Document Qk7ByG6npMZV0BOgm2x3OvyKE
M SLAG _ 0733
BIODEGRADATION (OECD 301E)
TEST SUBSTANCE ________________________________________
Identity: A mixture containing perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-203A. (1Octanesulfonic acid) (CAS # 2795-39-3).
Remarks: The 3M production lot number was not provided. The test sample is FC-203 NFP which is equivalent to FC-203A. Current information indicates it is a mixture of 1.34% PFOS, 25% diethylene glycol butyl ether, 67.85% water, 2.66% Sultone foamer, 3% sodium octyl sulfate, 0.1% sodium lauryl sulfate, and 0.05% tolyltriazole.
The following summary applies to a mixture with incompletely characterized concentrations o f impurities. Data may not accurately reflect the biodegradability o f the fluorochemical component o f the test sample.
METHOD____________________________________________________
M ethod: Modified OECD Screening Test, OECD 301E with DOC Analysis Test type: Static acute GLP: No Year Completed: 1984 Analytical m onitoring: Dissolved organic carbon (DOC) S tatistical methods: Results were determined by calculation of the % DOC removal and graphic interpretation. Test organism source: A 50:50 mix of soil extract and secondary effluent. The secondary effluent was the supernatant of an activated sludge mixed liquor sample taken from an aeration basin at the Metro Wastewater Treatment Plant, St. Paul, MN, while tine soil was a mixture of fresh, sandy loam garden soils obtained from Ramsey and Washington Counties in Minnesota.
Test condition: D ilution water: Not given. Mineral nutrient medium: Nutrient medium per OECD 301E method using either synthetic vitamin solution or yeast extract. Stock and te st solution preparation: Solutions were prepared on a weight/volume basis by dissolving the test substance in OECD nutrient medium. Initial concentrations were brought to the following DOC concentrations: sodium benzoate 20 mg DOC/L, linear alkylbenzene sulfonate (LAS) -1 5 mg DOC/L, and the test substance -4 0 mg DOC/L. Test vessels: Not given. Incubation conditions: Not given.
000972
Number o f concentrations: one for test substance yeast extract, one sodium benzoate yeast extract, one sodium benzoate vitamin solution, and one LAS yeast extract, all in duplicate. Test substance fla sk conditions: Not given. Total suspended so lid s and pH on day o f testing: Not given. Element Basis: Decrease in dissolved organic carbon.
Remarks: There is no mention of blank controls, therefore it is questionable whether they were included in the study
RESULTS____________________________________________________
Nominal concentrations: Reference standards: sodium benzoate at 20 mg DOC/L and LAS at -1 5 mg DOC/L; test substance: ~ 40 mg DOC/L.
Element values: 28-day degradation: Duplicate 1 = 87.2% Duplicate 2 = 96%. Mean value = 92%.
Remarks: Testing was conducted on a mixture as described in the Test Substance Remarks field. The values reported apply to that mixture and not the fluorochemical proportion alone.
CONCLUSIONS__________________________________________'
The test substance % degradation based on the mean DOC removal was 92% after 28 days.
The reference substance, sodium benzoate, obtained 95% degradation by 7 days, however, th LAS only obtained 43% by 28 days.
Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133
DATA QUALITY_______________________________________________
Reliability: Klimisch ranking 3. Study lacks complete description and records of the method followed, as well as raw data records. The inoculum is not properly characterized. There is no characterization of the test substance purity, and the study lacks analytical confirmation of the amount of fluorochemical proportion in the solutions.
REFERENCES_________________________ ______________________
The studies were conducted by the 3M Company, Environmental Laboratory, St. Paul, MN, Lab Request number 9611,1984.
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OTHER Last changed: 6/26/00
000974
F o rm 6 7 4 7 -1 1-D
TECHNICAL REPORT SUMMARY
TO: TECHNICAL COMMUNICATIONS CENTER - 201-2C-12 (Important -- Ifreport isprinted on both sides of paper, send two copies to TCC.) Guidelines on reverse side.
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Notebook Reference
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N o. o f Pages In clu d in g C ov erth ee t
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S E C U R IT Y 3 Open R epo rt& Summary D Closed Report--Open Summary 3M C H E M IC A L R E G IS T R Y
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Q Check box if new chemicals are reported. Use Chemi _ cal Registry Form 6 0 9 2 to report all new substances.
KEYWORDS: Lab Code
1:I1:'' -1.J-1
Other Keywords
C U RRENT OBJECTIVE:
To test the repeatability of the modified Test in m e a s u r i n g the b i o d e g r a d a b i l i t y of products.
OECD Screening Light Water
R EP O R T ABS TR A C T: This abstract information is distributed by the Technical Communications Center to alert 3M'ers to Company R&D.
This study again used the modified OECD Screening Test to evaluate the biodegradability of Antwerp Light Water products. The products studied in this set of tests were FC-203, FC-203 NFP (equivalent to FC-203A), and FC-600. Also tested was U.S. FC-203 Lot 3072. One of JL-i-JL these products, FC-203 NFP, was also i n cluded in the previous set of tests done in 1980. The results of this testing were consistent with previous OECD Screening Test studies on Light Water products. The results indicate that all of the tested products are readily biodegradable.
ce: R.L.Bohon-21- 2W-05 D.R.Ricker-23 5-1B-10 D.W.Kent-236- 2A-04
InformatiqpTLiaison
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000375
MODIFIED OECD SCREENING TEST ON FC-203, FC-203A, AND FC-600
INTRODUCTION
This study was undertaken to demonstrate the biodegradability of two Light W ater (L/W) products, FC-600 and FC-203, using the-., internationally recognzied Modified OECD Screening Test' . This testing was requested by 3M Germany because of inconsistency in the results of past biodegradation tests done on these products.
Modified OEC D Screening Tests conducted in 1980 by the 3M Environmental Laboratory showed that three L/W products were highly biodegradable 2 . The products tested were FC-203A (previously identified as FC-203 NFP) , FC-206, and FC-3017 (FC-206 freeze protected). Greater than 90% of the dissolved organic carbon (DOC) of these 3 products was removed during the 1980 testing. See Table 1 for a summary of these results.
Table 1
Results of 1980 Testing on Light Water Products
Product
FC-203 NFP1
FC-206 ,
FC-3017^
3
HydroquinoneJ
7
13 23 37 89
% Degradation at Day;
11 11
27
85 93 91 90 94 93 94 96 96
92 97 94
28
93 92 95 93
Footnotes :
1 FC-203 NFP is nonfreeze protected FC-203 and is equivalent to 2 FC-203A. , FC-3017 is freeze p r o t e c t e d FC-206.
Hydroquinone was the reference product.
These 1980 results c o n t r a d i c t those of H. H e l l m a n n and.D. M u l l e r (3) w h o used a similar test method, the TOC Degradation T e s t 1 . H e l l m a n n 's TOC (total organic carbon) test results, however, are an exception from normally obtained results. His finding of 8% TOC removal for FC-3017 and 6% TOC removal for FC-206 in the 21-day long TOC Degradation Test contradict his own BOD5/COD data. His 5-day biochemical oxygen demand (BOD) results were 50%3and 40% of the chemical oxygen demand (COD) of FC-3017 and FC-206, respectively. This is a s i g n i f i c a n t level of degradation for a 5-day BOD test. These opposite results within his own paper clearly are an inexplicable discrepancy.
Hellmann's TOC Degradation Test results are also inconsistent with BOD20/COD measurements made by the 3M Environmental Laboratory and by other independent laboratories on 3M AFFF products. Such results typically show B O D 20 values to range between 60% and 90% of the COD.For example, a collection of such data on 3 U.S. military specification AFFF products m a n u f a c t u r e d by 3M is shown in Table 2.
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OECD Screening Page 2
J u l y 9, 1894
Table 2
BOD, Carbonaceous BOD, and COD Data on Mil-Spec AFFF Product
O^20
C-BOD,,,,
COD
C - B O D ,, rt
Lab (mg/Rq) (mg/k3? (mq/kq)
COD^U
FC-203 C Lot 501
3M
Pace
Serco Capsule Galbraith
inoculum #1 Galbraith
inoculum #2
580,000
800,000*
440,000 570,000 616,000
670,000
600,000
730,000*
440,000 620,000 671,000
641,000
730.000 740.000 810,000 730,000 737,000 950,000 776,450
--- --
776,450
.79
.60 .6 .79 .86
.81
.60 .65 .86
00 to
Average S. D.
575,000 85,000
594,000 90,000
782,000 80,000
.73 .12
.75 .12
* Calculated BOD's from different dilutions were very inconsistent.
FC-206C Lot 502
3M
Pace Serco Capsule Galbraith
inoculum #1 Galbraith
inoculum #2
290,000
350,000 240,000 260,000 416,500
395,500
290,000
370,000 260,000 320,000 411,000
374,000
380.000 360.000 450,000 370,000 410,000 407,250
407,250
0.78
0.78 0.65 0.63 1.02
.97
0.78
0.82 0.70 0.78 1.01
.92
Average S. D.
325,000 73,000
338,000 57,000
396,000 33,000
.81 .16
.83 .11
FC-780B Lot 501
3M
Pace Serco Capsule
Average S. D.
240,000
250,000 210,000 240,000
235,000 17,000
230,000
250,000 220,000 230,000
232,000 13,000
320.000 330.000 350,000 287,000 360,000
329,000 28,000
.74
.71 .73 .67
.71 .03
.71
.71 .77 .64
.71 .05
;*ft
OECD Screening
Page 3 J u l y 9, 1984
H
METHODS AND MATERIALS
1. P r o c e d u r e
T e sting was p e r f o r m e d in a c c o r d a n c e wi t h t h e .O E C D G u i d e l i n e s for testing of c h e m i c a l s a d o p t e d May 12, 1981. '
2. C h e m i c a l s
The reference materials used were laboratory grade sodium benzoate, (C^H-NaO) F.W. = 144.11 and linear alkylbenzene sulfonate (LAS). The LAS solution used was a 5.68% active solution supplied by the U . S .E n v i r o n m e n t al P r o t e c t i o n A g e n c y as a r e f e r e n c e m a t e r i a l for biodegradation testing. The Light Water (L/W) test mateials used were U.S. FC-203 Lot 3072 p r ovided in 1983 by the Commercial Chemicals Division, FC-203 and FC-600 samples provided by E.T.S.L. Antwerp in 9/82 and FC-203 NFP provided by E.T.S.L. in 1980. Antwerp provided no lot numbers with their samples. FC-203 NFP (nonfreeze protected) is equivalent to FC-203A.
Prior to testing, the L / W and re f e r e n c e m a t e r i a l s w e r e d i s s o l v e d in the OECD nutrient solution and brought to the following initial DOC concentrations: sodium benzoate 20 m g / 1 , LAS a p p r o x i m a t e ly 15 m g / 1 , and L/W products ap p r o x i m a t e ly 40 mg/1. The L / W TOC was higher than that used in previous testing (20 mg/1) because our experience has shown that L/W at 40 mg/1 is not toxic. Also higher concentrations improve the accuracy of the TOC analysis.
For this study, nutrient solutions were prepared using both vitamin sources allowed by the OECD Screening Test, yeast extract and synthetic vitamin solution. This was done to d etermine if the vitamin source affected the extent of L/W degradation.
INOCULUM
The inoculum was a 50/50 mixture of soil extract and secondary effluent prepared in accordance with OECD procedures. The soil, which was extracted, was a mixture of fresh, sandy loam garden soils obtained from Ramsey and Washington Counties in Minnesota. The secondary effluent sample was the supernatant of an activated sludge mixed liquor sample taken from an aeration basin at the St. Paul Metro Wastewater Treatment Plant. The c o m bined inoculum was passed through Wh a t m a n 54 filter paper prior to usage.
INSTRUMENT
The organic carbon analyzer used was a Dorhman DC-52A. Its sensitivity limit is a p p r o x i m a t e l y 2 mg of c a r b o n per liter.
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OECD Screening Page 4 J u l y 9, 1984
s
SAMPLE HANDLING AND STORAGE
The sample preservation method used was that-prescribed by the manufacturer of the organic carbon analzyer. ' The method involves a dding 1 d r o p of c o n c e n t r a t e d HC1 p er 10 ml of filtered sample. This b rings the s a mples to less than pH 2. The samples were stored under refrigeration in vials with aluminum foil lined caps. Our experience is that this storage m e thod can preserve L/W containing samples for several months without affecting the DOC. All DOC analyses on samples from this study were done within one week of its completion.
RESULTS AND DISCUSSION
Table 3 summarizes the results of this study. This table shows that sodium benzoate, the reference compound, was_nearly completely degraded (95%) within 7 days. Every replicate of all of the L/W products showed greater than 80% TOC removal within the 28-day test period. Seven of the ten test flasks containing the various L/W products showed greater than 90% TOC removal. The average DOC removal for all four L/W product was greater than 90%.
The results of this testing are shown g r a p h i c a l l y in Figures 1 and 2. These results are averaged, and because of this, do not show the actual pattern of degradation in the individual cultures. Figure 3 is an example graph of 2 cultures degrading the same product, FC-203 NFP. It shows that once degradatio n of this product began that it was very rapid, but that the lag prior to the onset of degradation was variable. The reason for this variability between the duplicate cultures was not known nor was it expected. It may have been due to the fact that the cultures received different levels of viable microorganisms capable of degrading the major components of the Light Water products. Thus, the population of bacteria with these capabilities had to build up in the cultures prior to the onset of rapid (exponential) degradation.
Review of the data in Table 3 indicates that results of replicate testing of the o t h e r L / W pro d u c t s also varied c o n s i d e r a b l y at d a y s 7, 14, and 21. Again, this variation appears to be due p r i m a r i l y to the length of the lag phase prior to the onset of biodegradation. However, due to the small number of samples taken, one frequently could not tell how long biodegradation of individual L/W containing cultures took following the initial lag.
000979
OECD Screening Page 5 J u l y 9, 1984
4
Table 3
Biodegradation of LIGHT WATER Products and Refernce Materials
Product/Vitamin Source
Sodium Benzoate/Yeast-1 (1)
Sodium Sodium
B B
e e
nnzzooaattee//YVeiats.t--1212)
Sodium B e n z o a t e / V i t .-2
Mean
F C - 2 0 3 (3 V Y e a s t - 1 FC-203/Yeast-2 FC-203/Vit.-1 FC-203/Vit.-2
Mean
___________ % DOC Removal A f t e r X Days 7 1_4 1 1 21 2 1
98.8
99.6 94.4
88.6 95
11.7 29.5 29.4 24.8
30.5 29.1 32.6 88.6
__(4 ) --
28.4 27.0
27.7 90.2
89.8 91.0 80.5 95.6
95.3 92.1 83.6 95.2 92
U.S. FC-203/Yeast-l
U.S. FC-203/Yeast-2 Mean
26.9 64.3
25.1 90.8
...
79.2 90.7
95.5 96.0
96.5
97.5 97
F C - 2 0 3 A (5)/ Y e a s t - l FC-203A/Yeast-2
Mean
F C - 6 0 0 3/ Y e a s t - l FC-600/Yeast-2
Mean
12.6 13.2
8.5 89.1
__
6.6 75.5 ---- 7.7 10.5
11.0 85.1
86.4 92.5
__(6 ) 89.3 76.3 87.0
87.2 96.0 92
94.2 88.8 91
LAS/Yeast-1
LAS/Yeast-2 Mean
22.8 5.9
7.8 8.8
25.1 20.4
49.1 l _ d ) 29.7
52.1
33.4 43
Footnotes:
Used yeast extract as vitamin source.
Used OECD synthetic vitamin solution as vitamin source.
From Antwerp 1982.
17-day samples were only taken for LAS.
From Antwerp 1980. Originally labelled FC-203 N F P .
' ' Sample contaminated, not used.
0003S0
Figure 1
BIODEGRflDflBILITYJ Modified Screening Test OECD 301E -- Adopted 12 May 81
Environmental Lab Request No. 9611
100
90
80
70
60
50
10
30
20
10
0
Figure 2
READY BIODEGRADABILITY: Modified Screening Test OECD 301E -- Adopted 12 Mag 81
Environmental Lab Request No. 9611
Figure 3
DY BIODEGRADABILITY: Modified Screening Test OECD 30IE -- Adopted 12 May 81
Environmental Lab Request No. 9611
100
90
80
70
60
^D
50
40
30
20
Legend
10 A re-205, ANTWERP '80 NFP (FLASK NO. 1)
X F0-203, ANTWERP *00 NFP (FLASK NO. 2) 0
DAYS
i p q: . V
Figure 4
DY BIODEGRADABILITY: Modified Screening Test OECD 301E -- Adopted 12 Mag 81
Environmental Lab Request No. 9611
100 THIS SERIES HRS RUN USING 'STflhffiRRD1 NUTRIENT SOLUTION CONTAINING TERST EXTRACT.
90
THE LAS REFERENCE HAS DILUTED HITH FRESH NUTRIENT SOLUTION 90 ON TEST DAT 29 AND RE-INOCULATED.
70
60
50
40
30
20
10
0
DAYS
OECD Screening Page 9
J u l y 9, 1984
It
The m o d i f i e d O E C D Screeni n g Test is intended for use on s i ngle c h e m i c a l substances. L/W products, on the other hand, are aqueous solutions containing a mixture of chemicals. Pure chemicals, which have greater than 70% loss of DOC w i t h i n 28 days, are regarded by the O E C D guidelines as being readily biodegradable. Also, this result has to be reached w i t h i n 10 days of the DOC removal first e x c e e d i n g 10%. On l y one of the replicates of each of the four L/W products tested met this second OEC D requirement of 70% degradation within 10 days of first reaching 10% degradation. This requirement, however, is not realistically applicable to L/W or other formulated products (mixtures). The chemicals within mixtures will frequently have differing susceptibilities to biodegradation. Readily degradable chemical components of such products may start to degrade immediately, while the onset of degradation of other chemicals in these products ma y be delayed. Thus, disregarding this second criteria, which is not reasonable for mixtures of chemicals, the results show that the mixture of chemical components in each of these products is readily biodegradable.
Cultures tested with the synthetic vitamin solution showed, on average, a slightly lower level of DOC removed than cultures using yeast extract as the vitamin source. Future OECD screening tests should thus use yeast extract since the synthetic vitamin solution is more diff i c u l t to prepare and does not give improved degradation.
LAS, which is a readily biodegradable and commonly used surfactant in detergents, did not degrade fully under these test conditions. This occurred in spite of the fact that its concentration was only 15 mg/1 of DOC c o m p a r e d to the 40 rag/1 of DOC used for the Light W a t e r products. The reason for the slow rate of LAS biodegradation appears to be that LAS,inhibited microbial degradation at the test concentration' . To check this hypothesis, at the end of the 28-day test period, the remaining LAS containing test cultures were split and half were diluted to twice their volume with fresh inoculated nutrient media. At this point, the rate of degradation in the diluted cultures increased substantially. Seventy percent of the DOC remaining at the time of dilution was removed within 15 days. Results of this work on LAS are shown g r a p h i c a l l y in Figure 4. A n o t h e r r e s earcher, has similarly reported a low level of biodegradation of LAS in the modified O E C D screening test. D. Liu found that_ M a r l o n A ( d o d e c y l b e n z e n e sulfonate) had a half life of 39 days. '
CONCLUSIONS
The present studies repeated the findings of previous OECD Screening Tests on Light Water products done by the 3M Environmental Laboratory. Both sets of tests showed that L/W products are "readily biodegr adable." In all cases, the average DOC remo v a l for L / W p r o d u c t s was greater than 90% after 28 days. L/W products were much more degradable than the very commonly used and "readily biodegradable" surfactant, LAS.
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OECD Screening Page 10 J u l y 9, 1984
REFERENCES Organization for Economic Cooperation and Development, Guidelines For Testing of Chemicals, S e c t i o n 301 E, R e a d y B i o d e g r a d a b i l i t y : Modified OECD Screening Test, May 12, 1981.
(o \ E. A. Reiner, B i o d e g r a d a t i o n of " L I G H T WATE R " P r o d u c t s in O E C D Test 6/80, 3M Technical Report No. 40, Dept. 0535, Project 9970012600, 6/30/80.
(3 ) Dr. H. H e l lmann and D. Mul l e r , " E n v i r o n m e n t a l I m pact of Fire E x t i nguishing Foam C o m p o u n d s (U m w e l t g e f a h r d u n g d u r c h F e u e r l o s c h - S c h a u m m i t t e l l )." T he s t u d y was c a r r i e d out by the West G erman Institute of H y d r o l o g y (B u n d e s a n s t a l t fur g e w asserkunde), April 18, 1979.
(4) D. M u l l e r and T. T i t t i z e r , "The TO C D e g r a d a t i o n T e s t - A P r o c e s s to Test Organic Materials for Complete Biodegradation (Per TOC Abbautest - ein Verfahren zur Prfung von Organbischen Substanzen auf V o l l s t n d i g e n B i o l o g i s c h e n A b b a u )." D e v e l o p e d at the B u n d e s a n s t a l t for G e w a s s e r k u n d e , K o blenz, Z. F. W a s e r - u n d Abwasser-Forschung (1979). Dohrman DC-52A Operating Manual, 4th Ed., 1978. R. D. Swisher, S u r f a c t a n t B i o d e g r a d a t i o n , p a g e s 16-17 and 147, Marcel Dekker, Inc., 1970.
(7) D. L i.u , S t u d y on B i o d e g r a d a t i o n of A n i l i n e and M a r l o n A, B i o d e t e r i o r a t i o n 5 , Edit e d by T. A. O x l e y and S. Barrry, 1983.
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