3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

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# Final Report Water Solubility of Laboratory Project ID: Method or Regulatory Requirement: Non-GLP
Testing Laboratory 3M Environmental Health and Safety Operations 3M Environmental Laboratory

3M Environmental Laboratory Cleston Lange, Ph.D. 3M Environmental Health and Safety Operations 3M Environmental Laboratory

3M Center, Bldg 260-5N-17 St. Paul, MN 55144 Phone: 651-733-9860

clange@mmm.com

Client
Jeff Stolte 3M Materials Resource Division

3M Center, Bldg 236-1B-10 St. Paul, MN 55144 Phone: 651-575-0856

jstolte@mmm.com3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 2 of 9 1 Introduction/Summary The fluorinated polyurethane test substance was received in February 19, 2015 from 3M Materials Resource Division (MRD) for evaluating its water solubility at ambient room temperature via limit testing using a modified shake flask procedure. The test substance properties are described in Table 1

. The material was anticipated to be practically insoluble in water; therefore, solubility testing was performed as a limit test and conducted to evaluate whether a nominal 1 mg visible sample (actual 1.02 mg) would dissolve in 18 L of Mill-QTM water during > 24 hours at ambient temperature (22 + 1 °C) with gentle stirring. After the incubation, the glass vial was retrieved and the water decanted off and the recovered solids air dried. The air-dried sample was visibly examined for the presence non-solubilized test substance and photographed. Then the substance was dissolved into 0.5 mL acetone, transferred to a pre-weighed aluminum dish and acetone evaporated away and the sample air dried at ambient temperature, then accurate weight of recovered residue determined. Results showed that 1.02 mg of solid was recovered at 77% after a 44 hour solubility test period in 18 L water. Visual results recorded via photography added a second level of confirmation that the test substance did not significantly dissolve in the water. The results demonstrate that the water solubility of is significantly less than nominal 0.057 mg/L (< 57 ppb).3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 3 of 9 2 Experimental & Analytical 2.1.1 Test Substance The test substance is the dried fluorinated polyurethane . The substance was referred to as dried solids and identified as dried solids.
Table 1. Test Substance
Substance ID Alternative Name dried solids, urethane Source 3M Received Date 2/19/2015 Expiration Date 2/25/2020 Storage Frozen TCR No. Physical Descrip tion solid Purity 97.4%
2.1.2 Laboratory Equipment Laboratory temperature was recorded as facility data using a REES temperature monitoring system and calibrated thermocouples. The temperature of the laboratory where water solubility testing was conducted was maintained at within 22 + 1 °C between March 24 and March 26, 2015.

2.1.3 Balance Mettler Toledo SAG285 SemiMicro Balance SN: 1120370839 3M Metrology ID: 148930 LIMS ID: BAL ROBOT Functional Range 0.1 mg to 210 g Repeatability: 0.1 mg Linearity: + 0.2 mg
Note:The balance was verified accurate to 1.0 mg using a 1.0 mg calibrated weight, the smallest calibration verification weight available at the time. Readings below 1 mg were assumed3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 4 of 9 accurate based on the accuracy of the 1 mg weight and a stable tare reading at 0.00 mg. Precision was demonstrated in the range of 0.5 to 1.0 mg by repeated measurements of a aluminum foil weight prepared at nominal 0.6 mg, as discussed herein. 2.1.4 Calibration Verification Weight Set ID: 0222-8007 Class F Weight Set (1.00 mg-100 g) Serial Number: 7937 3M Metrology ID: 161204 2.1.5 Milli-Q® Element DI Water System Millipore Provides ASTM type-1 water 3M Metrology ID: 161236
2.1.6 Camera Fujifilm FinePixTM S9000 Digital Camera 28-300 mm, 10.7X optical zoom Serial Number: 61A51564

2.1.7 Solubility Test
The test substance was provided as a solid substance in February 19, 2015. The solubility testing was conducted in March 2015. Estimation of water solubility was conducted per a modification of the “Preliminary Test” procedure described in OECD-105. These modifications were performed to enhance the outcome of the evaluation by providing a water solubility value that is in the low part per billion (μg/L) concentration range. Due tothe anticipated poor solubility of the test substance at less than nominal 1 mg/L (< 1 ppm) and lack of reliable analytical methods to quantify the polymers at low ppm or ppb levels, the following procedure was performed to provide a water solubility limit based on visual observation of significant non-solubilized material remaining after being placed in a large volume of water (18 liters) for > 24 hours. Below is a detailed description of the test, as performed:
Step 1: An optically clear glass ~ 20 mL I-CHEM® vial had its weight determined and then was tared on a 5-place balance. Step 2: On 3/24/2015 a visible and measurable quantity of dried solids was accurately weighed into the bottom of a tared clear glass vial and recorded as 1.02 mg. A photograph was taken as a record of the visibility of the material before dissolution testing. A laboratory control sample was similarly prepared with 1.05 mg of test3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 5 of 9 substance, but not exposed to wa ter solubility testing and was retained for later stages of the testing. For each, the test substance was gently heated to adhere it to the bottom of the vial. Step 3 : The vial with 1.02 mg of test substance was then filled with MilliQTM water and carefully submerged into the final test volume of water (18L) contained in a 5 gallon HDPE pail. A magnetic stir bar was placed in the bottom and used for gentle stirring du ring the incubation using a magnetic stir plate. Step 4 : The solubility test was conducted from 2:45 PM on March 24, 2015 until 10:45AM on March 26, 2015 (44hrs,). The temperature of the ambient room air was recorded at 22°C+ 1°C during the water solubility experiment and assumed equal to the water temperature at the end of the experiment. Step 5: After the incubation period. The vial was carefully recovered and inspected for any visible, non-solubilized test substance. The test substance was visibly present as a disintegrated powder in the vial. The water phase was then carefully decanted off and the recovered solids air dried at ambient temperature and photographed. Step 6: The air-dried solids of the test sample and control sample were then dissolved into 0.5 mL acetone and transferred to a pre-weighed aluminum weigh boat. The acetone was evaporated away and the final recovered mass of accurately determined and recorded on 4/2/2015. A maximal solubility value was determined based the initial weight divided by the volume of water tested. For example, visible remaining material after dissolution testing for a 1.02 mg weight of test substance tested in 18 L water would result in a reported water solubility of less than 1.02 mg÷18 L (i.e. < 0.057 mg/L; < 57 ppb). Because solid non-dissolved material was recovered, the actual water solubility is confidentl y expected to be significantly less than this value.3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 6 of 9 2.1.8 Quality Controls
2.1.9 Laboratory Control Samples
A 1.05 mg aliquot of the test substance was accurately weighed into a clean clear I-CHEM® vial. The material was then air dried similar to the water solubility sample at ambient temperature. The results of LCSs were used to demonstrate no loss of test substance due to the drying process and to demonstrate accurate recovery of the substance via the drying procedures. The results of the LCS are shown in Table 3

.

2.1.10 Precision Evaluations
A small piece of aluminum foil (nominal mass 0.6 mg) was prepared as a precision evaluation weight. This precision weight was weighed 10 times prior to each balance use to validate the balance precision between 1 mg and 0.5 mg. The results determined for two different days of weight determination are shown in Table 4

.

3 Results

3.1.1 Balance Calibration Verification Results
Calibration verification of the balance was performed following ETS-9-006 “Use of Analytical Balances” using a 1 mg verification weight and demonstrated at within 100% +5% accuracy.3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 7 of 9 3.1.2 Solubility Test Sample Results
Recovery of Test Substance from the solubility test samples is shown in Table 2.

3.1.3 Photographic (Visual) Results
Photographs of the test substance were taken before and after the solubility test and are shown in Figure 1. The loss of the test substance was not observed. Slight changes in the color from yellow-tinted to white were observed, indicating potential loss of colored impurities during the solubility testing. The substance also appeared to disintegrate during the incubation period, originally starting as a single flake of material and ending as several small pieces and powdered substance after solubility testing.

Figure 1. before ( left ) and after ( right ) the solubility test. Table 2. Test Substance Recovery from Solubility Testing Substance ID Original Mass (mg) [a] Recovered Mass (mg) Percent Recovery [a] 1.02 0.79 77% [a] Values shown at 2 significant figures due to variability at the 0.01 mg position, however recoveries were determined using full precision3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 8 of 9 3.1.4 Laboratory Control Sample Results
A laboratory control sample was prepared by weighing 1.05 mg into a clean I-CHEM® vial, but not exposed to the water solub ility testing. The control sample was dried in parallel to the wate r solubility test samp le. Percent recovery of the dried laboratory control samples are reported in Table 3

.

To evaluate the precision of the balance in the mass range used, a sliver of aluminum foil was cut and weighed 10 times prior to weight determination on 3/24/2015 (initial weight determinations) and prior to weight determinations on 4/2/2015 (final recovered weight determinations). The average (+ std. dev.) determined mass was 0.582 +0.084 mg (RSD 14%), on 3/24/2015 and 0.63 + 0.048 mg (RSD 7.6%) on 4/2/2014. Results are shown in Table 4. Table 3. Laboratory Control Sample Recovery Substance ID Original Mass (mg) Recovered Mass (mg) Percent Recovery [a] control 1.05 0.980 93% [a] Values shown at 2 significant figures due to variability at the 0.01 mg position, however recoveries were determined using full precision

Table 4. Balance Precision (1.0 to 0.5 mg mass range)
Substance ID Determined Masses on 3/24/2015 (mg) Determined Masses on 4/2/2015 (mg) Measurement 1 0.56 0.56 Measurement 2 0.54 0.67 Measurement 3 0.57 0.68 Measurement 4 0.74 0.57 Measurement 5 0.48 0.58 Measurement 6 0.54 0.59 Measurement 7 0.55 0.64 Measurement 8 0.50 0.65 Measurement 9 0.68 0.66 Measurement 10 0.66 0.68 AVERAGE 0.58 0.63 STD. DEVIATION 0.084 0.048 RSD 14% 7.6%3M ENVIRONMENTAL LABORATORY PROJECT NO. Water Solubility of

Page 9 of 9 4 Conclusion The solubility of the test substance was investigated through limit testing using a modified shake flask procedure. These results were determined empirically through weighing of sample before and after solubility testing as well as visually recording via photographs. The water solubility of was determined to be negligible and less than 0.057 mg/L (< 57 ppb) at 22°C + 1°C. The percent recovery of test material during dissolution testing was 77% by mass. The recovery of the laboratory control sample was 93%. Precision of the analytical method was good based on repeat measurement of a control weight at between 1 mg and 0.5 mg, with an RSD of < 15% (n = 10).
5 Data/Sample Retention Data and samples will be retained according the 3M Environmental Laboratory SOPs. Data will be maintained and archiv ed within a study file identified as study . It is anticipated that the raw samples and the data files will be retained indefinitely.
6 Approval Signatures The following persons have reviewed and approved this report:

Cleston C. Lange, Ph.D. Project Lead Date

William K. Reagen, Ph.D., Technical Director Date

The 3M Environmental Laboratory’s Quality Assurance Unit has audited the data and report for this project.

Quality Assurance Unit Representative Date Digitally signed by Cleston C. Lange DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, email=clange@mmm.com, o=3M, cn=Cleston C. Lange Reason: I am the author of this document Date: 2015.04.30 08:28:33 -05'00'

Digitally signed by William K. Reagen DN: c=US, st=MN, l=St. Paul, ou=Laboratory Director, ou=3M Environmental Laboratory - authenticated by LRA, email=wkreagen@mmm.com, o=3M, cn=William K. Reagen Reason: I am approving this document Date: 2015.04.30 08:48:24 -05'00'

Digitally signed by Daryl K. Peterson DN: c=US, st=MN, l=St. Paul, ou=3M Environmental Laboratory - authenticated by LRA, email=dpeterson2@mmm.com, o=3M, cn=Daryl K. Peterson Reason: I have reviewed this document Date: 2015.04.30 09:22:27 -05'00'