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OCTANOUW ATER PARTITION COEFFICIENT
TEST SUBSTANCE_____________________________________________________
Identity: N-ethylperfluorooctane sulfonamidoethanol; may also be referred to as N-EtFOSE Alcohol or FM-3422. (1-Octanesulfonamide, N-ethyl1 ,1 ,2 ,2 ,3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 ,8 ,8 ,8 -h e p ta d e c a flu o ro -N -(2 -h y d ro x y e th y l)-, CAS # 1691-99-2)
Rem arks: Material is an off-white, waxy solid. The test laboratory identifies the compound as "T-5874" Batch 2334.
M E T H O D ______________________________________________________________
Method: OECD 117 & EEC-Directive 92/69 EEC, Annex V, Part A.8 GLP (Y/N): Yes Year com pleted: 1994 Analytical: HPLC with Spectrophotometric detector
Rem arks: Testing used six substances with known log Paw values as references. These substances were used to calibrate the elution time in units of log Pow-
Reference substance Benzylalcohol Toluene 1 ,4-dichlorobenzene Fluoranthene (98%) Dibenzyl (99% ) 2,4-DDT (99% )
log Pow 1.1 2.7 3.4 4.7 4.8 6.2
A stock solution of the test substance was prepared by dissolving 165 mg in 50.0 mL acetonitrile and sonicating for 3 minutes. The stock solution was diluted 10 times with mobile phase, resulting in the test solution.
Mobile phase is a 75/25 (v/v) solution of acetonitrile / Milli-Q water respectively.
RESULTS______________________________________________________________
Substance Reference chemicals
Benzylalcohol Toluene 1,4-dichlorobenzene Fluoranthene Dibenzyl
log Pow
1.1 2.7 3.4 4.7 4.8
000009
2 ,4 -D D T
6.2
Test substance
Peak 1
5.6*
Peak 2 (major comp.)
4.4*
Several small peaks
2 .2 /4 .4 *
* Interpolated from the regression line: y = 0.288x - 0.730 (r=0.972, n=6)
C O N C L U S IO N S _________________________________________________________
This study estimates the log Pow for N-EtFOSE alcohol.
Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133
DATA QUALITY_________________________________________________________ Reliability: Klimisch ranking 2
-per OECD. HPLC methods enables partition coefficients to be estimated in the log Pow range between 0 and 6.
-Notox states impurities are of minor importance in HPLC method, however OECD states, HPLC method is less sensitive to the presence of impurities in the test substance than the Shake Flask method. Nevertheless, in some cases impurities can make the interpretation of the results difficult due to uncertainty in peak assignments. Mixtures which result in an unresolved band, upper and lower limits of log Pow should be stated. Duplicate analysis should be reported in order to show confidence in the measurement (log Powvalues should fall within a range of +/- 0.1 log units) - data provided mean value therefore can't show confidence. pH of eluant is critical of ionizable compounds. The study did not include any fluorochemicals among the reference substances. Without fluorochemical reference compounds, it is not known whether the same relationship between the capacity factor k" and Kow exists for compounds with perfluoroalkyl portions as exits for nonfluorinated reference materials such as those used in this study. The reference compounds should have been also injected independently to insure appropriate retention time assigned to each reference compound. Reference substances were injected twice, however only the mean retention time data is given for the reference substances thus repeatability of the retention times is not clear. It was not demonstrated that the test material was soluble in the acetonitrile stock solution or in the mobile phase. No demonstration that the major components of the test substance are detectable at UV X = 210 nm (Generally, UV absorbance detectors poor choice for N-EtFOSE alcohol and related fluorochemicals). UV adsorption spectra is needed of the purified main components of the test substance. Assumptions are made that the major peak from the HPLC of the test substance is the major component. No attempt was made to confirm this (e.g. Mass spec analysis to show the material detected has the appropriate mass). It is not known whether
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the major components even come off the column. Some k' values reported are calculated incorrectly. R E F E R E N C E S ____________________________________________________ Study conducted at the request of 3M Company by NOTOX Safety & Environmental Research B.V., The Netherlands, April 7,1 99 4.
OOOOll
I I' l
REPORT
DETERMINATION OF THE PARTITION COEFFICIENT (N-OCTANOL/WATER) OF T-5874
BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)
1.A
NOTOX Project 121275 NOTOX substance 38187
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received
NOV - 9 1994
TUa iCOLOGY
T-5874
NOTOX Project 121275
STATEMENT OF GLP COMPLIANCE
NOTOX B.V., 's-Hertogenbosch, The Netherlands
The study described in this report was conducted in compliance with the most recent edition of: The OECD Principles of Good Laboratory Practice which are essentially in conformity with: The United States Food and Drug Administration. Title 21 Code of Federal Regulations Part 58. The United States Environmental Protection Agency (FIFRA). Title 40 Code of Federal Regulations Part 160. The United States Environmental Protection Agency (TSCA). Title 40 Code of Federal Regulations Part 792.
Study Director:
Drs. R. de Vries
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QUALITY ASSURANCE STATEMENT NOTOX B.V., 's-Hertogenbosch, The Netherlands.
Study procedures were subject to periodic inspections and general non study specific processes were also inspected at periodic intervals.
This report was audited by the NOTOX Quality Assurance Unit and the methods and results accurately reflect the raw data.
DATES OF QAU INSPECTIONS/ AUDITS
REPORTING DATES
25 March 1994 28 March 1994 21 April 1994
25 March 1994 28 March 1994 21 April 1994
Quality Assurance Manager
C .3. Mitchell B.Sc.
Date: Page 3
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T-5874 REPORT APPROVAL STUDY DIRECTOR:
MANAGEMENT:
NOTOX Project 121275
Drs. R. de Vries C[cx
w.V Date: J.A.M.W. van Helvoirt Section head Physico Chemistry
Date: 0 < J Io b /
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T-5874
NOTOX Project 121275
PREFACE Sponsor
Study Monitor Testing Facility
Study Director Study plan
TEST SUBSTANCE
Identification Description Batch Purity Storage conditions Stability under storage conditions Expiry date
3M Belgium - Chemical Canadastraat 11 B-2070 ZWIJNDRECHT Belgium
EBC
Mr. R.H. Cox
NOTOX B.V. Hambakenwetering 3 5231 DD 's-Hertogenbosch The Netherlands
Drs. R. de Vries
Start: 30 March 1994 Completed: 07 April 1994
T-5874 Cream solid 2334 100% At room temperature in the dark
Stable January 01, 1996
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T-5874
NOTOX Project 121275
PURPOSE AND PRINCIPLE
The purpose of the study was to determine the partition coefficient of the test substance between n-octanol and water.
The partition coefficient (n-octanol/water) (P0w)
defined as the ratio
of the equilibrium concentrations in a two phase system consisting of
n-octanol and water.
The retention time of a substance in a reversed-phase High Performance liquid Chromatography (HPLC) chromatographic system is related to its partition coefficient (n-octanol/water). The HPLC method is useful for log Pow values between 0 and 6. Using the HPLC method, impurities are of minor importance. The HPLC method must also be applied if the test substance is a mixture of compounds but is not applicable to strong acids and bases, metal complexes, substances which react with the eluent or surface-active agents.
GUIDELINES
The study procedure described in this report was based on the following guidelines:
Organization for Economic Co-operation and Development (OECD), OECD Guideline for Testing of Chemicals, guideline no. 117: "Partition coefficient (n-octanol/water) High Performance Liquid Chromatography (HPLC) method" (adopted March 30, 1989).
European Economic Community (EEC), EEC-Directive 92/69 EEC, Annex V, Part A, Methods for the determination of physico-chemical properties, A.8: "Partition coefficient". EEC Publication no. L383, December 1992.
ARCHIVING
NOTOX B.V. will archive the following data for at least 10 years: protocol, report, test substance reference sample and raw data.
TEST SYSTEM AND RATIONALE
A High Performance Liquid Chromatograph with a spectrophotometric detector. The stationary phase was bonded silica C^g. The mobile phase was 75/25 (v/v) acetonitrile/water. Both HPLC instrumentation and conditions are described in the section "method of chemical analysis".
The test system was recognized by the international guidelines (OECD, EEC).
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T-5874
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REFERENCE SUBSTANCES
Six chemicals for which log Pow has been reported were used to calibrate the elution time in units of log Po w . The mixture of reference substances
consisted of:
Reference substance
- benzylalcohol (p.a., Merck) - toluene (p.a., Merck) - 1,4-dichlorobenzene (z.s., Merck) - fluoranthene (98%, GC, Aldrich Chemie) - dibenzyl (99%, GC, Aldrich Chemie) - 2,4-00T (99%, HPLC, Riedel de Han, Seelze,
FRG)
1 log PQW values according to the OECD guideline.
log Pq w 1
1.1 2.7 3.4 4.7 4.8 6.2
PERFORMANCE OF THE TEST
Preparation of the solutions
Solutions of the reference substances (except for ethylmethylketone) were prepared in methanol (HPLC-grade, Labscan Limited Co., Dublin, Ireland) at a concentration of 1.5-2 g/1. A mixture of the reference substances was prepared by adding 125 ul of each solution to a volumetric flask. Subsequently, this flask was made up with mobile phase to a final volume of 25.0 ml. For the determination of t0 (retention time of the unretarded component), a solution of formamide (p.a., Merck, Darmstadt, FRG) in methanol was prepared at a concentration of 1.7 g/1 and thereafter diluted 10 times with mobile phase. A stock solution of T-5874 was prepared by dissolving 165 mg test substance in 50.0 ml acetonitrile (3 minutes sonication). The stock solution was diluted 10 times with mobile phase, resulting in the test solution.
Performance of the test
The solutions were injected in the following sequence: the mixture of reference substances, mobile phase, the formamide solution, the test solution (in duplicate), mobile phase, the mixture of reference substances and the formamide solution.
Temperature of measurement
The temperature of the mobile phase was recorded several times during the measurements.
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METHOD OF CHEMICAL ANALYSIS
The conditions used for the High Performance Liquid Chromatographic method are described below:
Analysis
Column
Mobile phase
Flow Detection Injection volume
LiChrospher 100 RP-18; 125 x 4 (I.D.) mm;
dg= 5 vm (Merck, Darmstadt, FRG) 75/25 (v/v) acetonitrile (HPLC-grade, Labscan Limited Co., Dublin, Ireland)/Mi 11i-Q water (Mi Ili pore Corp., Bedford, MA, USA)
1 ml/min UV at X= 210 nm 10 yl
Instrumentation
HPLC Pump Autosampler Detector
Integrator
Series 410 LC (Perkin Elmer, Norwalk, CT, USA) ISS-200 (Perkin Elmer) SpectroMonitor 3100 (LDC Analytical, Riviera Beach, FL, USA) SP 4290 (Spectra Physics, San Jose, CA, USA)
DATA HANDLING
Using High Performance Liquid Chromatography, especially large log Pow values can be accurately determined?from the chromatographic retention data. To this end, the capacity factor (k') was used, since it is proportional to the partition coefficient. The capacity factor was calculated from the retention of the substance concerned (tr) and the unretarded component (t0 ):
k = (tr - t0)/t0
From the results of the reference substances, a plot of log Pow (x-value) versus log k ' (y-value) was constructed, using linear regression analysis. The log k f value of each component of the test substance was compared with the log k ' values of the reference substances with known log Pow values.
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RESULTS
Representative HPLC chromatograms of the test solution, the blank (mobile phase), the mixture of reference substances and the formamide solution are shown in Figures 1 to 4.
In the HPLC chromatograms of T-5874, using detection at 210 nm, one large peak at 4.1 minutes and a small peak at 7.7 minutes were observed. Between 1.6 and 4 minutes, several small peaks were observed. It was assumed that the large peak derived from the major component of test substance whereas the small(er) peaks derived from impurities.
The t0 was determined to be 0.90 minutes as a mean value of both measurements (i.e 0.89 and 0.90 minutes).
The mean values of the retention times, k ' values, log k ' values, log Pow and Pow v a l u e s ^ r e summarized in Table 1. The plot of log Pow (x-value) versus log k ' (y-value) from the reference.substances is shown in Figure 5.
Table 1 Results of the test.
Substance
V
k'
log k ' log Pow
Pow
benzylalcohol toluene 1,4-dichlorobenzene fluoranthene dibenzyl 2,4-DDT
1.14 2.24 2.89 5.67 4.07 9.12
0.274 1.503 2.229 5.330 3.547 9.190
-0.563 0.177 0.348 0.727 0.550 0.963
1.1 2.7 3.4 4.7 4.8 6.2
test substance peak 1 peak 2 (major comp.) several small peaks
7.70
7.598
0.881
5.6 2
4.05
3.525
0.547
4.4 2
1.6 / 4 0.79/ 3.47 -0.10/0.54 2.2/4.4 2
1 Mean value of the retention times of both chromatograms. 1 Interpolated from the regression line: y = 0.288x - 0.730 (r=0.972, n=6) Note : The calculations were performed using not rounded values.
39.8 xlO4 2.51X104 1.50x102 / 2.51X104
The temperature of the mobile phase was 20.2-20.6C during the measurements.
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T-5874 CHfiHHEL fl
NOTOX Project 121275
INJECT 87-04-94 08:44:55 S T O R E D TO BIN # 53
38136/121286
FILE 1.
METHOD
ANALVST: KRH
PEAK#
AREAX
1 8. 435
2 2. 453
3 1. 683
4E*
18.732 1. 288
6 2. 538
7 0. 468
8 2. 476 9 1. 977
18 0. 636
11 1. 864
12 2. 067
13 1. 718
14 11.232
15 10.435
16 38. 458
17 2. 814
TOTAL
100.
0.
RT 8. 15 0. 25 8. 34 0. 53 0. 73 1. 01 1. 39 1. 6 1. 71 1. 91 2. 37 2. 62 3. 13 3. 51 3. 67 4. 05 7. 69
07-84-94 08i44:55
RUN 18
INDEX 10
AREA BC 1399 82 6951 0 ? 3861 02 53119 08 3640 0 5 7175 0 5 1322 0 ? 7000 02 5588 02 1737 93 5268 02 5842 83 4857 02 31758 82 23435 02 188707 03 5634 01 282665
CH= "A" F'S= 1. BIN 53
Figure 1 HPLC chromatogram of the test solution of 330 mq/1 T-5874 in mobile phase.
Column Mobile phase Flow
Detection Injection volume
LiChrospher 100 RP-ld; 125x4 (I.D.) mm; dn=5 Um 75/25 (v/v) acetonitrile/Milli-Q water H 1 ml/min
UV, at X = 210 nm 10 yl
Jte'.Thf peaks between 0 and 1.6 minutes were also observed in the chromatograms of the blank (see Figure 2). Therefore It was assumed that these peaks did not derive from the test substance.
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T-5874
NOTOX Project 121275
CHANNEL ft
INJECT 87-04-94 09:74:84 STORED TO BIN # 56
DATA SAVED TO BIN # 56
38136/121286
FILE 1.
METHOD
ANALYST: KRH
ZAK#
BREAM
1 1. 543 18. 515
s 3. 853 4 55. 335 5 7. 768 6 6. 301 i 2. 583 s 11. 576
TOTAL
180.
9.
RT 8.15 8. 25 8. 34 8. 52 0. 67 8. 99 1. 18 1. 61
07-04-94 09:34:04
RUN 13
INDEM 13
AREA BC
877 02 5976 02 2198 02 31449 02 4415 03 3922 82 1426 03 6579 01
56834
CH= "fl" PS= 1. BIN 56
Figure 2 HPLC chromatogram of a blank (mobile phase).
Column Mobile phase Flow Detection Injection volume
LiChrospher 100 RP-18; 125x4 (I.D.) mm; dD=5 ym
75/25 (v/v) acetonitrile/Milli-Q water H 1 ml/min
UV, at X = 210 nm 10 yl
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T-5874 CHANNEL fi
INJECT 07-04-94 09:50:17
NOTOX Project 121275
DfiTfi SAVED TO BIN # 57
38136/1212 86
FILE 1.
METHOD
ANALYST: KRH
PERK*
-1
d
4 5 --6 89 10 11 12 1_< 14 15
AREfiX
0. 823 0. 145 0. 06 0. 879 0. 873 8O>-*.O1?313"1J 8. 112 11. 317 0. 013 10.567 15. 524 38. 584 0. 316 13. 272
TOTAL
100.
07--04-94 0. RUN 14
RT
0. 14 0. 25 0. 34 0. 53 0. 73 8. 9A 1. 14 1. 61 2. 24 2. 61 2. 89 4. 08 5. 68 6. 38 9. 13
AREA BC -1131 02 7039 02 291 7 02 42751 88 3542 05 6771 06 476774 03 5468 81 550640 01
61-I 02 514173 83 755334 01 1877333 01
15361 01 645770 01 4865613
INDEX
14
CH= ufi" PS= 1. BIN 57
Figure 3 HPLC chromatogram of the mixture of reference substances in mobile phase.
Column Mobile phase Flow Detection Injection volume
LiChrospher 100 RP-18; 125x4 (I.D.) mm; dp=5 urn 75/25 (v/v) acetonitrile/Milli-Q water 1 ml/min
UV, at X = 210 nm 10 yl
Page 12
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T-5874
NOTOX Project 121275
CHANNEL A
INJECT 0 7 - 0 4 - 9 4 07:77:4 4 STORED TO BIN # 49
DATA SAVED TO BIN # 49
38136/121286
FILE 1,
METHOD
ANALVS;T: KRH
PEAK#
a r e a ;/
1 0. 35 2 1. 189 s 0. 73 4 10. 44 5 1. 884 6 54. 548 7 6. 246 8 0. 12 9 3. 034 10 0. 424 11 20. 315
TOTAL
100.
07-04-94 07:37:44 0. RUN 6 INDEX 6
RT
0. -16 0. 77
-.5 ....55 0. 78 0. 89 1-11 1. 42 1. 87 2. 97 3. 65
AREA BC 2624 02 8926 02 5930 02 78363 08 14143 86 409437 08 * J79 85
899 05 23224 82
3185 0 < 156989 01 75R599
CH= "A" PS= 1. BIN 43
Figure 4 HPLC chromatogram of a formamide solution of 0.2 g/1 in mobile phase.
Column Mobile phase Flow Detection Injection volume
LiChrospher 100 RP-18; 125x4 (I.D.) mm; dD=5 ym
75/25 (v/v) acetonitrile/Milli-Q water H 1 ml/min
UV, at X = 210 nm 10 yl
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T-5874
NOTOX Project 121275
Figure 5 Plot of log Pow (x-value) versus log k ' (y-value) from the reference substances.
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