Document dQB62VwGoXnp60qOwZ3L8k8qq
@
AR226-3349
Development of analytical methodology for
determination of Telomer B Alcohols, Telomer-derived
anionic, nonionic fluorosurfactants and polymers.
Bogdan Szostek, Keith B. Prickett, Janet C. Maslanka, and EE EEE
1puPont Haskell Laboratory for Health'and Environmental Sciences, Newark, DE, USA
Telomer B Alcohols and Telomer-derived Surfactants and Polymers Telomer alcohols: CF5-(CF,),-CH-CH,-OH n=3,5,7,9,10, 8-2 Telomer B Alcohol: CF,-(CF,),-CHy*CH,-OH
A]
Polymers:
(Ces(CF I Cit Ci OLPOOL?) BTS | TEL
CeWCTRI TRG Re cote m Ei f URW =
CF3=(CF)CHsS-O;CCHNHy,*
Non-ionic Surfactants:
|
CF3(CFy)aCHy CHyO-(CH,-CH,-0),H
ee] environmental fate, and environmental effects studies for these materials,
an
|
Analytical options for 8-2 Telomer B Alcohol
Properties
Structure: CF=(CF,),-CH,-CH,-OH
Water solubility: 150 pg/L
NEE =Boiling point: 213C
at
760
mm
Hg
|
- Vapor pressure: 3 Paat 21C
LR
2. GC. + GEMS! -mostoften used
ACE, | Sr
CPUS
eT
1. GC-FID
-
ERR
=|
oq Siwg/mi
FETC
EER,
+ | TET 40ug/mi
Len
odes
==
S
L
@
Basics of GE-MS method-- EI spectra
DHE
THT imam, 24, 24 perfuoradecan-i-ol
=| sameusaremmaearns
-r
=] HHH
-
oar
k
Lo
@
8-2 TBA -- GC-MS method issues
(SUE Eye
BiV Ae
- Methanol; IPA
IE et
"
fo
Le
EN
a
TTT
Time [hrs]
ol
TT
Slump performance
TT.=
vl | Inj.#7
z
11
=
rn
~
-
Inj.#85
:z
rE ET
mm DE
Environmental waters -- method validation and sample storage
Experiment
mw
=fe
i
hf
A.
|
en
COa L
CREE
Results (% recovery t st. dev.)
Te tt ST | a
R n i e E |Fro| za eRnT |e RT(Nofoil|) Frozen Lud
THI 102s | sess eau asad | 100k | 24st
se
LTH 9822 | otke
S7#2
3082
1042 | 261s
ETRY ois sexs | sass 2eas 10082 15
I oez2 mors | oasy 2esy sem: smi
ah
LER: ATe
S 52 TBAcar n bo ionized by electroA spray RS arBaEdient bf walbri0msi)hanolis used; aqueous samplesin 60% acetonitrile HL RT
am Stduirnesoo|| CC CRAr lT7 E7o o 0 S5% n a= 5t
hl|
ant |
wea
Resorts orl (R42) fe (Sur 548)
|QtLin QighBccWight 1 AstarsNore:
|
ES|
Ba;| 25-2550 ngimL 8-2 TBA
LL ee
SatsaraniS)|
o
so= m
acme
o === | |
sBr e t an e an r anem w C wm S mam a oa)
E
@
Ethoxylate nonionic fluorosurfactant
CF 3(CF)x-CHp-CH-0-(CH,-CH,-0),-H
x=35,7911,13,... n= 0-25
Analytical methods:
GC-FID
eg)
a
Ethoxylate nonionic fluorosurfactant by GC-FID
SE
8
=| |
i
=|
=|
2]
wo)iis
o
[I]t 2
i
| | | | | 1a
LUA AA
.
ol
-
3.3 mg/mL ethoxylate fluorosurfactant imn ethanol
Tis 5
7s
Bo
Tus 5
ws| m mn
an | HASKELL
Ethoxylate nonionic fluorosurfactant by LC-MS
fCormiadtducits WR BN, in EE 5i+ ch HEN
.
6-2 TBA ethoxylates
8-2 TBA ethoxylates 10-2 TBA ethoxylates
12-2 TBA ethoxylates
J\ 14-2 TBA ethoxylates
aTn Ebenie s
@
EOCENE eT cyId Ae
CF y-(CF)y-CH,-CH,-0-(CH,~CH,-0),H NH;
"
L 2d 10
ES
o? ~
nett
--
|
+
w $
"
=e
nets
S5
J i"
= ws
33
T i
~7
ow i-s eto
5s]
r SlI bm ime
|7
7nets
Alltt a
an |
miesr ae ]
<i
&
@
Ethoxylate nonionic fluorosurfactant by LC-MS
samples a[ nd standar) ds need to contain 50% acetonitrile otherwise are unstable quantitation can be achieved by monitoring peak areas for individual TBA quantitatiE on can alse o be done n by monitoring selected group @fions for each TBA
ethoxylates;
CCoteset rieosebm 2Rr2a=e03t5213
CabistgeroaariosenetruineeS:ot58o5r0Ca9Sg1a64B00eg5sts2e+V23i80r74040s7 *rx4s116e47r7s
on)
1
|
|
|
||
M om e ow r ow ome ih
ozscout
om || 1saBma|1
Rises]
25a]
ons:
|
l 6905
|
il
734.5
|
7786
Il
8226
i 866.6
|
|
| d I| e
rr r ww r www
Acrylate Telomer-based polymer
BcRoepAoelyEmerof vr inylidene chloh rideP , TaloRmor HAcere and saary methacrylate
5000 -- =
4000 -
a0 2% 200
1000 . 2000
A
E 3 EFIn
ag. :3
J/ \d
Lei
a0C0o0ncentration, m10r0t0.0 14000
Acrylate telomer-based polymer -- method validation and method
application
Buffertype | (9% recovery
Fo 3
a Err)
[oEes
Te
101212
es
10005
Len
[LEAN
10113
LC
ILIA
ET]
100210
-15000 mglLstd
-SeDmay e5,npH40 ~~ [
,|
Rng
7
-
|\ |
i\ |
J 7 \Non |
|
Ll
1
id
=):
A
iin asca .
Summary
General remarks
- discussed analytical methodology for analysis of 8-2 TBA, nonionic ethoxylate fluorosurfactant, and acrylate polymer;
- cach analyte, even though derived from telomer chemistry, required individual and different approach; Is a single method for Ee
_ analytical methods for many of the fluorinated compounds Gf interest are being established; rigorous method validation
| |
demonstrating proper spike recoveries in the matrix of interes |
SE
RR SS Ele SRC eee) |
|
O
@
Summary
Specific recommendations for analytes studied
ERIN
- can be analyzed either by GC/MS or LC/MS
- volatility losses from water are rapid and significant;
- aqueous samples should be stored frozen;
- GC/MS methods are problematic for trace level analysis in
complex matrices;
- aqueous samples can be extracted with 60% MeCN for LEMS;
ethoxylate fluorosurfactant:
R
- LC-MS analysis is advantageous: sensitivity and clear
|
identification of chemical species;
|
lo EeCE RA (Ee
Ea
- polymer can be isolated from aqueous matrix after wetting
|
with the help of fluorosurfactant;
|
- quantitative method was established based on LC-GPC analysi$:
with RI detection;
|
|