Document Zne4xOdKw60RLGO38q9265Y0Y
, FoS6747-l1-B
TECHNICAL REPORT SUMMARY
TO: TECHNICAL COMMUNICATIONS CENTER - P O I - X N
flinpoftant - If report is printed on both sides of paper, send t w copies to TCCJ
Division
-Environmental Laboratory (EE & PC)
Proiuci
Commercial C h e m i c a l s
Report Title
C h e m i c a l Oxygen Demand of CS-2151
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IIDept. Number 0535
lProioc1 Numhor
9970012600
Report Number
05 7
Author(4
E r i c A . R e i n e r , Environmental Laboratory/EE & PC,
Nolulmok Rulurorico
None ( S e e Environmental Lab Request #6260S:,
SECURITY
?o%Ey Confidential)
0 Closed
(Special Authorization)
3M CHEMICAL
REGISTRY
21-2W-5
Employee Number(r)
47816
NO. of P q o r Including Covorshooc
la New Chemicals Reported
0
No
(Select terms from 3M Thesaurus. Suggest other applicable terms.
To d e t e r m i n e t h e chemical oxygen demand of CS-2151
Chemical Oxygen Demand
f TITI )
ji(:gi'aUaL 3 011
Oxidat i o n E E U C Div. Fluorochemical Surf acta n t
~
~~
3EPORT ABSTRACT (200-250words) This abstract information is distributedby the Technical CommunicationsCenter ilert 3M'err to Company RLD. It i s Company confidontial material.
The chemical oxygen demand (COD) of CS-2151 w a s determined i n accordance w i t h t h e Standard Methods r e f l u x method and
a c c o r d i n g t o t h e S t a n d a r d Ampule COD Method of Oceanography I n t e r n a t i o n a l . The r e f l u x p r o t o c o l gave a COD of 66,000
mg/kg. The ample method gave a COD of 81,000 mg/kg. E x p e r i e n c e w i t h a wide va:riety of p e r f l u o r i n a t e d o r g a n i c s '
h a s shown t h a t t h e p e r f l u o r i n a t e d p o r t i o n s a r e n o t o x i d i z e d
under t h e c o n d i t i o n s of the COD test. The potassium s a l t
of t h e p e r f l u o r i n a t e d p o r t i o n of t h e s u b j e c t material w a s p r e v i o u s l y t e s t e d and showed no clhemical oxygen demand.
Thus t h e o b s e r v e d COD a p p e a r s t o lbe due t o t h e d i e t h a n o l amine p o r t i o n of t h e chem.lca1. Tlhe t h e o r e t i c a l oxygen demar of CS-2151, assuming comp'lete o x i d a t i o n of o n l y t h e diethanolamine p o r t i o n is 77,000 mg/kg.
bo lnformoti n Liaison
Iniiiuls:
L I $" I ntrod u c tion
COD OF CS-2151
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The c h e m i c a l oxygen demand (COD) t e s t measures t h e oxygen e q u i v a l e n t of a c h e m i c a l u n d e r s t r o n g o x i d i z i n g c o n d i t i o n s . When compared t o theoretical oxygen demand, COD can g i v e a n i n d i c a t i o n
of t h e s t a b i l i t y of t h e component t o chemical o x i d a t i o n . S i n c e most o r g a n i c compounds are c o m p l e t e l y d e g r a d e d i n t h e COD t e s t , t h i s test is frequently used f o r comparison with t h e biochemical oxygen demand (BOD) t e s t . F o r t h o s e materials degraded by t h e COD t e s t , t h e BOD/COD r a t i o g i v e s a n i n d i c a t i o n of t h e
completeness of biodegradation.
T h i s r e p o r t describes t h e t e s t performed on CS-2151 t o e v a l u a t e i t s COD. I t p r o v i d e s t h e d a t a g e n e r a t e d i n t h i s s t u d y and
compares t h e chemical oxygen demand t o t h e t h e o r e t i c a l oxygen
demand.
Methods and Materials
The 3 M , Environmental Lab- r e c e i v e d t h e liest s u b s t a n c e o n 11/4/80. The sample was a l i g h t , y e l l o w l i q u i d . I t was r e p o r t e d t o c o n t a i n 25% s o l i d s i n water. S o l i d p o r t i o n of t h i s p r o d u c t i s d e s i g n a t e d CS-2070.
Wade S c h i e l performed t h e c h e m i c a l oxygen demand t e s t i n
accordance with the standard Environmental Laboratory Protocol
( a t t a c h e d ) t h i s protocol is based on t h e Standard Methods chemical oxygen demand p r o c e d u r e . The COD was a l s o measured a c c o r d i n g t o t h e Oceanography I n t e r n a t i . o n a 1 S t a n d a r d Ampule COD Method ( c o p y a t t a c h e d ) . F o r b o t h p r o c e d u r e s , COD'S were a l s o r u n i n p a r a l l e l on p o t a s s i u m hydrogen phtha-late (KHP) r e f e r e n c e samples.
R e s u l t s and Discussion
D u p l i c a t e d e t e r m i n a t i o n s by t h e r e f l u x method gave COD f o r CS-2151 of 67,000 mg/kg and 6 6 , 0 0 0 mg/kg. A patassium hydrogen
p t h a l a t e s t a n d a r d r u n i n p a r a l l e l w i t h a t h e o r e t i c a l COD of 4 0 5 m g / l w a s determined to have a COD of 3 9 2 m g / l . Duplicate COD
measurements on CS-2151 by t h e a m p u l e p r o t o c o l were b o t h 81,000 mg/kg. The p a r a l l e l s t a n d a r d w i t h a t h e o r e t i c a l COD o f 176 mg/l
was d e t e r m i n e d t o have a COD of 1 7 0 m g / l .
P r e v i o u s s t u d i e s o n FC-98, which i s t h e same f l u o r o c h e m i c a l
e x c e p t t h a t p o t a s s i u m replaces t h e diethanolamine, showed t h a t FC-98 had no chemical oxygen demand. Therefore, it appears t h a t t h e chemical oxygen demand of CS-2151 i s due o n l y t o o x i d a t i o n o f t h e d i e t h a n o l a m i n e p o r t i o n of t h e molecule. The t h e o r e t i c a l COD of t h e CS-2151 s o l i d s (CS-2070), assuming i t s f l u o r o c h e m i c a l p o r t i o n and NH3 are n o t o x i d i z e d , is 307,000 mg/kg. Thus, t h e t h e o r e t i c a l COD of CS-2151, which is a 25% aqueous s o l u t i o n is
7 7 , 0 0 0 mg/kg.
Conclusion
The measured COD v a l u e s are consistent w i t h t h e h y p o t h e s i s t h a t o n l y t h e d i e t h a n o l a m i n e p o r t i o n of t h e molecule is d e g r a d e d i n t h e COD test.
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E
Environmntal Lab
Data Sheet AWULE
C.O.D.
Date analyzed / /2
Analyst y ,ri' L w
OCEAWOGRAPHY INTERNATIWL COD PROCEDURE
Sam1 e
Description
I
/L
m1 Simp1e
14
4 0 :w
2.r
I
I
I
TECHNICAL REPORT SUMMARY
TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN
(Itwortant - I f report i s printed on both sides of paper, send two copies to TCC.)
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Date
8/31/81
1'
Division
-E n v i r o n m e n t a l L a b o r a t o r y (EE & PC)
Proiocf
Commercial C h e m i c a l s D i v i s i o n
Report Title
B i o d e g r a d a t i o n of CS-2151 (CS-2070)
Don liicker , Commercial C h e m i c a l s D i v i s i o n , 53-4N
Au thor(r)
E r i c A. Reiner, Environmental Laboratory(EE & PC),
N l ~ l c i l i o o kl3ulurijiti:ir
Dept. Number
0535
Promct Nirmhor
9970012600
Report Number
053
I Employee Numbodd
SECuR'TY
?o:g:y
K EYWOR OS: (Select terms from 3 M Thesaurus. Suggest other applicable terms.)
Confidential)
0 Closed
(Special Authorization)
CURRENT OBJECTIVE:
3M CHEMICAL
REGISTRY
b
New Chemicals Reported
0 yes
Q No
To e v a l u a t e t h e s u s c e p t i b i l - i t y of CS-2151 t o biodegradation.
Biodegradation EEWC D i v . (Env. Lab) BOD
Fluorochemical Surfactant
REPORT ABSTRACT: (200-250 words) This abstract information is distributedby the Technical CommunicationsCenter to alert 3M'ers to Company R&D. It i s Company confidentialmaterial.
88 A 20-day b i o c h e m i c a l oxygen demand (BOD ) t e s t u s i n g
c o n c e n t r a t i o n s of CS-2151 r a n g i n g from t o 540 m g / l g a v e a BOD f o r CS-2151 of 6 9 , 4 0 0 mg/kg ( 2 7 8 , 0 0 0 mg/kg f o r CS-20787. Oxygen demand is presumed t o be d u e t o t h e d i e t h a n o l a m i n e p o r t i o n of t h e molecule since a p r e v i o u s l y
c o n d u c t e d BOD t e s t on t h e sodium s a l t o f t h e f l u o r o c h e m i c a l portion of CS%151 showed no oxygen uptake. The BOD was
e q u i v a l e n t t o 90% o f t h e theoretical oxygen demand f@ t h e
diethanolamine portion of t h e molecule assuming its
. c o m p l e t e c o n v e r s i o n t o C O Z i H 2 0 , and NH The p o s s i b i l i t y
of p a r t i a l d e g r a d a t i o n of t h e fl u o r o c h e h c a l p o r t i o n o f
. CS-2151 c a n n o t be e l i m i n a t e d by t h i s t e s t i n g However,
e x p e r i e n c e w i t h a w i d e v a r i e t y of s i m i l a r compound
i n d i c a t e s t h a t t h e p e r f l u o r i n a t e d p o r t i o n of t h i s m o l e c u l e w i l l not biodegrade.
Information Liaison
Initials: V \ n G
3M CONFIDENTIAL
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BIOCHEMICAL OXYGEN DEMAND OF CS-2151
Int r o d u c t ion
T h e o b j e c t i v e of t h i s s t u d y w a s t o o b t a i n a n i n d i c a t i o n of t h e
. b i o d e g r a d a b i l i t y of CS-2151, which is t h e d i e t h a n o l a m i n e s a l t o f
p e r f luoro ethylcyclohexane s u l f o n i c a c i d Its intended u s e is as a surfactant for m i s t suppression i n anodizing, electroplating, and e t c h i n g b a t h s . As a r e s u l t of t h e s e u s e s , it w i l l be d r a g g e d o u t w i t h p a r t s and w i l l e n t e r t h e e n v i r o n m e n t w i t h t h e water used
t o r i n s e t h e s e parts. When used i n s t r o n g - a c i d , e t c h i n g s y s t e m s , t h e e t h a n o l a m i n e p o r t i o n of t h e molecule would l i k e l y b e p a r t i a l l y or completely oxidized prior to its entry i n t o the
environment.
Methods and Materials
The E n v i r o n m e n t a l L a b o r a t o r y r e c e i v e d t h e test sample on 11/4/80. The sample was a l i g h t , y e l l o w l i q u i d . I t was r e p o r t e d t o
c o n t a i n 25% s o l i d s i n water. W. A. S o h i e l and M. R o b e r t s
performed t h e 5, 10, and 20-day biochemical oxygen tests
according to the attached standard Environmental Laboratory
p r o t o c o l . I n t h i s t e s t i n g , f o u r c o n c e n t r a t i o n s were used r a n g i n g from 68 t o 540 m g of CS-2151 per l i t e r of BOD d i l u t i o n water. T h e r e w a s l i t t l e oxygen d e p l e t i o n d u r i n g t h e frirst f i v e d a y s , b u t
a t 1 0 a n d 20 d a y s o n l y t h e BOD b o t t l e c o n t a i n i n g 68 mg/l of CS-2151 c o n t a i n e d g r e a t e r t h a n 0.5 mg/'l of oxygen r e s i d u a l . The oxygen d e p l e t i o n due t o t h e samples is; shown i n Table 1 below:
- T a b l e 1 Oxygen d e p l e t i o n d u e t o CS-2,151 (io!., oxygen d e p l e t i o n
i n sample bottle c o r r e c t e d for oxygen d e p l e t i o n due t o s e e d and
. w a t e r )
CS-2151
. - Conc (mg/l)
Oxygen D e p l e t i o n Due to Sam l e ( m /1)
!2L2 Day2 9-
68
0.06
4.17
4.69
140
0.16
>7,65
-e.
270
0.20
>7.65
-.-
540
0.31
>7.6
-. -
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-2-
When t h e r e is l e s s t h a n 2 mg/l oxygen d e p l e t i o n , t h e Environmental L a b o r a t o r y Protocol c a l l s f o r r e p o r t i n g BOD a s less t h a n t h e BOD v a l u e which would h a v e been c a l c u l a t e d i f t h e h i g h e s t t e s t material c o n c e n t r a t i o n had shown a n oxygen depletion of 2 mg/l. The 5-day BOD was t h u s r e p o r t e d t o be less t h a n 3,700 mg/kg. The BOD a t 5 and 10 d a y s w a s calculated based on t h e oxygen d e p l e t i o n of t h e 68 mg/l c u l t u r e i n accordance with t h e a t t a c h e d protocol. The reported BOD v a l u e s are, t h e r e f o r e :
BOD5 - (3,700 mg/kg
BOD10 - 62,000 mg/kg
BOD20 - 69,000 mg/kg
BOD tests have a l s o b e e n - d o n e on t h e pcltassium salt o f p e r f l u o r o
e t h y l c y c l o h e x a n e s u l f o n i c a c i d . The 20-day BO11 was found t o be
l e s s t h a n 3,800 mg/l. These r e s u l t s i n d i c a t e t h a t u n d e r t h e s e c o n d i t i o n s t h a t t h e p e r f l u o r i n a t e d port i o n of t:he molecule is u n l i k e l y t o degrade. Assuming n o n i t r i f i c a t i o n and no
b i o d e g r a d a t i o n of p e r f l u o r i n a t e d portion of t h e m o l e c u l e , t h e
t h e o r e t i c a l b i o c h e m i c a l oxygen demand would be 77,000 mg/kg (307
mg/kg for t h e 1 0 0 % s o l i d s m a t e r i a l ) . The o b s e r v e d BOD v a l u e was,
t h u s , 90% of t h e t h e o r e t i c a l assuming t h a t o n l y t h e
d i e t h a n o l a m i n e w a s biodegraded. S i n c e BOD v a l u e s r a r e l y r e a c h
t h e o r e t i c a l oxygen demand, these results i n d i c a t e e s s e n t i a l l y
complete molecule
. d
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a
d
a
t
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of
the
diethanolamine portion
of
the
Discussion
The r e s u l t s of t h i s t e s t i n g when e v a l u a t e d i n c o n j u n c t i o n w i t h BOD r e s u l t s on t h e p o t a s s i u m s a l t of t h e f l u o r o e h e m i c a l p o r t i o n of t h i s m o l e c u l e i n d i c a t e t h a t the fluorochemical portion of the
molecule would n o t biodegrade under t h e test colnditions, while
t h e d i e t h a n o l a m i n e p o r t i o n would be c o m p l e t e l y degraded. The
20-day b i o c h e m i c a l oxygen demand t e s t (BODZO) is a t e s t f o r r e a d y biodegradability. This test alone cannot exclude the possibility
t h a t t h e f l u o r o c h e m i c a l p o r t i o n of t h e m o l e c u l e may b i o d e g r a d e a f t e r l o n g e r p e r i o d s of a c c l i m a t i o n or u n d e r more favorable conditions. Such degradation is, however, very unlikely.
Literature studies conducted on an ongoing basis f o r several years have not uncovered articles t h a t describe t h e b i o d e g r a d a t i o n of a c o m p l e t e l y p e r f l u o r i n a t e d o r g a n i c material.
The 3M Environmental Laboratory h a s a l s o n o t s e e n t h e biodegradation of any 3M p e r f l u o r i n a t e d o r g a n i c materials.
A m m e n i a l Laboratory
BOD Work Shmt - Sampler
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ml with DI water
Note:
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2.- Sample Size = ml or g of sample or diluted sample added to BOD I3ottle.
Comments
Form 19756 PWO
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