Document 4J3dr4K5KOOB4g471ad72E3Rj
\
AR226-2728
W.f.'iSIIII Economists
Scientists
September 9, 1991
LMG32550.MD
Mr. Michael McClusky
E.I.
P.O.
Dupont de Box 1217
Nemours
Parkersburg, West. Virginia 26102
RE: Progress Report for PC-143 Method Development.
Dear Sir: Since the beginning of work we have talked by telephone frequently concerning the FC-143 method development in progress at our laboratory. In brief summary, we have developed an analytical method capable of measuring FC-143 at levels below 0.1 ppb in water matrix. Further method refinement and ruggedness testing continue on schedule. Development costs to date are approximately $16K and
are below projected estimates. The final costs are not expected to exceed plan. Details of the technical progress will be
described below followed by a breakdown of the current expenses.
TECHNICAL PROGRESS
The analytical method uses liquid/liquid partitioning to extract
FC-143 from a one-liter acidified water sample into an organic
solvent. Method validation has already been completed using
separatory funnel technique with diethyl ether as the solvent. We
are hopeful that the approach can be expanded to include continuous
extractors using dichloromethane solvent. Continuous extractors
are less likely to-produce emulsions with difficult samples,, and
dichloromethane is a less hazardous solvent.
Solid state
extraction using granular activated carbon was briefly investigated
but failed to offer early success.
Sample extracts are concentrated by boiling off the solvent using
standard Kadurna Danish technique on a steam bath. A few
milliliters of 1 N NaOH is mixed into the sample as a keeper before
concentration. We have not yet tested the use of nitrogen blowdown to complete this procedure step where a large volume of solvent must be removed. There is some concern that the boiling action may
be necessary to rapidly convert the acid form of the analyte to its salt and avoid volatility losses. Our laboratory is equipped with Zymark nitrogen blowdown units to test this option.
The MaOH concentrate is transferred to a 4-dram screw cap vial and
washed with dichloromethane to remove neutral and basic interferences. A centrifuge may be necessary to separate the liquid phases before discarding the organic phase. Sulfuric acid
CH2MHILL
duality Analytical Laboratories
2567 Faiflane Drive, P.O. Box230548. Montgomery, Alabama 36116
205.271.1444
V
MPrro. gMreiscshaReel pMorctC, lufoskryFC-143 Method Development.
page 2
"
is then from the
added to the aqueous concentrate
salt to the associated acid before
to convert performing
the analyte a last mini-
extraction into ether.
Early
work
attempted
to
dry
the etherial extract after the final
Anhydrous potassium carbonate was
extraction tested for
using drying salts. speedy drying. Deactivated
anhydrous
sodium
sulfate
was
also loss
toefstaenda.lyteBoathnddwryeirneg thsearltesfowr erreemofovuendd frtoomptrhoeducperocmeedausrueraabnled
replaced by concentration to dryness described below.
One
to
hundred microliters of concentrated
the final "wet" etherial extract
ammonium hydroxide is added immediately before micro-
concentration on a steam bath. from approximately
The final extract is
10 mL to approximately
quickly 0.5 mL.
concentrated Ether is used
to
quantitatively
transfer the extract blowdown is used
to to
a 5-mL
finish
reaction vial. Gentle nitrogen
concentrating the sample to dryness.
Acetyl chloride a very dry 3%
is carefully mixed with absolute ethanolic HC1 solution. The
ethanol
sample
to prepare residue is
dissolved in 1.0 mL of the ethanolic HC1 solution and heated at
60C for 30 minutes to form the ethyl ester.
Two final After the
cleanups
reaction
are performed before the
vials have cooled, 1.0 mL
esters are analyzed. of hexane and 1.0 mL
of blank water is mixed into
ester will partition into
the the
sample with top liquid
vigorous phase.
shaking. Most of
The
the
floating phase is transf
containing approximately
er 1
red
mm
to of
a
Fl
2-mL
orisi
l
autosampler vial . After shaking
alr the
eady
vial
for a few seconds, chroroatography with
the extract is electron capture
ready for analysis detection (GC/ECD).
by
gas
TEwicoosaflsuuorrroougnadteecsanoic (paecridfl)uoarroenospniaknedoicinto
acid
every
and sample
11H-
at the
beginning of sample preparation to monitor-othe success of that
sample prep. Three internal standards are portion of the final extract to monitor
mixed into a the success
measured
of data
acquisition. esters because
FC-143 and the surrogates are derivatized to form neither the acid nor the salt forms are amenable to
gas chromatography.
If How should the instrument be calibrated, and how should sample
results be options.
calculated? These are pure and accurate ester
issues which standards were
have several
available for
FC-143 and the surrogates, then these could be diluted and used for
instrument from three
calibration directly.
sources: PCR Research
Several Chemicals,
standards were secured MTM research Chemicals
of
For
Ltahnec apsetrefrl u oSryonot hcet as inso i Icn ca.c,i danbdothF Ct-h1e1 8 tewcahs nipcraolv iadnedd
by the
Dupont. pure
\
Mr. Michael McClusky
Progress Report for FC-143 Method Development.
page 3
grades were purchased from PCR. Disturbing discrepancies were observed when various standards were compared.
If calibration standards were to be prepared through the entire
lengthy procedure for every batch of samples, one would worry about
the variability of calibration from batch to batch. A reasonable
alternative would be to prepare a calibration standard using only minimum preparation to reduce variability. This approach was taken for the validation work. The PC-118 supplied by Dupont was blown to dryness and assumed pure as a primary standard for FC-143 determination. A mixture of this FC-143 and the surrogate acids was introduced to the procedure at the derivatization step and carried from that point to the end of the preparation. Instrument calibration was performed by diluting the final preparation to create five concentrations injected into the instrument. Calibration curves were constructed to calculate FC-143 and
surrogate recoveries for all subsequent samples. To test the linearity of the derivatization itself^ the first five samples
analyzed were five discrete samples at variable masses of FC-143 taken only through the derivatization and final cleanup steps. These five discrete partial preparations were virtually identical to dilutions of the one partial preparation diluted for calibration. Linearity of samples processed through the entire
preparation is still under investigation.
Ten samples were processed through the entire analytical method and are summarized in the table below.
FC-143 SPIKED
0.0 ppb 0.1 ppb 0.1 ppb 0.1 ppb 0.1 ppb 0.1 ppb 0.1 ppb 0.1 ppb 0.2 ppb 0.4 ppb
FC-143
FOUND
0.000 ppb 0.062 ppb 0.052 ppb 0.061 ppb 0.059 ppb 0.058 ppb 0.062 ppb 0.062 ppb 0.11 ppb 0.23 ppb
ET-C9
SURR. 52% 51% 44% 49% 53% 50% 51% 54% 48% 53%
ET-C11
SPRR. 47% 48% 41% 46% 47%
-48%
47% 50% 48% 46%
These samples used laboratory blank water as the matrix. A significant bias is observed in the FC-143 data and is reflected in the surrogate recoveries. Analytical precision was good. Three standard deviations of the seven 0.1 ppb replicates was 0.011 ppb. Typical chromatograms are enclosed as well as the calibration curve described in this text.
Y
Mr. Michael McClusky
Progress Report for FC-143 Method Development.
;
page 4
Confirmation analysis may be accomplished by using a dissimilar
analytical column. for two dissimilar
Chromatographic conditions have been developed
columns. A second approach to confirmation is
possible by derivatizing the acids to a different ester. The
methyl, ethyl, n-propyi, and n-butyl esters have been successfully
prepared.
CURBEMT PROJECT COSTS
The table below offers a current breakdown of costs. Some figures are estimated since shipping costs or effective discounts are-not yet known.
Labor - Consulting Chemist.....
Labor Labor -
SEexntriaocr tiCohnemSuispte..r.v.i.s.o.r....
(129Hr) ($71.07/Hr) (2Hr) ($48.93/Hr) (4Hr) ($50.00/Hr)
= $9168.03
=$ 97.86
= $ 200.00
Labor - Associate Chemist......
Instrument Time - GC...........
(24.7Hr) ($35.33/Hr) = $ 872.65 (40.75HT)($85.00/Hr)= $3463.75
instrument Time - GC/MS........ (OHr) ($150.00/Hr) =$ 0.00
Reagents and supplies
ARTnXa-l2y0t0icCalapSitlalandryardCsoluOmrndeOrerdde7re/d318./.1.......................
$ 274.00 $ 450.00
REtehaacntioolnRVeiaalsgeOrndetr.e.d...8../.1.............................................
$ 78.92 $ 150.00
A24c/e4t0yl SCt ohpl oprei dr se........................................................... .. .. ..
$ 126.88 $ 100.00
ARenaaclytitoincaVl iSaltaSnedpatrad.s......................................................
$ 75.00 $ 130.24
Miscellaneous Supplies.........................
$ 100.00 $ 200.00
Communication.......................................
Total............................................... $ 15487.33
The next written report will accompany the final analytical
method as well as summarize complete costs for the project.
^ ^ ^ i ^ Sincerely,
i.
-
r^&^
Jewell W. Smiley Consulting Chemist
Gas Chromatography Supervisor
cc: Craig Vinson/LMG Herb Kelly/LMG David Smith/LMG
Analysis of Perfluoro-Octanoic Acid Samples Dave DuBois, Betsy McCord and Liz Lozada 10/2/2000
Summary and background:
We received 4 samples from M. Kaiser to analyze for chemical structure. We analyzed them by ^F and ^ NMR. One sample was also analyzed by ^C NMR.
Samples:
Notebook 88570-8-1 88570-8-2 88570-8-3 88570-8-4
LIMS 68425 71402 71404 71405
Description
.3M FC-118 20% PFOA Miteni RM 350T 20% PFOA
MDF Recovered C-8 20% PFOA Dynan 30% PFOA GUS-NR-69641
Results:
Sample 8-1 was typical of the 4 samples. It contains the following groups:
CF3(CF2)x (CF3)2CF(CF2)x 3 types ofCF3(CF2)xCF(CF3)(CF2)y
Thus there are 4 types of CFsCF (-71 to -75 ppm; -184 to -188 ppm) groups and 4 additional types of -CFs groups (-82 to -85 ppm), as shown in the about structures. There are a large number of signals in the -110 to -130 range which are CFz groups.
There was an unidentified signal at -63 ppm which might be -CFgCI, CFzl,
CFzBr, CHaORf, or possibly a vinylidene CFs or a tBu CFa.
Sample 8-3 was almost identical to 8-1 except that it contained a small amount of CFsCFHCOOH (-76, -196 ppm). This material had sharper NMR lines. The 1 H NMR showed a doublet of quartets at about 5.2 ppm that supports this assignment. The j values observed agreed with that of an authentic spectrum of A. Sievert.
Samples 8-2 and 8-4 were almost identical to 8-1.
Quantitative Results, relative mol%:
Sample (ppm)
81
82
8 3
84
CF3(CF;), -83.5 78.9 79.0 72.4 83.0
(CF3)2CF(CF2), -73.9 8.6t 7.9 10.2 7.4
CF3(CF2),CF(CF3)(CFz)y CF3CFHC02H
A,-71.7) B.-71.9' C,-72.3 -75.8,-195.5
4.3
3.3
4.4
0.0
3.9
3.5
4.7
0.0
5.1
4.4
5.7
1.2
3.3
2.3
3.6|
0.0
pentad -63.3 0.7 1.0 1.0 0.5
Experimental:
^F NMR spectra were obtained on a 400 MHz Varian Inova
spectrometer on a 5 mm probe on samples run neat with a DzO containing capillary for lock. Spectra were externally referenced to a capillary containing F-11 (0 ppm). Spectra were acquired at 30 C using an rf pulse of 2 usec (pw90 = 14 usec), a spectral width of 90 kHz, an acquisition time of 1.28 sec and a recycle delay of 20 sec. A total of 256 transients were
acquired. ^ (with water suppression) and ^C (10 mm) spectra were
obtained on the same instrument using standard conditions.
Acknowledgement:
We would like to thank A. Sievert for his help and advice with the ^F NMR spectra.
F c\
G
A
r
0
G
i \ ^CF. ^CF, ^ ' c.
--"^ F CFa
CFz
CFa
CFa
0
0
CF3 D
s,
^^
CF
CF2
--
's, CFz
C^3
CFa ^i.
'S.. CFs
'< 0
BCFa
^
H,/ A E CF3
C ^
^c\ Fg^o /y
\
E|
.1 J B 1
x3 , 1
,Jj i J^
A.?
-60
-80
-100
-120
-140
-160
-180
-2
Figure 1. ^F NMR of Sample 88570-8-1, 3M FC-118 20% PFOA
-n-
-60
-80
-100
-120
-140
-160
-180
Figure 2. ^F NMR of Sample 88570-8-2, Miteni RM 350T 20% PFOA
F c
G
A
/"
G 0
1 ^CP. ^
^ ' c.\
-^'-\ F CF,
^CFg
^-CF;
CF;
0
0
CF3 D
CF ^
'
c^3
E
CF;
'
^
.
C
F
'
z
CFg
\
.^ '
CFa
'^. 0
B CFa
^
CF ^3 . . 1 </CA^l^;0^< ^\
1. \
H0 -.^CFH
0
E J BH
x3
ijlj J 11
AD '
111
.
-80
-100
-120
-140
-160
-180
-200
Figure 3. ^F NMR of Sample 88570-8-3, MDF Recovered C-8 20% PFOA
-T-J-T-
' ' ' ' 1
Tl|ll ' I '
-60
-80
-100
-120
-140
-160
-180
-200
Figure 4. ^F NMR of Sample 88570-8-4, Dynan 30% PFOA GUS-NR-69641
Analysis of Perfluoro-Octanoic Acid Samples Dave DuBois, Betsy McCord and L'z Lozada 10/2/2000
Summary and background:
PFOS chemicals are used in a wide range of products from fire-fighting foams, coatings for fabrics, leather, and some paper products, to industrial uses such as mist suppressants in acid baths. DuPont produces
fluorochemicals based on the perfluoroctanyl iodide chemistry such as Telomer B alcohol. If DuPont can replace materials made with 3M's PFOS with materials based on DuPont's telomer chemistry, there would be a large potential replacement market for us. Our knowledge of persistence, bioaccumulation, and toxicity (PBT) of DuPont materials is incomplete based on the possible applications in the marketplace. CTO Dr. Joseph Miller established a team to quickly address the issues. The team's charter
is to provide the science and technology basis to proactively address SHE
concerns related to our products. Subteams on Toxicology, Exposure, Environmental Fate and Effects, and PFOA alternatives are working on solutions. Key to each of these teams is the Analytical subteam, which will need to provide product analysis via existing or newly developed methods.
We received 4 samples from M. Kaiser to analyze for chemical structure. We analyzed them by ^F and 1!-! NMR. One sample was also analyzed by ^C NMR.
Samples:
Notebook 88570-8-1 88570-8-2 88570-8-3 88570-8-4
LIMS 68425 71402 71404 71405
Description
3M FC-118 20% PFOA Miteni RM 350T 20% PFOA MDF Recovered C-8 20% PFOA Dynan 30% PFOA GUS-NR-69641
Results:
Sample 8-1 was typical of the 4 samples. It contains the following groups:
CF3(CF^
(CF3)2CF(CF2), 3 types of CF3(CF2)xCF(CF3)(CF2)y (CFa)3C(CF2)x
Thus there are 4 types of CFaCF (-71 to -75 ppm; -184 to -188 ppm) groups and 4 additional types of -CFa groups (-82 to -85 ppm), as shown in the about structures. There are a large number of signals in the -110 to
-130 range which are CFz groups.
There was a signal at -63 ppm which was assigned to (CF3)3C(CFz)3
group. Its chemical shift and multiplicity correspond to values found in the
literature.
Sample 8-3 was almost identical to 8-1 except that it contained a small amount of CFsCFHCOOH (-76, -196 ppm). This material had sharper NMR lines. The 1H NMR showed a doublet of quartets at about 5.2 ppm that supports this assignment. The j values observed agreed with that of an authentic spectrum of A. Sievert.
Samples 8-2 and 8-4 were almost identical to 8-1. The ^H NMR spectrum of 8-4 showed a singlet at 3.4 ppm, which may be methanol; spiking experiments are underway to verify this.
Quantitative Results, relative mol%:
} Sample I CF-s{CF^ (CF3)zCF(CFz),
i
(ppm)!
-83-5
-73.9
,
81
78.9|
8.6
':
82
79.0
7.9
i 83
72.4
10,2
j 84
83.0
7.4
CF3(CF2),CF(CF3)(CF;)y
A,-71.7 4.3 3.9
5.1
3.3
B.-71.9
3.3 3.5 4.4 2.3
C, -72.3 4.4 4.7 5.7 3.6
CFgCF-HCOzH -75.8.-195.5 0.0 0.0 1.2 0-0
[CF3)3C(CFa)3
-63.3 0.2J
0.3 0.3 0.2
Experimental:
^F NMR spectra were obtained on a 400 MHz Varian Inova
spectrometer on a 5 mm probe on samples run neat with a DzO containing capillary for lock. Spectra were externally referenced to a capillary containing F-11 (0 ppm). Spectra were acquired at 30 C using an rf pulse of 2 usec (pw90 = 14 usec), a spectral width of 90 kHz, an acquisition time of 1.28 sec and a recycle delay of 20 sec. A total of 256 transients were
acquired. ''H (with water suppression) and ^C (10 mm) spectra were
obtained on the same instrument using standard conditions.
Acknowledgement: We would like to thank A. Sievert for his help'and advice with the ^F
NMR spectra.
~n C--Q
C
0
v '
^
Z
;o
0 --h
C/3
CD
3
-0
CD
00 00
CJ;
0
CO
J-^
CO ^
-n
0
00
g
^00^
~D ~n
0 ^>
. -
: 03 --
o -
:
^
:
^
^
1
^ -
o
'
:
:
-
,
-
-
^~-
-^ J
0
-
'-
:
^ ^
s--
=
^ :
00 -
0
-
I
ro '
0
-
0
-
? :
3 -
x CO
( -
.
03
'^:--------------o
m
-n
.
----
LE"-------
0
^
-/
" > -
^
1 -------
m
\^/
0 0
"
"^ ? m
'
/
"\-n0 " 9--\" -- Y
/ 0 -n
0
-n
M
o
"n
-^"
-^\^ro--oCD
>!
\
^
"n
'-~0 ^
-n
\ \
0r^ 0 /^ \------Q
-<-:"-A\)------0
^ o ^ /"n \ 'o "n 0 /" A N o ^ / /(1 "'n \ \ )===0
0
o^
U'^
!
-
-n
"\
9
,,/"' "Y Tl
0 0 ^ ^ /
?
M \\
^
M
/
0
/ = 0 \ -n
M \
/
3
0:0
e_, -.:.:-:-: -.yy.'-.y.V^
w
'
-60
-80
-100
-120
-140
-160
-180
Figure 2. ^F NMR of Sample 88570-8-2, Miteni RM 350T 20% PFOA
v^^y
F - -CFa
CFa
s.
^
CFz
CFa
.CFz
^
v, CFa
s,
'CFz
F c
E
J BH
x3
A.,
-60
-80
G
r
A-
l^ljJ 11
-100
-120
-140
CFa D
CF *IW
<^
cFa
^.
<^
CFa
. CFz <", CFaf
CFa
B CFa
f^ E CFa \
^CAFf^cF^^'
/x '> /y
0
1
H c^. cp^ 1
AD
-160
-180
Figure 3. ^F NMR of Sample 88570-8-3, MDF Recovered C-8 20% P
-60
11111--I I I I I I I I I I I I I I
-80
-100
-120
-T-T-T-
-140
III IIIII
-160
-180
-20
Figure 4. ^F NMR of Sample 88570-8-4. Dynan 30% PFOA GUS-NR-6964
For Sample 88570-8-1
Compound:
0
^CF, ^.CF,
CF3
^CFz
^CF,
CPz
^ ^ CF;
"0-
NMR mol%
JQ Q
' -'"-'
3M Fax mol%
Oo^Uo/O/
CFa ^CFz
--
--
"s- CF
'^'CFz
^. CFz -^ ' CF;
'^ 0-
CF3
CFa
0
CF3
^CF
.J^.
TCF^ r-CF^ "0-
V YX \ /V
CFa
0
^4 ^cp ^
CF, CF'
CF'
"-
8.6 12.0 0.2
8.5 11.3 0.3
