Document JrJ97zNbD7rdOXaadJ1e5xJa
BIODEGRADATION (OECD 301E)
TEST SUBSTANCE
Identity:A mixturecontainingperfluorooctanesulfonawthei,ch may alsobe referredtoas PFOS, FC-95,oras a component ofFC-203A. (1Octanesulfoniaccid)(CAS # 2795-39-3).
Remarks: The 3M productionlotnumber was notprovided.The test sample isFC-203 NFP which isequivalentoFC-203A. Currentinformation indicateistisa mixtureof 1.34% PFOS, 25% diethyleneglycolbutylether, 67.85% water,2.66% Sultonefoamer,3% sodium octylsulfate0,.1% sodium lauryslulfatea,nd 0.05% tolyltdazole.
The followingsummary appliesto a mixture with incompletely characterizedconcentrationsof impurities.Data may not accurately retlectthebiodegradabilityof Me fluorochemicalcomponent of the test sample.
METHOD
Method: ModifiedOECD ScreeningTest,OECD 301E withDOC Analysis Test type: Stateacute GLP: No Year Completed: 1984 Analyticamlonitoring:Dissolvedorganiccarbon(DOC) Statisticmaelthods: Resultswere determinedby calculatiofnthe% DOC removaland graphicinterpretation. Test organism source: A 50:50 mix ofsoilextractand secondaryeffluent. The secondary effluenwtas thesupernatantofan activatedsludgemixed liquorsample takenfrom an aerationbasinatthe Metro Wastewater Treatment Plant,St.Paul,MN, whilethesoilwas a mixtureoffresh,sandy loam garden soilsobtainedfrom Ramsey and Washington Countiesin Minnesota.
Test condition: Dilutionwater: Not given. Mineral nutrientmedium: Nutrientffiediumper OECD 301 E method usingeithersyntheticvitaminsolutionoryeastextract. Stock and testsolutionpreparation:Solutionswere preparedon a weighvvolume basisby dissolvintghetestsubstanceinOECD nutrient niedium. Initicaolncentrationwsere broughttothefollowinDgOC concentrationss:odium benzoate 20 mg DOC/L, linearalkylbenzene sulfonate(LAS) -15 rngDOC/L, and thetestsubstance-40 mg DOC/L. Test vessels: Not given. Incubationconditions:Not given.
I
Number
of concentrations:
one for test substance
yeast extract,
one
sodium benzoate yeastextracto,ne sodium benzoate vitaminsolution,
and one LAS yeastextracta,llinduplicate.
Test substance flaskconditions: Not given.
Totalsuspended solidsand pH on day of testing:Not given.
Element Basis: Decrease indissolvedorganiccarbon.
Remarks: There isno mentionof blankcontrolst,hereforeitisquestionable whether theywere includedinthe study
RESULTS
Nominal concentrations: Reference standards:sodium benzoate at20 mg DOC/L and LAS at-15 mg DOC/L; testsubstance:- 40 mg DOC/L.
Element values:28-day degradation: Duplicate1 = 87.2% Duplicate2 = 96%. Mean value= 92%.
Remarks: Testingwas conducted on a mixtureas describedintheTest Substance Remarks field.The valuesreportedapplytothatmixtureand not the fluorochemicaplroportionalone.
CONCLUSIONS
The testsubstance% degradationbased on the mean DOC removal was 92% after28 days.
The referencesubstance,sodium benzoate,obtained95% degradationby 7 days, however,the LAS onlyobtained43% by 28 days.
Submitter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St. Paul,Minnesota,55133
DATA QUALITY
ReliabilitKyJ:imischranking3. Study lackscompletedescriptioannd records ofthe method followeda,s wellas raw data records.The inoculumisnot propedycharacterizedT.here isno characterizatioofnthetestsubstance puritya,nd the studylacksanalyticaclonfirmatioonftheamount of fluorochemicaplroportioninthe solutions.
REFERENCES
The studieswere conducted by the3M Company, EnvironmentalLaboratory, St.Paul,MN, Lab Request number 9611,1984.
OTHER Last changed: 6/26/00
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TECHNICAL REPORT SUMMARY
TO: TECHNICAL COMMUNICATIONS CENTER - 201-2C-12
(Importan-t Ifreportisprintedon bothsideosfpaper,sendtwocopiesto TCC.)Guidelineosn reversseide.
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KEYWORDS: "b Code
Other Keywords
CURRENT
OBJECTIVE:
To test the repeatability of the modified
Test in measuring the biodegradability
of
products.
OECD Screening
Light Water
..........
REPORT A13STRACT: This abstractinformation is-distbruited by the Technical Communications Center to alert3M'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
these products, FC-203 NFP, was also included 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
biod gradable.
cc: R.L.Bohon-21-2W-05 D.R.Ricker-235-lB-10 D.W.Kent-236-2A-04
nfo :niti
MODIFIED OECD SCREENING TEST ON FC-203, FC-203A, AND FC-600
INTRODUCTION
This study was undertaken to demonstrate the biodegradability
Light Water (L/W) products, FC-600 and FC-203, using the internationally recognzied Modified OECD Screening Test@ i)
testing was requested by 3M Germany because of inconsistency
results of past biodegradation tests done on these products.
of two
This in the
Modified OECD Screening Tests conducted in 1980 by the 3M Environme?,, Laboratory showed that three L/W products were highly biodegradable 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 I for a summary of these results.
Table I
Results of 1980 Testing on Light Water Products
Product
7
FC-203 NFP 1
13
FC-206
23
FC-3017 2
37
3
Hydroquinone
89
% Degradation at Day:
14
21
27
28
85
93
91
93
90
94
93
92
94
96
96
95
92
97
94
93
Footnotes:
I FC-203 NFP is nonfreeze protected FC-203 and is equivalent to FC-203A.
2 3 FC-3017 is freeze protected FC-206.
Hydroquinone was the reference product.
These 1980 results contradict
those of H. Hellmann
a?J)D.
Muller
(3) who'
used a similar test method, the TOC Degradation Test
. Hellmann'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 contradict his own
(BOD) results were
for FC-206 in the 21-day long TOC Degradation Test BOD 5 /COD data. His 5-day biochemical oxygen demand 50% and 40% of the chemical oxygen demand (COD) of
FC-3017 and FC-206, respectively. This is a significant 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 BOD /COD measurements made by the 3M Environmental Laboratory and by othgp independent laboratories on 3M AFFF products. Such results typically show BOD values to range between 60% and 90% of the COD. For example, a colirction of such data on 3 U.S. military specification AFFF products manufactured by 3M is shown in Table 2.
OECD Page July
Screening 2 9, 1894
Table 2
BOD, Carbonaceous BOD, and COD Data on Mil-Spec AFFF Product
BOD
C-BOD
COD
BOD
C-BOD
Lab
(mg/i8) (mg/
(mg/kg)
COBO
20 COD
FC-203 C Lot 501
3M
580,000
600,000
730,000
.79
.81
740,000
Pace
800,000* 730,000* 810,000
730,000
Serco
440,000
440,000
737,000
.60
.60
Capsule
570,000
620,000
950,000
.6
.65
Galbraith
616,000
671,000
776,450
.79
.86
inoculum #1
Galbraith
670,000
641,000
776,450
.86
.82
inoculum #2
Average S. D.
575,000
594,000
782,000
.73
.75
85,000
90,000
80,000
.12
.12
Calculated BOD's from different dilutions were very inconsistent.
3M
Pace Serco Capsule Galbraith
inoculum #1 Galbraith
inoculum #2
Average S. D.
3M.
Pace Serco Capsule
Average S. D.
FC-206C Lot 502
290,000
350,000 240,000 260,000 416,500
290,000
370,000 260,000 320,000 411,000
380,000 360,000 450,000 370,000 410,000 407,250
395,500
374,000
407,250
325,000 73,000
338,000 57,000
396,000 33,000
FC-780B Lot 501
240,000
250,000 210,000 240,000
230,000
250,000 220,000 230,000
320,000 330,000 350,000 287,000 360,000
235,000 17,000
232,000 13,000
329,000 28,000
0.78
0.78 0.65 0.63 1.02
.97
.81 .16
.74
.71 .73 .67
.71 .03
0.78 0.82 0.70 0.78 1.01
.92
.83 .11
.71
.71 .77 .64
.71 .05
OECD Page July
Screening 3 9, 1984
METHODS AND MATERIALS
1. Procedure
Testing was performed in accordance with T@T)OECD Guidelines for testing of chemicals adopted May 12, 1981.
2. Chemicals
The reference materials used were laboratory grade sodium benzoate, (C H NaO ) F.W. = 144.11 and linear alkylbenzene sulfonate (LAS). Thz EAS iolution used was a 5.68% active solution supplied by the U.S.Environmental Protection Agency as a reference material for
biodegradation testing. The Light Water (L/W) test mateials used were U.S. FC-203 Lot 3072 provided 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 reference materials were dissolved in
the OECD nutrient solution and brought to the following initial
DOC concentrations:
sodium benzoate 20 mg/l, LAS approximately 15
mg/l, and L/W products approximately 40 mg/l. 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/l 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 determine 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 Tre'atment Plant. The combined inoculum was passed through Whatman 54 filter paper prior to usage.
INSTRUMENT
The organic carbon analyzer used was a Dorhman DC-52A. limit is approximately 2 mg of carbon per liter.
Its sensitivity
OECD Page July
Screening 4 9, 1984
SAMPLE HANDLING AND STORAGE
The sample preservation method used was that(?yescribed by the
manufacturer of the organic carbon analzyer.
The method involves
adding 1 drop of concentrated HC1 per 10 ml of filtered sample. This
brings the samples to less than pH 2. The samples were stored under
refrigeration in vials with aluminum foil lined caps. Our experience is that this storage method 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 graphically 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 degradation 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 other L/W products also varied considerably at days 7, 14, and 21. Again, this variation appears to be due primarily 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.
OECD Page July
Screening 5 9, 1984
Biodegradation
Table 3 of LIGHT WATER Products and Refernce materials
Product/vitamin Source
Sodium Sodium Sodium Sodium
Mean
Benzoate/Yeast-1(1) Benzoate/YeastBenzoate/Vit.-I ?2) Benzoate/Vit.-2
(3)
FC-203
/Yeast-1
FC-203/Yeast-2
FC-203/Vit.-l
FC-203/Vit.-2
Mean
U.S. FC-203/Yeast-1 U.S. FC-203/Yeast-2
Mean
FC-203A(5) /Yeast-1 FC-203A/Yeast-2
Mean
FC-6003 /Yeast-1 FC-600/Yeast-2
Mean
LAS/Yeast-I LAS/Yeast-2
Mean
7
98.8 99.6 94.4 88.6 95
11.7 29.5 29.4 24.8
26.9 64.3
12.6 13.2
6.6 7.7
22.8 5.9
% DOC Removal After X Days
14
17
21
27
28
30.5 29.1 32.6 88.6
25.1 90.8
8.5 89.1
75.5 10.5
7.8 8.8
25.1 20.4
28.4 27.0 27.7 90.2
89.8 91.0 80.5 95.6
79.2 90.7
95.5 96.0
11.0 85.1
86.4 92.5
--(6) 89.3
76.3
87.0
30
49.1
--tg) 29.7
95.3 92.1 83.6 95.2 92
96.5 97.5 97
87.2 96.0 92
94.2 88.8 91
52.1 33.4 43
Footnotes:
(1) Used yeast extract as vitamin source,
(2) Used OECD synthetic vitamin solution as
(3 From Antwerp 1982. (4)
17-day samples were only taken for LAS. (5) (6)From Antwerp 1980. Originally labelled
Sample contaminated, not used.
vitamin source. FC-203 NFP.
READY 100
Figure 1
BIODEGRADABILITY: ModLfLed ScreenLng OECD 301E -- Ado ted 12 Ma@ 81
EnvLronmentaL Lob Pequest No. 9611
THIS SERIES WAS RUN USING
90
'STHNDHRD' NUTRIENT SOLUTION
CONTHINING YEAST EXTRHCT.
BG --- -------- --- ------------.-.............................................................
.. ...........
C) 70
C3
........
....... .........................................................../........ ........
Z 50
cc C3 4o ............ cr_
............................. ......................../.................................
C9
ELI
C3 M
C:)
LiBge
m
I& uts
20 ..../.............. 10
.. ... ....................................
............x....s.mi
Mg 0 M:z
Mg
0
7
14
21
DRYS
Figure 2
READY BIODEGRADABILITY: ModLfLed ScreenLng T
OECD 301E -- Ado ted 12 Ma@ 81
EnvLronmenta@ Lob @equest No. 9611 100
THIS SERIES WAS RUN USING
90
STANDARD NUTRIENT SOLUTION
WITH VITAMIN SOLUTION.
80 ................................................................................................. / ...........
cc
c3 n
C.)
.....................................................................
0
..................................
:z so 0
cr_
CCr3_ 40 ...................................../...................................................................................
C9 w
C3 3o 0
m
20 .............................................................................................
Lege
10
A saoiu
X FO@-2a
0
7
14
21
DAYS
Figure 3
READY BIODEGRADABILITY: ModLfLed ScreenLng T OECD 301E -- Ado ted 12 Ma@ 81
EnvLronmentaL Lob Nequest No. 9611
THIS SERIES WAS RUN USING 90 'STANDARD' NUTRIENT SOLUTION
CONTAINING YEAST EXTRHCT.
00 ...........................................................................................
cr_
C3 70
C.3
...........................................................................................
C3
:Z 50
cr_ CCr3_ 40 .................................. C-9
..............................................................
C3 m 0
m
20 .................................. .....................0...............................................................
10
0
v
w
0
7
... ...
14
21
DAYS
Legenc
X rC@-2M,
Figure 4
RE19DY BIODEGRADABILITY: ModLfLed ScreenLng I
OECD 301E -- Ado ted 12 Ma@ 81
EnvLronmentaL Lob Request No. 9611
ioc THIS SERIES WAS RUN USING OSTANDHRD* NUTRIENT SOLUTION CONTAINING YERST EXTRACT.
90
THE LRS REFERENCE WAS DILUTED
WITH FRESH NUTRIENT SOLUTION
00
*ON
TEST
DAY
29
AND
RE-INOCULATED
. .................. . ........
.
. .. .. . .. . .. . .. ... .
cr_
70
C.) so . ....... 0
C3
--i -- - ------------
cr_ C3 4c cr_
C3 30 m
10
a
.....
---------- -------- ..............
--------------------
------
Of'Legend
A uts IV mom DIUMM uts
7
14
21
28
35
42
DAYS
OECD Page July
Screening 9 9, 1984
The modified OECD Screening Test is intended for use on single chemical 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 within 28 days, are regarded by the OECD guidelines as being readily biodegradable. Also, this result has to be reached within 10 days of the DOC removal first exceeding 10%. only one of the replicates of each of the four L/W products tested met this second OECD 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 may 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 difficult 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/l of DOC compared to the 40 mg/l of DOC used for the Light Water products. The reason for the slow rate of LAS biodegradation appears to be that LA Inhibited microbial degradation at the test concentration @6 . 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 graphically in Figure 4. Another researcher, has similarly reported a low level of biodegradation of LAS in the modified OECD screening test. D. Liu found tha larlon A (dodecylbenzene sulfonate) had a half life of 39 days. t7
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
biodegradable."
In all cases, the average DOC removal for L/W products
was greater than 90% after 28 days. L/W products were much more
degradable than the very commonly used and "readily biodegradable" surfactant, LAS.
OECD Page July
Screening 10 9, 1984
REFERENCES
(1) Organization for Economic Cooperation For Testing of Chemicals, Section 301 Modified OECD Screening Test, May 12,
and Development, Guidelines E, Ready Biodegradability: 1981.
(2) E. A. Reiner, Biodegradation of "LIGHT WATER" 6/80, 3M Technical Report No. 40, Dept. 0535, 6/30/80.
Products in OECD Test Project 9970012600,
(3) Dr. H. Hellmann and D. Muller, "Environmental Impact of Fire
Extinguishing Foam Compounds (Umweltgefahrdung durch
Feuerlosch-Schaummittell)."
The study was carF-il-ed-outby the
West German Institute of Hydrology (Bundesanstalt fur
gewasserkunde), April 18, 1979.
(4) D. Muller and T. Tittizer, "The TOC Degradation Test - A Process to Test Organic Materials for Complete Biodegradation (Der TOC Abbautest - ein Verfahren zur Prufung von organbischen Substa-nzen auf vollstandigen Biologische'n Abbau)." Developed at the Bundesanstalt for Gewasserkunde, Koblenz, Z. F. Waser-und Abwasser-Forschung (1979).
(5) Dohrman DC-52A Operating Manual, 4th Ed., 1978.
(6) R. D. Swisher, Marcel Dekker,
Surfactant Biodegradation, Inc., 1970.
pages 16-17 and 147,
(7) D. Liu, Study on Biodegradation of Aniline and Marlon A, Biodeterioration 5, Edited by T. A. Oxley and S. Barrry, 1983.