 Reactive Chemicals 9 Salts (Organic Salts) h++p://www.pb+profiler.ne+/chemicals.asp
Uniqueness of Fluorina+ed Comp
Bond energy 9 C-F
-C-H
^C-CI
C-F bond
116 kcal/mole
99 kcal/mole 79 kcal/mole
Pyrolysis
9 Fluorocarbons tend to split the C rather than the C-F bond
Uniqueness of Fluorina+ed Compounds
"Many of these compounds have chemi
physical properties strikingly differen
the hydrogen analogs or from analogou compounds of the other halogens whe
exist.
Advanced Inorganic Chemistry, F. A. C and &. Wilkinson, Interscience Publish New York. 1966,
Method Development Considera
Use governmental resources as guid Maximize use of blanks and spikes Use iso+opically enriched or radiola
standards
The rnlresctes'a/sciences
US
V-^^y^SPiyS
^ ^ \.-.:.Wf-:V^/
Governmental
Resource
WWW.EPA.9ov/quality/
* "...goal is to ensure that environmental progr decisions are supported by data of the type quality needed and expected for their intend and that decisions involving the design, cons and operation of environmental technology a supported by appropriate quality assured en
standards and practices/'
m ERA Quality Manual for Environmental Progr Al, May 5, 2000, page 1-1.
US Governmental Resource
WWW.OSHA.gov/dts/sltc/methods/omep /index.html Method Evaluation Guidelines
- "...a uniform and practical means for
evaluating air sampling and analytical
methods."
US Governmental Resources
WWW.FbA.gov/cder/guidance/index.htm
Guidance for Industry, Bioanalytical M
Validation "...procedures such as gas chromatogra
(.GC), high-pressure liquid chromatogra (LC), combined GC and LC mass spectr
(MS) procedures such as LC-MS, LC-M 6C-MS. and 6C-MS-MS..."
Method Validation
Critical to demonstrate:
a Accuracy Precision
Specificity Linearity . LLOQ
Recovery
Storage stability
bata Acceptability Criteria
Resolution of the chromatographic peak
befined accep+abili+y criteria for recove
Non-defects in instrument blanks Analyte response at LLOQ >5x matrix bl <20% deviation of standards from nomin
concentration at LLOQ (<157o above LLO Quality control samples (QC's) within 15%
nominal value
vy
Criteria for Repeat Analyse
Poor chromatography
Retention times drift more than +4% wit
analytical run Unacceptable calibration curve (correlat
coefficient <0.9925 i.e.. R2 should be >0 QC'sfail
Samples outside assay range Inconsistent replicate analyses Sample processing errors; equipment fai
Ill
What do we know today?
What information is currently avail
What additional information is need
What level of scientific certainty i
required?
Physical Properties
The miracles a/sciences
Fluoro+elomer Alcohols: Physical Pro
4-2
Fluoro+elomer Alcohol
2043-47-2
6-2
Fluoro+elomer Alcohol
647-42-7
8-2
Fluoro+elomer Alcohol1
678-39-7
8-2
Fluoro+elom
Olefin 21652-58-
Vapor Pressure (Pa)
264
140-143* 1200 (at 50C)2'' 992 (at 25C)4-' 252 (at 25C)5
364.1
75-80/14mm* 108 (a+350)^ 713 (a+ 25C)4;
464.12
446.11
46-47*
112-114 G+
r
10mm*
146-147*
3 (a+ 21C);
254 (a+25C)4''
45.90 (a+
14.9 (a+
25C)**
Fluorotelomer Alcohols: Physical Pro
Vapor Pressure (Pa)
Water solubility (mg/L at 25C)
1200 (at 50C)2; 108(0135^ 3(a+21C);
992 (at 25C)4; 713(at25C)4; 254 (at 25^ 14.9(at
252 (at 25 Q5 145.2 (at 25C)5 45.90 (atZSC)5?^)**
0.'n+OW663 0,137+0:053 0.001**
References for Fluoro+elomer Alcohol: P '$-;^>---K';-i?
v - ^ ^ W><'-y:'::-'a>
Properties (previous slide)
1 Data are taken from Kaiser, Cobranchi.Kao, Krusiv, Marchi Buck, J. Chem. Eng. Data. 49(4), 912-916, 2004, unless o
noted. 2 Krusic, Marchione, bavidson. Kaiser, Kao, Richardson, Bo+
Wa+erland, and Buck, submitted. 3 Cobranchi and Kaiser, EAS, 2001
4 Stock, Ellis, Deleebeeck, Muir, and Mabury, ES&T. 38,169 2004.
5 Lei. Wania. Mothers, and Mabury. J. Chem. Eng. Data. 49, 2004.
* Oakwood Products, Inc., http://www.oakwoodchemical.com
**TRP
Physical Properties of Perfluorocarboxylic
Shinoda et aUCF^C^CF^COO^ Melting Point, 13-14 C.
WSWs
Physical Properties of Perfluorocarboxylic
[VapoPrressure (Pa) acid) iWatesr olubilit(ymg/Lat 37QO3;400-
^2
Shinoda et a/.,(CF^CF{CF^COOH Melting Point, 13-14 C.
"s.is-""
References for Physical Properties
Perfluorocarboxylic Acids (previous slid
1. US EPA Hazard Assessment of Perfluorooc+anoic Acid a Salts, OPPT, Risk Assessment Division, US EPA, 2002 an
Franklin, "Screening Assessment of the Potential for Lo
Transport of Perfluoro-oc+anoic Acid", Solvay Research Technology, 2003. 2. Detecting and Quantifying Low Levels of Fuoropolymer Polimeriza+ion Aids", SPI, Washington, DC 2003.
3. Shinoda, Hato, and Hayashi, J. Phys. Chem., 7, 909,1972. 4 Note: Shinoda et al.,(CF2)2CF(CF2)4COOH Melting Point =
* Oakwood Products, Inc., http://www.oakwoodchemical.com
# Sigma -Aldrich Co., https://www.sigmaaldrich.com
ANALYSIS
919
^-ew
Analytical Options for 8-2 Telomer B
Properties:
- Structure; CF^CF^-W^W^-OH
- Water solubility: 150 pg/i
- Melting point: 44C - Boiling point: 213C at 760 mm Hg - Vapor pressure: 3 Pa at 21C or 254 at 25 C
- UV: none for 225-400 nm
1. 6C-FIb
- limited sensitivity and selectivity
pA'
23-
15-
^
5,1
10-
W
00 Q
40
NJ
5-
033446
0-
u^. >-
-6-
0
2
4
6
8
run
2. GC-MS
-must have volatile materia
- Martin et al., Anal. Chem. 584;
- PCI and NCI with me
sampling
- Ellis et al., J. Am. Soc. Ma 14 (2003) 1177;
- NCI, PCI spectra int Telomer alcohols;
3. LC-MS - desirable for compat
acid-type compounds;
Background and Matrix Effe
Blanks, spikes, matrix, and calibration standard medium are ve
Solvent may contain low-levels of PFOA th
be enriched in the sample work up process Spike recovery data are essential for each Matrix can interfere, especially if chromato
resolution is insufficient
Calibration standards should be made in s matrix as sample
Isotopically enriched standards are preferr available
Guard column is helpful for gradient runs
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Guard Column
Useful in gradient measurements
05102004-05
^
QAA592
Internal standard
2: MRM of 1 Ch 414
05102004-05 100^
%
1: MRM of 1 Ch
From guard
column
-H^SiM
Analytical Issues
Standards
Telomers(no certified standards)
telomers come as even numbered mix Perfluoro Acids
' Telomer acids are even numbered Carboxylic acids are made either by t
telomer process (even numbered) or electrofluorination (up to 15 % branc
See: Martin et al., ESAT, 38(13), 248A-2 (2004)
Standards?": Perfluorooc+anoic acid produ electrochemical processes
FC96 Assav-1-2 Quattro LC Q2--3718 100-)
SotierisorbOBS 200X2.1m,En 20%2mMAMM AC80% MeOtt
IS415>370
^ linear
Q24-3719 100-]
C8413>369
branching ^
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1.00
2.00
3.00
4.00
S.OO
O.OB
linear
Branched distribution
considerably
to lot.
7.00
S.03
8.BO
10.00
11.00
12.00
13.00
The mtmctes c^fsctetcr|
"S+andords?": Surf Ion Sill (perfluorononan
S111 A Assav-1-1 Quattro LC Q24-3 692
100-
IS415>370
B %-:
0-
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SoherisorbODS 200X2.1 mm 20%2mMAMIVIAC80% MeOH
12
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11?"
The mfmctes q^sctewj
8-2 TBA Soil and Sediment Adsorption
Within three hours (less than one hour in fr dried activated sludge), 100% of ^C-labele TBA initially added to the test system partit soil and sediment
KQCranged from 572 to 4941 (mean for 5 s 2272)
Note: This is a short-term (24 hour) adsorp
study.
OEC[) 106: Guidelines for the testing of chemicals. "Adsorption/desorp+ion using a batch equilibriu January 21,2000.
Implications of 8-2 TBA Soil Sediment Adsorptio
If the 8-2 Telomer B alcohol is forme
degradation product in soil or in sedimen
stick to the soil or sediment and not be generally available for transport.
PFOA Soil and Sediment Adsorption
Within 24 hours, equilibrium was reache some PFOA remaining in water phase.
KQCranged from 48.8 to 229 for one slu
4 soils.
Note: This is a short-term (24 hour) ad
study.
06CD 106: Guidelines for the testing of chemicals, "Adsorp+ion/desorp+ion using a batch equ January 21,2000.
More Analytical Issues
Fluorina+ed Polymer Samples made from mixtures of mixtu
not soluble in common solvents
usually available as dispersion surfactan+s, etc.
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Fluorotelomer-Based Polyme
Sample Issues
Difficult to remove fluorina+ed poly
from dispersed system
Difficult to determine sorbed resid
unless compete dissolution is perfor Difficult to get molecular weight distribution due to solubility, "mixe composition", lack of standards
(MALDI/MS may be required)
've/
S-2 TBA - plasma and tissues proce
Fat
Liver
Pla
Kidney
Extraction:
0.3 g fat, (spike),
dissolve in 6 mL heptane
Clean-up:
SPE: Si, 500 mq /10 mL (1ST)
1. 1 mL acetone and 2 mL heptane
2. Load heptane extract
3. Wash with 6 mL heptane 4. Elute with 1 mL IPA
Extraction:
0.5 g tissue; (spike), add 2 mL water, 15 pL HCIO^
extract with 6 mL hexane; 15 min vortex; centrifuge
Clean-up:
SPE: Si, 500 mg /10 mL (1ST)
1. 1 mL IPA and 2 mL
hexane
2. Load hexane extract
3. Wash with 6 mL hexane
4. Elu+e with 1 mL IPA
Extra
0.25 mL p mL water +
15 min
cent
No C
for p
Challenges (biological and environmental m
Complex mixtures of chemical species
Need multiple methods (no one size fits all) Need clean matrix for calibration curves
Need well characterized standards
Validation Considerations
9 Matrix-based six (6) points (nonzero) standard 8 Simplest curve fitting* 8 3 x 3x 3 demonstration (high QC, LLOQ, mid Q
three days in triplicate to access accuracy and
precision*
9 Stability studies for sample, extracts, and stan
8 Iso+opically enriched materials (13C-13C, 0, etc also be strongly considered in complex matrices
9 Data review (internal and 3rd party)
9 *Guidance for Industry: Bioanalytical Method V
US PDA, May, 2001
Physical property and analytical d
to stand the test of time......
Thank you for your attention,
