- Email: [email protected]
Fate of acetone in water
mosphere, Vol.ll, No.ll, nted in Great Britain
pp
1097-1114,
1982
0045-6535/82/111097-18503.00/ ©1982 Pergamon Press Ltd.
FATE OF ACETONE IN WATER Ronald E. Rathbun*, Doyle W. Stephens, Davzd J. Shultz, and Doreen Y. Tai U.S. Geological Survey, NSTL Station, Mississippi 39529
Abstract
The physical, chemical, and biological processes that might affect the concentration of tone in water were investigated in laboratory studies. Processes considered included atilization, adsorption by sediments, photodecomposition, bacterial degradation, and orption by algae and molds. It was concluded that volatilization and bacterial degradati, e the dominant processes determining the fate of acetone in streams and rivers. roduction The fate of organic compounds in streams and rivers is determined by the interactions o: plex physical, chemical, and biological processes.
Among the physical processes are
vective mass transport, dispersion, volatilization, and adsorption by sediment. mical processes are photodecomposition, hydrolysis, and chemical reaction.
Among th,
Among the
logical processes are bacterial degradation and absorption by biota. Acetone is infinitely soluble in water and therefore, it was selected as a model compoul resentative of the very water soluble class of organic compounds. sons for selecting acetone as the model compound. d.
There are a number of
It is a common solvent and is widely
Determination of organic compounds in various types of waters showed that acetone was
compound occurring most frequently I.
Also a survey of trace organics in the finished
nking water of 10 cities in the United States showed that only acetone and chloroform werd sent in all the waters 2.
Acetone has been identifled in leachates from landfills 3, in
er effluents from energy-related processes4, and also may be present in wastewaters from age treatment plants operated above optimum capacity 5 where it is formed as an intermedia omposition product.
Under some conditions, acetone may be a precursor in the formation o
orinated hydrocarbons during the chlorination of drinking water supplies 6. This report describes the results of laboratory studies of the processes affecting the centration of acetone in water.
Reports describing the results of field studies are also
nned.
1097
The s t u d i e s of acetone were l i m i t e d to systems in w h i c h b a s i c a l l y one p r o c e s s was rative.
In n a t u r a l streams, however,
several p r o c e s s e s will
/sly, r e s u l t i n g in effects that may be nonadditive. one p r o c e s s
likely be o p e r a t i n g simulta-
C o n s i d e r a t i o n of systems w h e r e m o r e
is o p e r a t i v e is b e y o n d the scope of this study.
~ry
Brief s u m m a r i e s of the general a s p e c t s of v o l a t i l i z a t i o n , ~mposition, b a c t e r i a l degradation,
a d s o r p t i o n by sediments, phot
and a b s o r p t i o n by a l g a e and m o l d s a n d a brief d i s c u s s i
the e x p e c t a t i o n of the i m p o r t a n c e of each of these p r o c e s s e s
for a c e t o n e will be given.
~ective m a s s t r a n s p o r t and d i s p e r s i o n have been d i s c u s s e d in detail p r e v i o u s l y 7, and will be c o n s i d e r e d .
In general,
the i m p o r t a n c e of these two p r o c e s s e s
relative to the other
zesses will d e p e n d on h y d r a u l i c c o n d i t i o n s in the stream; t h e s e c o n d i t i o n s d e t e r m i n e the nsport and d i s p e r s i o n c h a r a c t e r i s t i c s .
Therefore,
because of the wide range of h y d r a u l i c
ditions in s t r e a m s and rivers, a wide range of t r a n s p o r t and d i s p e r s i o n c h a r a c t e r i s t i c s expected.
H y d r o l y s i s and c h e m i c a l r e a c t i o n were c o n s i d e r e d not to have s i g n i f i c a n t effec
Icetone in streams. •t i l i z a t i o n -- V o l a t i l i z a t i o n is the t r a n s f e r of an o r g a n i c c o m p o u n d from the w a t e r acros water-air
i n t e r f a c e into the air as a result of the r a n d o m kinetic m o t i o n s of the m o l e c u
the c o m p o u n d a n d the c o n c e n t r a t i o n d i f f e r e n c e between the w a t e r and air.
This p r o c e s s
is
st orderS, 9 and t h e r e f o r e can be d e s c r i b e d by
dc --= dt
~e K v is the v o l a t i l i z a t i o n c o e f f i c i e n t ,
K v ( C - CE)
(
C is the c o n c e n t r a t i o n of the c o m p o u n d in the
er at time t, a n d C E is the c o n c e n t r a t i o n that the c o m p o u n d w o u l d have in the w a t e r if it • in e q u i l i b r i u m with the p a r t i a l p r e s s u r e of the c o m p o u n d in the air. The t w o - f i l m m o d e l of Lewis and Whitman10 ion of o r g a n i c c o m p o u n d s from water.
is f r e q u e n t l y u s e d to d e s c r i b e the v o l a t i l i -
T h i s model assumes u n i f o r m l y - m i x e d w a t e r and air
ses s e p a r a t e d b y thin films of w a t e r and air in w h i c h m a s s t r a n s p o r t is by m o l e c u l a r fusion.
The e q u a t i o n r e l a t i n g the film c o e f f i c i e n t s of the t w o - f i l m m o d e l is11, 12
I
I
RT
+ KOL
kL
--
(
Hk G
~e K O L is the o v e r a l l m a s s - t r a n s f e r c o e f f i c i e n t based on the liquid phase, k L is the aid-film mass transfer coefficient,
R is the ideal gas constant, T is the a b s o l u t e temper
ce, H is the H e n r y ' s Law constant, and kG is the g a s - f i l m mass t r a n s f e r c o e f f i c i e n t . The v o l a t i l i z a t i o n c o e f f i c i e n t of E q u a t i o n ~quation
(2) are related12,13
by
(I) and the o v e r a l l m a s s - t r a n s f e r c o e f f i c i e n
i0!
KOL = KvY
q
~re Y is the depth of the water phase. Because follows
the r e c i p r o c a l that
I/Ko L in E q u a t i o n
liquid p h a s e ~pectively. 3istance
of a m a s s - t r a n s f e r
and
Analysis
of Equation
in the air
is r e s i s t a n c e
between
~uming s p e c i f i c
into high,
npounds
having
3istance
films d e p e n d s
conditions
low,
to v o l a t i l i z a t i o n
Latilization
is in the air film.
resistance
~ay -I and a k G value Acetone
has b e e n
volatility
film.
to v o l a t i l i z a t i o n .
compound
aqueous
solutions
[m.
Therefore,
3orption
on s e d i m e n t s
depends
the s e d i m e n t :ticle, hural
H values have
are based on a k L value
of 4.~
by Liss and Slater 11. in the high volatilit) Law c o n s t a n t ,
of the solute,
The a c t i v i t y
coefficient
std arm,
is s l i g h t l y
larger
and P
is s and the vapor
respectively, than the
giving
1.2 x 10-5
resistances
will
be i m p o r t a n t
in the volatilizatJ
will
be in the air film.
that b o t h
-- Adsorption
are the p h y s i c a l
the o r g a n i c
:ent of a d s o r p t i o n 17. tendency
of an o r g a n i c
of the sediment
and c h e m i c a l
compound
content
characterisics
The most i m p o r t a n t
property
of the c o m p o u n d
properti~
of the s e d i m e n t
surface
a l s o has a strong
from the water 18.
onto a sediment
Important
of the surface
and the a v a i l a b l e
of the sediment
of the c o m p o u n d
from s o l u t i o n
and of the compound.
sites on the surface,
}
from
but that most of the resistance
on the p r o p e r t i e s
sediments,
having
and air films
is in the air
the type of b i n d i n g
the e s c a p i n g
This value
H to
to v o l a t i l i z a t i o n
it is e x p e c t e d
from water,
~ticle
in std arm.
having
t
s
coefficient
limit at which most of the resistance
acetone
compounds
can be c a l c u l a t e d
at 2 5 ° C from P e r r y 16 are 6.7 and 0.301
H of 3.6 x 10 -5 std a t m m 3 mol -I.
compounds
of
of the r e s i s t a n c e
be c o n s i d e r e d
18 x 10 -6 ~ P
o5
organic
than 95 p e r c e n t
also has an e f f e c t on the Henry's
~re H is in std a r m m 3 mol -I, y is the a c t i v i t y of the pure solute
volatility
both the water
might
Division
Law constant,
For the high v o l a t i l i t y
for the open ocean
and therefore
of a c e t o n e
that th{
in the wate,
Smith et al. 15 d i v i d e d
classes.
These c a l c u l a t i o n s
H =
a t m m 3 mol -I
b a s e d on
significantly.
of the Henry's
For low v o l a t i l i t y
For i n t e r m e d i a t e
shown TM t h a t H for dilute
vapor pressure
transfez
films,
m a y be l a r g e l y
x 10 -3 std atm m 3 mol -I , m o r e
of 720 m day -I e s t i m a t e d
the s o l u b i l i t y
~ssure of a c e t o n e
from w a t e r
films may c o n t r i b u t e
1.2 x 10-5 std a t m m3 mol-1,
is a v o l a t i l e
However,
to mass t r a n s f e r
1.2 x 10 -5 std atm m 3 mol "I, more than 95 p e r c e n t
hween 4.4 x 10-3 and
iss.
compounds
is in the water
than
to m a s s
of the liquid and gas
in the water and air.
larger than 4.4
[ueS s m a l l e r
anificant
resistance
on the m a g n i t u d e
and i n t e r m e d i a t e
H values
is the r e s i s t a n c e
(2) by a number of r e s e a r c h e r s 8 , 14,15 has shown
of o r g a n i c
film, or that b o t h the
mixing
,pounds
is the overall
I/k L and RT/Hk G are the r e s i s t a n c e s
to the v o l a t i l i z a t i o n
[m, l a r g e l y
(2)
coefficient
area 17.
influence
is the f u g a c i t y
Solubility
is o f t e n
For
on the which
used as an
)0
ex of this
fugacity
with
ever,
approach
may not a l w a y s
this
Studies slightly osure
ever,
of the a d s o r p t i o n sorbed
carbon
to a d s o r b
of a c e t o n e
Giusti
are
limited.
but o n l y
of a c e t o n e
et al. 20 studied
was observed.
with montmorillonite.
t adsorption
will c o n t r i b u t e
todecomposition
-- P h o t o d e c o m p o s i t i o n
esult of the a b s o r p t i o n nsfer of e n e r g y
absorption
endent
on the
differ
intensity
which
of the
light,
of c o m p o u n d
processes
from rates
in d i s t i l l e d
the
light
incident
reactions
information
of
light
occurrlng
absorption
of
6
light,
which
is d i r e c t l y
of the c o m p o u n d ,
Photodecomposition
energy
and th~
absorbed.
but are b e l i e v e d
rates
of s u s p e n d e d
occurring
in stream~
The rate of d e c o m p o s i t i o r
per unit of light
water b e c a u s e
on
increa~
it is not e x p e c t e d
is the d e g r a d a t i o n by d i r e c t
I
were a l s o
fate of a c e t o n e
the c o n c e n t r a t i o n
degraded
ketones
diketones
however,
p r o c e s s e s 18.
of n a t u r a l l y
available
a photodecomposition
go to c o m p l e t i o n .
Acetone
erally agreed23
atmosphere
can occur
of
prior
compounds
in natural material
to
waters which
that q u e n c h
or
r e a c t i o n s 9.
is l i m i t e d
ctions 22.
and b e c a u s e
weight
are not as well u n d e r s t o o d ,
considerably
There
shows
of the c o m m o n
a weak
that s u n l i g h t
because
solvents
used
s t u d i e s 2 4 , 2 5 , 26.
rt w i t h
regard
There
energy.
characteristics of ethane
however,
in c y c l o h e x a n e
of acetone.
and c a r b o n
on the p r o d u c t s
at 280 nm,
however,
in p h o t o c h e m i c a l
by a t m o s p h e r i c
studies, suggest
but
gases.
it has b e e n
that a c e t o n e
monoxi
of
the
it is
less than 295 ~, are not t r a n s m l t t e d
and a b s o r p t i o n
These o b s e r v a t i o n s
-- B a c t e r i a l
ource of f o o d a n d / o r
is d i s a g r e e m e n t ,
wavelengths
to p h o t o d e c o m p o s i t i o n
degradation
on the p h o t o c h e m i c a l
at 313 nm with p r o d u c t s
absorption
of s c a t t e r i n g
several
terial
process
or by indirect
incident
and i n d i r e c t
dependence
vapor u n d e r g o e s the
This
compounds
vapor
with w a t e r
as the s o l u b i l i t y
to the
on the rate of a b s o r p t i o n
is the q u a n t i t y
increases.
that a c e t o n e
of a s e r i e s
decreased
Generally,
of o r g a n i c
i n t e n s i t y 18.
the
the a d s o r p t i o n
significantly
on light
enuates sitize
light.
is d e p e n d e n t
reactions
e a similar
of
from a s e n s i t i z e r ,
direct
sitized
G l a e s e r 19 found
Higher-molecular
o r t e d 21 to f o r m c o m p l e x e s on s e d i m e n t s
as the s o l u b i l i t y
if the c l a y was h y d r a t e d
a n d found that the e x t e n t of a d s o r p t i o n
adsorption
ntum yield
decreasing
be v a l i d 18.
by m o n t m o r i l l o n i t e ,
to the a c e t o n e .
ivated
the t e n d e n c y
through
Acetone
is not
used as a sensitiz
is p r o b a b l y
not c o m p l e t
processes.
degradation
This p r o c e s s
is the use of o r g a n i c can be d e s c r i b e d
compounds
by an e q u a t i o n
by b a c t e r i a of the
a
form 17
-Kdt C=Coe
~e C is the c o n c e n t r a t i o n centration radation. bacterial
at time Equation
(5) is a v e r y
degradation
and pH,
compound
zero, and K d is the f i r s t - o r d e r
3ent, all the n e c e s s a r y forms,
of the o r g a n i c
(
to occur, nutrients
temperature,
simplified bacteria
in the w a t e r
representation
acclimated
and trace e l e m e n t s
dissolved
oxygen,
at time t, C O is the
rate c o e f f i c i e n t
for b a c t e r i a l
of a v e r y c o m p l e x
to the o r g a n i c m u s t be p r e s e n t
and the o r g a n i c
compound
process. must
in the p r o p e r
compound
must
be amount
be within
ii(
rain ranges of v a l u e s and c o n c e n t r a t i o n s . radation p r o c e s s ,
Equation
However, despite the c o m p l e x i t y of the
(5) is f r e q u e n t l y used as a first a p p r o x i m a t i o n of the p r o c e s s
T h e r e have been a limited number of studies of the bacterial degradation of acetone. and Agg 27 s u g g e s t e d that a c e t o n e was usually easily d e g r a d a b l e in a biological sewage atment plant. compound.
They
stress, however,
the importance of a c c l i m a t i z a t i o n of the b a c t e r i a to
Abrams et al. 5 s i m i l a r l y c l a s s i f i e d acetone as having low persistence.
Helfg+
al. 28 m e a s u r e d r e f r a c t o r y i n d i c e s for a number of organics where a value of 1.0 indicates dily b i o d e g r a d a b l e a v a l u e of 0.8,
c o m p o u n d s and a value of 0 indicates n o n - d e g r a d a b l e compounds.
i n d i c a t i n g a d e g r a d a b l e compound.
It was expected,
therefore,
Aceton
that
terial d e g r a d a t i o n will c o n t r i b u t e s i g n i f i c a n t l y to the fate of a c e t o n e in streams. 0 r p t i o n by a l g a e and m o l d s -- O r g a n i c compounds in water may be a b s o r b e d by biota within ecological
system.
bon a n d / o r energy,
Once absorbed, excreted,
the compound may be degraded and used as a source of
or s t o r e d by the biota, resulting in b i o a c c u m u l a t i o n .
The
ent of a b s o r p t i o n and b i o a c c u m u l a t i o n depends on the c h a r a c t e r i s t i c s of both the c o m p o u n d the biota. u b i l i t y 17.
The m o s t i m p o r t a n t p r o p e r t i e s of the compound are its stability and S t a b i l i t y in the w a t e r e n v i r o n m e n t is necessary for b i o a c c u m u l a t i o n
the o t h e r hand, umulation
to occur.
if the c o m p o u n d is very soluble In water, then excretion rather than
is m o r e likely.
The m o s t important property of the biota is the surface area
ause a d s o r p t i o n will likely be i n v o l v e d in the absorption process 17. T h e r e are no known s t u d i e s of the a b s o r p t i o n of acetone by biota; however, there have b~ i m i t e d number of s t u d i e s of o t h e r low m o l e c u l a r weight solvents.
Benzene and toluene w e r
nd to have both a s t i m u l a t i n g and an inhibiting effect on the growth of p h y t o p l a n k t o n 2 9 . ed s o l u t i o n s of aromatics,
alkanes, and alkenes resulted in increased rates of photo-
thesis
Also, it was found that several aquatic fungi were c a p a b l e of
in m a r i n e a l g a e 30.
f a d i n g a l k a n e s a n d a l c o h o l s 31. accumulation
Finally, an inverse relation between the l o g a r i t h m of the
factor for C h l o r e l l a fusca and the logarithm of the water solubility was fou
34 s o l v e n t s 32.
All these studies,
however, were for low solubility compounds, and the
a v i o r of a c e t o n e is very likely to be different. erimental Procedures lytical -- A c e t o n e c o n c e n t r a t i o n s
in w a t e r samples were d e t e r m i n e d using a Varian* gas
o m a t o g r a p h with a flame i o n i z a t i o n detector.
For c o n c e n t r a t i o n s in the low m i l l i g r a m - p e r
er range, the a c e t o n e was s e p a r a t e d from the water and pre-concentrated using a strip and p procedure
in w h i c h a 5-~i a l i q u o t of the sample was carried through a Tenax trap by a
eam of h e l i u m gas.
The a c e t o n e was a d s o r b e d on the Tenax at room temperature, and the
er was c a r r i e d on t h r o u g h the trap. o r b e d from the t r a p by h e a t i n g to concentrations
After a 15-minute stripping period, the acetone was
160-180°C, and flushed into the c h r o m a t o g r a p h for analy
in the m i c r o g r a m - p e r - l i t e r
range, a headspace s w e e p i n g and t r a p p i n g
c e d u r e was used in w h i c h the v a p o r a b o v e 20.0 ml of sample at 50°C was swept into a Tenax e use of the b r a n d names in this report is for identification p u r p o s e s only and does not ply e n d o r s e m e n t by the U.S. G e o l o g i c a l Survey.
by a s t r e a m
of h e l i u m
the t r a p by h e a t i n g i s i o n of
gas.
to
rption
plate
describing
The b a t h
conditions
id be c o n s i d e r e d produced
speed
nitrogen
gas,
calculated
were
of E q u a t i o n
was d e s o r b e d
for a n a l y s i s .
2 percent,
Details
and precis
of the technique
given
by R a t h b u n
using
27 m o n t m o r i l l o n i t e
a size
The e x p e r i m e n t a l 10 g w e t w e i g h t to g i v e
er s t o p p e r
ed in a f r e e z e r ared using b a t o r at
were
en as d e s c r i b e d media
erilized
the aJ
for all
ranging
from 0 to
the d i s s o l v e d
oxygen
concentration
Volatilization
coefficier
nonlinear
of the e x p e r i m e n t a l
least
a n d data analysJ
from a small
from Wards
concentration
sediment
was added,
Control
flasks
and all the flasks
then s a m p l e d
at p e r i o d i c
through
vial with
without
were p l a c e d
during
matter
and
of the p u r e flask.
clays
with a
the s e p t u m liquid
the s e d i m e n t s
on a shaker
with a
nitrogen
platform
The e x p e r i m e n t a l
the experiment,
and
were in an and
and the samples
previously. a high
from a small charge
sediment clay
water
stream.
on the clays.
conditions
he m o n t m o r i l l o n i t e
purity
local
were
from
in all e x p e r i m e n t s
In one experiment,
an o r g a n i c
carbon
Milli Q system,
a c t e d as a p e p t i z i n g
The pH was v a r i e d
used
was used.
giving
from a M i l l l p o r e The b u f f e r
content
3.4 to
except
natural of
c
Acetone
flask were m i x e d by shakinc
at one cycle p e r second. intervals
all o r g a n i c
The
Establishmer
the flask was c l o s e d
sample was w i t h d r a w n
analysis.
stream.
Science
in a 250-mi
of the
septum
in a seriE
was used w i t h no processin~
100 m g d r y weight
contents
in a small
local
Natural
in 100 ml of m e d i u m
immediately
was i n v e s t i g a t e d
of Hedges 34 to remove
s e p t u m port,
oscillated
Sterile natural
conditions
the water,
per minute rateg
of time.
sediment
of s u s p e n d i n g
sediment
The p l a t f o r m
the s u r f a c e
riments.
within
to give an initial
on s e d i m e n t s
The natural
a n d an initial
at - 2 0 ° C until
w e r e used,
and water
0.5 ~m.
initial
frozen
30 m min -I,
These
data a n d a t w o - p a r a m e t e r
9 kaolinite
consisted
the same p r o c e d u r e ,
20°C.
flasks
was
of
were of the oxyc
in the water was p r o v i d e d
of s t r i p p i n g
descriptions
a n d a natural
a sampling
one m i n u t e ,
sample
Mixing
acetone
as a function
to the p r o c e d u r e
the d e s i r e d
no m i x i n g
at 21 c y c l e s
consisted
of acetone
a n d no.
less t h a n
procedure
from water
the m e a s u r e m e n t
with r e v o l u t i o n
sufficient
Complete
of the n a t u r a l
containing
ly for a b o u t This
stirrer
the w a t e r
clays
according
fraction
with
a n d Tai 13.
s w e r e no.
e were prepared
with
surface.
which oscillated
-- The a d s o r p t i o n
two p u r e
of a c e t o n e
for all experiments.
because
of the water
procedure
(I).
xperiments
rsed
2 and 4 percent.
f r o m the c o n c e n t r a t i o n - v e r s u s - t i m e
r p t i o n on s e d i m e n t s
Three
than
in a fume hood w i t h a face v e l o c i t y
adding
130 m g 1 -I , a n d s a m p l i n g
er35,
less
the v o l a t i l i z a t i o n
electric
The e x p e r i m e n t a l
with
res a n a l y s i s
rol
the a c e t o n e
into the c h r o m a t o g r a p h
bath simultaneously
conditions
disturbance
and a variable
the w a t e r
nge.
was
as l o w m i x i n g
no v i s i b l e
0 rev m i n -I.
icient
period,
was g e n e r a l l y
in the air were constant
in the b o t t o m of the b a t h
riments
btain
sweeping
flushed
was b e t w e e n
constant-temperature
coefficients.
efore m i x i n g
edures
and
technique
technique
-- C o e f f i c i e n t s
in a large
bout
15-minute
by T a i 3 3 .
tilization ured
a
160-180°C,
the m i l l i g r a m - p e r - l i t e r
he m i c r o g r a m - p e r - l i t e r given
After
11.4
Run 4-35
McIlvaine's agent and
for the where
fulvic acids
the
were added
13 mg 1-1 for the mixture.
ii0
~odecomposition ~xperiments.
-- The p h o t o d e c o m p o s i t i o n
Rhodamine-WT
these e x p e r i m e n t s dispersion
first
procedure
in water,
ppers,
e used r a t h e r
of a c e t o n e
stock
than borosilicate
180 nm w h e r e a s
of the w a v e l e n g t h s
the d i s t i l l e d
8 hours
were
eriment terial
experiments
transferred
repeated
ium,
of
ficient
acetone
1-I.
Samples
il analysis.
test tubes,
experiment.
capped
longer
with
serum
Quartz
tube
to w a v e l e n g t h s than
the atmosphere
300 nm.
Th
is 295 t~. 23 giving
was for 7 hours
one da I
were
the d e s i r e d
cap,
initial
to e q u i l i b r a t e Initial
through frozen
technique.
sewa, wet
alone.
rod shaped and about
I ~m
and G a r d i n e r 37, and an i n o c u l u m
10-day intervals.
hours
A culture
The b a c t e r i a
No effort
the bacteria
in a sterile
medium.
was m a d e
to
were c e n t r i f u
This p r o c e d u r e
of an experiment.
all g l a s s w a r e
and the medium.
filled with the w a s h e d b a c t e r i a
oxygen.
in a serie=
from a p r i m a r y
and finally acetone
typically
to initiation
for several
with d i s s o l v e d
obtained
culture
of s t e r i l i z i n g
then
was i n v e s t i g a t e d
of each experiment,
prior
consisted
w%s s t i r r e d
septum
at about
by a of the
E / B O D respirometer.
and acetone, were
concen-
at the end of the experiment.
source was d e v e l o p e d
and then r e s u s p e n d e d
the b a c t e r i a
as a control.
were
medium
at the b e g i n m i n g
by b a c t e r i a
u s i n g an e n r i c h m e n t of glucose
of acetone
for d e t e r m i n a t i o n
International
that the bacteria
sterile
and a l l o w e d
served
h a teflon-faced
transp
water was used i
is t r a n s p a r e n t
solution
of acetone
to the i n i t i a t i o n
procedure
to give
of the c h a m b e r s
Distilled
in the second
for d e t e r m i n a t i o n
in the m e d i u m of Montgomery
the r e s p i r o m e t e r
the m e d i u m
rd c h a m b e r
showed
to wash
and the m e d i u m
saturate
concentrati~
exposure
in the test tubes
as a sole carbon
plant
grown
Prior
The e x p e r i m e n t a l ee c h a m b e r s
of the desired
to the sunlight.
through
a larger volume
for the stock
remaining
for 30 m i n u t e s
twice
mass
was for about 8 hours per day for 3 days,
u s i n g an O c e a n o g r a p h y
to a fresh,
rev m i n -I
quartz
water experiment,
required
then a m i x t u r e
were
p a pure culture. 2,000
which
use a c e t o n e
treatment
fed g l u c o s e ,
The b a c t e r i a
the convective
o n l y for w a v e l e n g t h s
w i t h a syringe
The d e g r a d a t i o n
ctron p h o t o m i c r o g r a p h s g.
exposure
periodically
--
that w o u l d
from a local
tially
to q u a r t z
for e x p o s u r e
transmitted
In the s t r e a m
solutions in water.
because
is t r a n s p a r e n t
the s o l u t i o n s
degradation
laboratory
tracer 36 was also c o n s i d e r e d
stream was u s e d
transferred
tubes
number
day.
removed
for
and dye
local
in a l i m i t e d
studies.
stock
outdoors
of s u n l i g h t
t e c h n i q u e 36 were m e a s u r e d
and
bacteria
were
glass
experiment,
Dye c o n c e n t r a t i o n s
orometric
ple
glass
23 hours.
the n e x t
Samples tions.
water
of
in water,
and p l a c e d
er limit
in stream
f r o m a small
solutions
to a rack,
get than
al e x p o s u r e
used as a water
of p r e p a r i n g
and dye
and water
of t h e s e attached
is c o m m o n l y
consisted
acetone
experiment
ntities
which
was i n v e s t i g a t e d
this dye was to be used to d e t e r m i n e
characteristics
The g e n e r a l acetone
because
of acetone
to obtain
temperature
suspended
The in th
equilibration
and
One liter of m e d i u m was u s e d in each flask. concentration before
acetone
was then added with a syringe
the initial
concentrations
samples ranged
a septum p o r t with a syringe, immediately
with
liquid
were withdrawn. from
16 to
transferred
nitrogen,
t T
158
to a vial
and stored
at - 2 0 ° C
In s e v e r a l
experiments,
nbers on the n i g h t tone.
Sufficient
~hese c h a m b e r s ~rption series Daena
of
te f l u o r e s c e n t
trol
flasks
eral
and
no a l g a
bacterial
from a small
of the p l a t f o r m
local
to a timer
stream.
as a function
sampled (algal
concentrations
were
flask-shakez
studles
by eight
was use
20-watt
descrlbed
c<
for the
the alga and a c e t o n e
of time.
and
Bristols 38, yeast-
potential) 40 media were used.
reduced
alga
Cladophora
set for a 12-hour cycle.
containing
growth
The
adsorption
the same as that p r e v i o u s l y
were
investigat
the b l u e - g r e e n
was p r o v i d e d
flasks
was
by the green algae
in the s e d l m e n t
wit~
was then add~ previously.
and molds
pyrenoidosa,
Experimental
AGP
as d e s c r i b e d
by algae
dominated
the b a c t e r i a
concentration
was c o n d u c t e d
were c o n n e c t e d
a n d 40 mg 1 -I of s t r e p t o m y c i n
by t r e a t m e n t
with
In
12 mg 1-I of
sulfate.
Discussion
atilization
-- The e x p e r i m e n t a l
tone and t h e a b s o r p t i o n atilization fficient
where
absorption
This
is v a l i d
all the r e s i s t a n c e
from Equation
liquid-film Mixing
are p l o t t e d
the o x y g e n
in the water.
volatilization
coefficients
coefficients
t virtually follows
mold
to the two e×perimenta]
to p r e t r e a t
acetone
Chlorella
described
was b a s i c a l l y
experiments.
experiments,
ditions
tubes
p r o t e o s e - p e p t o n e 39, and
icillin-G ults
procedure
containing
aquatic
were a d d e d
of acetone
green alga
at the s u r f a c e
These
initial
algal p o p u l a t i o n
previously
lumens
tubes.
adsorption
rogen 39,
the
natural
apparatus
The e x p e r i m e n t a l iment
-- The a b s o r p t i o n
a n d an u n i d e n t i f i e d
of 8,860
of a c e t o n e
of an e x p e r i m e n t
and the e x p e r i m e n t
using
a mixed
tform-incubator ~mination
day,
experiments
initiation
to give the d e s i r e d
and molds
flosaquae,
Spirogyra,
to the
acetone
the n e x t
by algae
~ g 1 -I q u a n t i t i e s
prior
(2) t h a t
coefficients
for o x y g e n in Figure
are given
by Equation I.
absorption
has been u s e d as an indicator
of oxygen
absorption
of m i x i n g
p r e v i o u s l y 4 1 , 42
is in the liquid
coefficient
(I) for
The acetone
of the o x y g e n
it has been e s t a b l i s h e d
to the a b s o r p t i o n the o x y g e n
in Table
I as a f u n c t i o n
coefficient because
defined
film;
is v i r t u a l l y
theref¢
identical
t
coefficient.
conditions
can a l s o be d e s c r i b e d
in terms of the s t i r r e r
Reynolds
Number
which
of the s t i r r e r
blade,
and v
i
i n e d 43 as
nL2 Re = - -
re n is t h e r e v o l u t i o n kinematic
viscosity
nt in F i g u r e The e f f e c t ults th of
of R u n s 200 mm.
rate of the stirrer,
of the water.
I, i n d i c a t i n g of w a t e r A-10,
L is the length
The stirrer
the d e p e n d e n c e
Reynolds
d e p t h on the v o l a t i l i z a t i o n
A-14,
and A-15
The s t i r r e r
Number
of both c o e f f i c i e n t s coefficient
for a depth of 267 mm with
Reynolds
Numbers
for these
is shown
next to each dat
on mixing. can be seen by c o m p a r i n g
t~
the result of Run A-2 for a
runs were v i r t u a l l y
identical;
how~
Table
I
E X P E R I M E N T A L V O L A T I L I Z A T I O N C O E F F I C I E N T S FOR ACETONE, AND A B S O R P T I O N COEFFICIENTS FOR O X Y G E N
Run
Stirrer Reynolds Number x 10-4
Water Temp. ("C)
A-I
7.90
25.0
200
2.23
A-2
2.71
25.1
200
1.34
A-3
4.89
25.1
200
1.67
A-4
9.41
25.1
200
2.22
30.1
Water Depth, Y (mm)
Acetone Volatilization Coefficient, K v (day-l)
Oxygen Absorption Coefficient, K o (da~-1)
25.4 4.00 8.62
A-5
5.95
25.0
200
1.68
11.3
A-6
7.00
25.2
200
1.91
14.8
A-7
3.80
25.1
200
1.55
A-8
0
25.1
200
A-9
9.43
25.2
200
A-10
2.69
24.8
267
A-11
1.58
25.1
A-12
0
25.1
A-13
0
A-14
2.70
A-15
2.71
.543 2.31
5.78 1.59 31.1
.995
1.88
267
.917
2.17
267
.683
1.54
24.9
267
.625
1.43
24.9
267
.968
2.45
25.1
267
.982
2.78
O o~
2 QSO
!
I
I
I
,
i
=
a<
Z 0 ~,,,
i 7.00 ® i
2.00
","
3.80 ~ . ~ . . Q / ( 9 ::~"'~ 4.89 fv
0,, p-
1.50
_
M.
/
9.4'1
~
5.95
12.69 / . 1.00"
Zr'J'
2.71
/
0 p-
<
N__
/
i
/
/ (92.71
_ u_ O
9.43
7.90
0.50
L
INDICATES STIRRER REYNOLD S
/ 1.58
NUMBER X 10 -4)
9
I--
< .J
o >
O
0
I
I
]
I
[
I
I
4
8
12
16
20
24
28
32
A B S O R P T I O N C O E F F I C I E N T FOR O X Y G E N ( D A Y S "1)
Figure l°--Volatilization coefficient for acetone as a function of the absorption coefficient for oxygen for various water mixing conditions
ii0
volatilization [ted data
coefficient
suggest
that,
~er should p r o b a b l y Acetone ients,
was a b o u t
to define
contain
volatilization
the water
coefficients
and the v o l a t i l i z a t i o n
In the low m i x i n g
volatilization
in the water
mixing
range would
urred b e c a u s e ing range.
showed m u c h
appear
Therefore,
The v o l a t i l i z a t i o n ing c o n d i t i o n s
for a c o n s t a n t
dition.
ing c o n d i t i o n s
resulting
condition
-- Results
in Table
All the e x p e r i m e n t s
and showed
no s i g n i f i c a n t
sterile
conditions
with natural
Run 4-35,
however,
with n o n s t e r i l e
loss after about
lag p e r i o d
luding the
being
lag period,
This d e v i a t i o n
natural
the i n i t i a t i o n
500 hours.
the f i r s t - o r d e r
in this
in lakes and ponds
for very low
days-1
conditions.
T h e s e measur(
stream
of acetone
for highel
situation. on s e d i m e n t s
and k a o l i n i t e
over
as a low mix~
considerably
for a natural
long time periods.
showed
no s i g n i f i c a n t
sedlment,
showed
significant
and r e s u l t e d
loss was a t t r i b u t e d
rate c o e f f i c i e n t
describing
this
Run 4-~ loss of
loss
in approximatel~
to b a c t e r i a l
to a c c l i m a t e
are
were done und(
similarly
for the b a c t e r i a
ic
from 0.625
of the e x p e r i m e n t
This
the time n e c e s s a r y
may have
water phase.
be i n c r e a s e d
loss of acetone
sediment,
in the
a uniformly-mixed
with m o n t m o r i l l o n i t e
e under
h the
on m i x i n g
was not f u l f i l l e d
of the study of the a d s o r p t i o n
rile c o n d i t i o n s
-percent
would
in the ware
the b e h a v i o r
be a p p l i c a b l e
I ranged
absorptior
0 and 6 days-1
dependence
however,
water p h a s e
in the air phase
on s e d i m e n t s
inning about 90 hours after
model,
of
coef-
o n l y about
conditions
in the air that s h o u l d be c o n s i d e r e d
coefficients
marized
tone.
and the small
to produce
in Table
increased
coefficients
days -I for very high m i x i n g
from winds
Reyno]
conditions
in the o x y g e n
on m i x i n g
with the model.
mixed
of m i x i n g
coefficient
model m a y not always
orption
2.
increase
absorption
of acetone
given
that these
absorption
independent
dependence
is i n s u f f i c i e n t
to 2.31
mixing
It is e x p e c t e d
oxygen
of a u n i f o r m l y
coefficients
in the water
These
than the o x y g e n
volatilization
to be i n c o n s i s t e n t
mixing
smaller
with the t w o - f i l m
the t w o - f i l m
depth.
the stirrer
for a f i v e - f o l d
larger
coefficients
the a s s u m p t i o n
re the rate of v e r t i c a l
ts were
Thus,
are c o n s i s t e n t
for the s h a l l o w e r more precisely,
was r e l a t i v e l y
range b e t w e e n
coefficient
The small v o l a t i l i z a t i o n ditions
were m u c h
from 6 to 30 days -I , the a c e t o n e
percent.
larger
conditions
depth.
coefficient
~he water over m u c h of the range. fficient
36 p e r c e n t
the m i x i n g
degradation,
to the acetone. loss was about
0.(
s-1. todecomposition centration taining
acetone
9 percent ing this
-- Results
exposure
centration
water
exposure
in the a c e t o n e
experiment
showed
o n l y and an 8.6 p e r c e n t period.
no change
decrease
in the acet(
in the tube
The dye c o n c e n t r a t i o n
and dye and dye o n l y solutions,
decreased
respectively,
period.
of the local in either
over a 15-hour
acetone
and dye over a 23-hour
and 24.0 p e r c e n t
Results
of the d i s t i l l e d
in the tube c o n t a i n i n g
stream water e x p e r i m e n t
the tube c o n t a i n i n g
exposure
period.
showed
acetone
no s i g n i f i c a n t
change
only or the tube c o n t a i n i n g
The dye c o n c e n t r a t i o n
decreased
in the aceton( acetone
13.9 p e r c e n t
and
and
16.2
108
Table 2 S U M M A R Y OF S E D I F ~ N T A D S O R P T I O N E X P E R I M E N T S AT 20 ° CELSIUS
Run
Sediment
Medium
pH
Duration of Run (hr)
Initial Acetone Conc. (m@ 1-I)
Results
4-I
Montmorillonite (100 mg)
McIlvaine buffer
7.7
4.67
160
No loss of a c e t o n e
4-11
Montmorillonite (100 mg) F u l v i c Acid
~4zIlvaine buffer
7.7
171
160
No loss of a c e t o n e
3-175
Montmorillonite (100 mg)
McIlvaine buffer
7.7
333
925
Small loss in both exp. and c o n t r o l flasks; all data s c a t t e r e d
4-47
Montmorillonite (100 mg)
Milli Q water
3.4
284
346
No loss of acetone
4-70
Montmorillonite (100 mg)
Milli Q water
8.9
101
38
No loss of a c e t o n e
4-23
Montmorillonite (100 mg)
Milli Q water
8.9
174
160
No loss of a c e t o n e
4-31
Montmorillonite (100 mg)
Milli Q water
11.4
175
160
No loss of a c e t o n e
4-43
Kaolinite (100 mg)
Milli Q water
6.9
503
150
No loss of acetone
4-25
Local stream sediment (2 g wet)
Local stream water
8.4
338
105
No loss of a c e t o n e
4-35
Local stream sediment (10 g wet)
7.3
502
120
Loss of a c e t o n e o c c u r r e d after 90 hours in exp. flasks; ~100 p e r c e n t loss after 500 hours
Local stream water (Not sterile)
=ent in the a c e t o n e
and dye and dye o n l y solutions,
respectively,
d u r i n g this e x p o s u r e
Lod. It was c o n c l u d e d acetone
that s i g n i f i c a n t
d i d not a f f e c t
dye was e x p e c t e d
photodecomposition
significantly
because
of a c e t o n e
the p h o t o d e c o m p o s i t i o n
it has been
reported
did not occur,
of the dye.
in the literature
that
and
that
Decomposition
rhodamine-WT
oJ
degrad~
~ o c h e m i c a l l y 3 6 , 44 . Zerial d e g r a d a t i o n times
-- The e x p e r i m e n t a l
for the b a c t e r i a l
before culated period
the b a c t e r i a from E q u a t i o n excluded
u s e d to o b t a i n
from the data.
s in which
ut 13 hours. hours.
are d i v i d e d
concentration
regression
difference
shows
the
3.
The
lag time
The c o e f f i c i e n t s
as a f u n c t i o n
is th~ were
of time data w i t h
of a log e t r a n s f o r m a t i o n
into two groups,
of
ranged
on w h e t h e r
overnight
significantly
the lag time
importance
depending
of a c e t o n e
the lag time
For runs with p r e t r e a t m e n t ,
This
and the a p p r o x i m a t e
t]
Equation
(~
to the data.
that this p r e t r e a t m e n t
was no p r e t r e a t m e n t ,
in Table
of the acetone.
with a small c o n c e n t r a t i o n
It was found there
Linear
rate c o e f f i c i e n t s
are given
degradation
fit of the e q u a t i o n
results
teria w e r e p r e t r e a t e d
of acetone
begin
(5) and the a c e t o n e
a best
The e x p e r i m e n t a l
experiment.
degradation
actively
first-order
or not the
before
reduced
initiation
the lag time.
from 5 to 19 hours
ranged
of a c c l i m a t i o n
from
and a v e r a g e d
I to 3 hours
of a c u l t u r e
o: FoJ
and averac
of b a c t e r i a
to i
anic s u b s t r a t e . The d e g r a d a t i o n
coefficients
9 to 7.9 days -I and a v e r a g i n g fficient
of v a r i a t i o n
degradation
of v a r i a t i o n
est also
shows
in Table
3 show c o n s i d e r a b l e
scatter,
3.9 days -I for those runs with no p r e t r e a t m e n t .
of these v a l u e s
coefficients
fficient
presented
ranged
from 0.43
of 79 percent.
that the means
was 63 percent.
are s i g n i f i c a n t l y
fr(
The
For those runs with p r e t r e a t m e n t ,
to 3.4 days-1
Comparison
ranging
and a v e r a g e d
of the mean values different
1.4 days-1
with a
using a t w o - t a i l e d
at the 5 percent
level
of
nificance. An e x p l a n a t i o n possible pirometer ium.
chambers
Thus,
acetone,
for the d i f f e r e n c e
explanation
at the b e g i n n i n g
the a c e t o n e
effectively
experiment
was still
reducing
for p r e t r e a t m e n t
s, the e f f e c t
might
tone c o n c e n t r a t i o n s
because
acetone
than e x p e c t e d
of an e x p e r i m e n t
going
K d value.
However,
runs.
than Also,
to have lower K d values
of this effect, A linear
for the no p r e t r e a t m e n t
resulting
regression data
-0.48.
This
coefficient
is s i g n i f i c a n t
at the
endence
of the K d v a l u e s
on the initial
acetone
uniformly
as the b a c t e r i a
shorter
for the p r e t r e a t m e n t
is not r e a d i l y
for the acetone
to become
into s o l u t i o n
the a p p a r e n t
be e x p e c t e d
concentration.
tone c o n c e n t r a t i o n
the m e a n K d values
runs was c o n s i d e r a b l y
w o u l d be g r e a t e r
tone c o n c e n t r a t i o n s
initial
between
is that it took longer
because
runs with
large
of
initial
small
relation
initial
between
Kd
of the initial
3 gave a c o r r e l a t i o n
concentration
degra,
the d u r a t i o n
than runs w i t h
level,
in the
for the no p r e t r e a t m e n t
in an inverse
in Table
mixed
to the
in the m e d i u m
of K d as a function
10 p e r c e n t
apparent.
added
indicating
coefficient
a weak
as hypothesized.
invers,
A linear
Table EXPERIMENTAL BACTERIAL
FIRST-ORDER DEGRADATION
3
RATE
COEFFICIENTS
OF A C E T O N E
FOR THE
AT 25 ° C E L S I U S
No Pretreatment
Initial Acetone Conc. (m 9 1 -I )
Approximate Lag Time (hr)
Degradation Coefficient, Kd ( d a y s -I )
IA
34
19
7.9 7.2
Ru___nn
IB
34
19
2A
35
19
5.8
2B
36
18
6.7
3A
78
6
2.6
3B
146
8
2.6
4A
16
5-10
3.6
4B
39
6-8
2.9
4C
55
8-10
5A
20
16
7.0
5B
37
17
I .3
13
4.8
6A
17
6B
38
.79
15-16
2.3
7A
77
10
I .4
7B
158
10
I .6 Mean
= 3.9
Cv!,/ = 63%
Pretreatment
8A
38
2
8B
53
2
I .2
8C
77
3
9A
20
I
3.4
9B
40
I
I .3
.89 .43
Mean
= 1.4
C I_/ = 79% v
C.I~/ = v
(Standard
deviation/Mean)
x 100%
iii]
~ssion of the p r e t r e a t m e n t ted d a t a ribute
set.
Finally,
ly ideal
olved o x y g e n , coefficients rption molds
are
2, 3-111, 5 with erial
and s u b s t r a t e
by algae
activity.
ribing
-I.
were e x c l u d e d
this o c c u r r e d
either
describing
degradation
studies
th c o n d i t i o n s
were
a long time p e r i o d first-order
of these
nonsterile
in Runs in Run
when
mold
from the local
of a b o u t
significantly
cultures
or a f t e r
long time p e r i o d s had declined.
in the r e s p i r o m e t e r a temperature
of 25=C used
studies.
studies.
the
describing
two factors
of 2 0 a C was u s e d in the a b s o r p t i o n
in the d e g r a d a t i o n
for b a c t e r i a
when
First-order
the c o e f f i c i e n t s At least
algal
was o b s e r v e d .
activity
First,
absorbe.
and a m i x e d
conditions
than
0.25
rate c o e f f i c i e n t s .
Some loss of a c e t o n e
however,
the
rate c o e f f i c i e n t
In Run 4-5 when anti-
was neither
of two u n i a l g a l
stream.
were not s p e c i f i c a l l y
not ideal
was o b s e r v e d
by algae
used to reduce b a c t e r i a l
of a c e t o n e
a r e d w i t h the t e m p e r a t u r e
was o b s e r v e d
rate c o e f f i c i e n t
that acetone
the loss were smaller,
to this difference.
he a b s o r p t i o n
suggest
that d e g r a d a t i o n
were not used to reduce
were used.
with a first-order
f r o m the local under
The
under
bacteria,
of a c e t o n e
In Run 3-149 with an aquatic
when a n t i b i o t i c s
the growth process
of the a n t i b i o t i c s
coefficients bacterial
mold
declined.
also
values.
Some loss of a c e t o n e
in the c a l c u l a t i o n
studies
affect
a n d an a q u a t i c
ributed
0.3 days -I.
of the a b s o r p t i o n
ctiveness
had a p p a r e n t l y
loss was o b s e r v e d
it s i g n i f i c a n t l y
ver,
cultures.
was o b s e r v e d
acclimated
loss of a c e t o n e
in Run 3-119 after
The lag p e r i o d s
lation
No appreciable
of the
would
in the l a b o r a t o r y
of the study of the a b s o r p t i o n
Loss was also o b s e r v e d
loss was about
in the m e d i u m
it is e x p e c t e d
than these
where a n t i b i o t i c s
not used,
Results did
Therefore,
because
3.
concentration,
s t r e a m algal p o p u l a t i o n
am, no loss of a c e t o n e ics w e r e
4.
in Table
meaningful
3 were d e t e r m i n e d
will be smaller
-- Results
of the a n t i b i o t i c s
this
in Table
concentrations.
in T a b l e
to mix r a p i d l y
observed
and trace element
3-127 w i t h u n i a l g a l
the local
ctiveness
given
streams
and molds
summarized and
of the acetone
of n u t r i e n t
in natural
3 was not c o n s i d e r e d
of the results
coefficients
conditions
in Table
failure
to the v a r i a b i l i t y
The d e g r a d a t i o n
data
Second,
made up for g r o w t h of bacteria,
as they were in the d e g r a d a t i o n
stud
the m e d i a
use.
therefore,
studies.
ary and Conclusions Laboratory one
rption s.
of several
and rivers
by sediment,
These esses
important
studies could
were
in d e t e r m i n i n g limited
Consideration
that m i g h t a f f e c t
These
studies
bacterial
that v o l a t i l i z a t i o n
be eliminated.
effects.
of the p r o c e s s e s
were completed.
photodecomposition,
It was c o n c l u d e d
ly to be
tire
studies
in s t r e a m s
degradation,
and bacterial
the fate of acetone
to s i n g l e - p r o c e s s In natural
systems
streams,
of m u l t i p l e - p r o c e s s
included
the c o n c e n t r a t i o n
and a b s o r p t i o n
degradation
of
volatilization, by algae
were the p r o c e s s e s
an mos
in streams. so that i n t e r a c t i o n s
however, systems
interactions was b e y o n d
among
may result
the in non-
the scope of this
studl
112
Table 4
SUMMARY OF ALGAE AND MOLD ABSORPTION EXPERIMENTS AT 20 ° CELSIUS
Run 3-102
Biota Chlorella
Medium Proteose-
Sterilit~
pH
Duration of Run (hr)
Not sterile
7.0
216
Initial Acetone Conc. (m~ 1-I) 400
peptone
Results No loss of acetone
3-111
Chlorella
Bristols
Antibiotics used but not sterile
7.0
264
40
No loss of acetone
]-127
Anabaena
Algal growth potential (5 times normal strength)
Not sterile (Aseptic lab culture)
9.3
451
40
Small loss of acetone; less than 8% in experimental flasks
]-119
Local stream algae
Algal growth potential (5 times normal strength)
Antibiotics used
8.0
672
32
No loss of acetone after 168 hrs; 36% loss after 360 hrs; -100 loss after 672 hrs
3-165
Local stream algae
Algal growth potential (5 times normal strength)
Antibiotics used (except in one expt. series)
8.4
592
40
13% loss in controls; 23% loss in experimentals
|-91
Local Milli Q stream water algal floc (200 mg dry)
Antibiotics used
7.3
93
30
No loss of acetone
)-149
Local stream mold
Yeastnitrogen
Antibiotics used
5.5
574
1.6
No loss of acetone
L-5
Local stream mold
Yeastnitrogen
Sterile 5.4 controls; no antibiotics in expt. series
356
80
No loss in controls; 97% loss in experimentals after 356 hrs
i11
~R/~NCES
W. M. Shackelford and L. H. Keith, "Frequency of Organic Compounds Identified in Water, EPA Report No. 600/4-76-062 (Dec. 1976). Environmental Protection A g e n c y , " P r e l i m i n a r y Assessment of Suspected Carcinogens in Drinking Water," EPA Report No. 560/4-75-005 (Dec. 1975). M. Khare and N. C. Dondero, Environ. Sci. Technol., 11, 814 (1977). E. D. Pellizzari et al., "Identification of Organic Components in Aqueous Effluents frol Energy-Related Processes," ASTM Spec. Tech. Publ. No. 686, p. 256 (1979). E. F. Abrams et al., "Identification of Organic Compounds in Effluents from Industrial Sources," EPA Report No. 560/3-75-002 (April 1975). A. A. Stevens et al., J. Am. Water Works Assoc., 68, 615 (1976). H. B. Fischer et al., Mixin@ in Inland and Coastal Waters (Academic Press, New York, 19 D. Mackay and Y. Cohen, "Prediction of Volatilization Rate of Pollutants in Aqueous Systems," in Program and Abstracts. S~mposium on Nonbiolo@ical Transport and Transformation of Pollutants on Land and Water, NTIS Report PB-257347, p. 122 (May 1976). J. H. Smith et al., "Environmental Pathways of Selected Chemicals in Freshwater Systems Part I.: Background and Experimental Procedures," EPA Report No. 600/7-77-113 (Oct. 1977). W. K. Lewis and W. G. Whitman, Ind. Eng. Chem., 16,
1215 (1924).
P. S. Liss and P. G. Slater, Nature, 247, 181 (1974). D. Mackay and P. J. Leinonen, Environ. Sci. Technol., 9,
1178 (1975).
R. E. Rathbun and D. Y. Tai, Water Res., 15, 243 (1981). D. Mackay, W. Y. Shi11, and R. P. Sutherland, Environ. Sci. Technol., 13, 333 (1979). J. H. Smith, D. C. Bomberger, Jr., and D. L. Haynes, Chemosphere, 10, 281 (1981). J. H. Perry, Ed., Chemical Engineers' Handbook, 3rd Ed. (McGraw-Hill, New York, 1950) p. 670. I. J. Tinsley, Chemical Concepts in Pollutant Behavior (John Wiley and Sons, New York, 1979), p. 14, 19, 139, and 185. G. L. Baughman and R. R. Lassiter, "Prediction of Environmental Pollutant Concentration ASTM Spec. Tech. Publ. No. 657, p. 35 (1978). R. Glaeser, Clay Minerals Bull., ~, 88 (1949). D. M. Giusti, R. A. Conway, and C. T. Lawson, J. Water Poll. Control Fed., 46, 947 (197 L. G. Tensmeyer, R. W. Hoffman, and G. W. Brindley, J. Phys. Chem., 64,
1655 (1960).
J. D. Roberts and M. C. Caserio, Basic Principles of Organic Chemistr~ (W. A. Benjamin, Inc., New York, 1965), p. 41, p. 1065. R. G. Zepp and D. M. Cline, Environ. Sci. Technol., 11, 359 (1977). W. R. Benson et al., J. Agr. Food Chem., 19, 857 (1971). O. G. Crosby and A. S. Wong, J. Agr. Food Chem., 21,
1049 (1973).
D. G. Crosby and A. S. Wong, J. Agr. Food Chem., 21,
1052 (1973).
N. S. Thom and A. R. Agg, Proc. Roy. Soc. London, B189, 347 (1975). T. F. Helfgott, F. L. Hart, and R. G. Bedard, "An Index of Refractory Organics," EPA Report No. 600/2-77-174 (Aug. 1977).
W. M. Dunstan, L. P. Atkinson, and J. Natoli, Marine Biology, 31, 305 (1975). T. R. Parsons, W. K. W. Li, and R. Waters, Hydrobiologia, 51, 85 (1976). J. D. Walker, L. Cofone, Jr., and J. J. Cooney, "Microbial Petroleum Degradation: The Role of C l a d o s p o r i u m resinae," in Prevention and Control of Oil Spills, Conf. Proc., r~rch 13-15, 1973, Wash. D. C., EPA. H. Geyer et al., Chemosphere, 10,
1307 (1981).
D. Y. Tai, "Determination of Acetone and Meth~l Eth~l Ketone in Water, U.S. Geological Survey Water-Resources Investigations 78-123 (Oct. 1978), available from U.S. Dept. of Commerce, National Technical Information Service as Report PB291 151. J. I. Hedges, Geochim. Cosmochimica
Acta, 4~I, 1119 (1977).
Handbook of Chem. and Physics, 31st Ed. (Chem. Rubber Publ. Co., Cleveland,
1949).
J. F. Wilson, Jr., Fluorometeric Procedures for Dye Tracin@, U.S. Geological Survey Tech. of Water-Resources Investigations, Book 3, Chap. A12 (1968). H. A. C. Montgomery and D. K. Gardiner, Water Res., 5, R. C. Starr, Am. J. Botany, 51,
147 (1971).
1013 (1964).
Difco Laboratories, Difco Manual of Dehydrated Culture Media and Reagents, 9th Ed. Labs., Detroit, 1974).
(Di{
P. E. G r e e s o n et al., Methods for Collection and Anal~sis of Aquatic Biological and Microbiological Samples, U.S. Geological Survey Tech. of Water-Resources Investigatlon~ Book 5, Chap. 4. D. Mackay and T. K. Yuen, Water Poll. Research J. of Canada, 15, 83 (1980). J. H. Smith, D. C. Bomberger, Jr., and D. L. Haynes, Environ. Sci. Technol., 14,
(1980). J. T. Davies, Turbulence Phenomena (Academic Press, New York, P. L. Smart and I. M. S. Laidlaw, Water Resources Res., 13,
(Received
in
The
Netherlands
20 August
1982)
1972) p. 149.
15 (1976).
1332
pp
1097-1114,
1982
0045-6535/82/111097-18503.00/ ©1982 Pergamon Press Ltd.
FATE OF ACETONE IN WATER Ronald E. Rathbun*, Doyle W. Stephens, Davzd J. Shultz, and Doreen Y. Tai U.S. Geological Survey, NSTL Station, Mississippi 39529
Abstract
The physical, chemical, and biological processes that might affect the concentration of tone in water were investigated in laboratory studies. Processes considered included atilization, adsorption by sediments, photodecomposition, bacterial degradation, and orption by algae and molds. It was concluded that volatilization and bacterial degradati, e the dominant processes determining the fate of acetone in streams and rivers. roduction The fate of organic compounds in streams and rivers is determined by the interactions o: plex physical, chemical, and biological processes.
Among the physical processes are
vective mass transport, dispersion, volatilization, and adsorption by sediment. mical processes are photodecomposition, hydrolysis, and chemical reaction.
Among th,
Among the
logical processes are bacterial degradation and absorption by biota. Acetone is infinitely soluble in water and therefore, it was selected as a model compoul resentative of the very water soluble class of organic compounds. sons for selecting acetone as the model compound. d.
There are a number of
It is a common solvent and is widely
Determination of organic compounds in various types of waters showed that acetone was
compound occurring most frequently I.
Also a survey of trace organics in the finished
nking water of 10 cities in the United States showed that only acetone and chloroform werd sent in all the waters 2.
Acetone has been identifled in leachates from landfills 3, in
er effluents from energy-related processes4, and also may be present in wastewaters from age treatment plants operated above optimum capacity 5 where it is formed as an intermedia omposition product.
Under some conditions, acetone may be a precursor in the formation o
orinated hydrocarbons during the chlorination of drinking water supplies 6. This report describes the results of laboratory studies of the processes affecting the centration of acetone in water.
Reports describing the results of field studies are also
nned.
1097
The s t u d i e s of acetone were l i m i t e d to systems in w h i c h b a s i c a l l y one p r o c e s s was rative.
In n a t u r a l streams, however,
several p r o c e s s e s will
/sly, r e s u l t i n g in effects that may be nonadditive. one p r o c e s s
likely be o p e r a t i n g simulta-
C o n s i d e r a t i o n of systems w h e r e m o r e
is o p e r a t i v e is b e y o n d the scope of this study.
~ry
Brief s u m m a r i e s of the general a s p e c t s of v o l a t i l i z a t i o n , ~mposition, b a c t e r i a l degradation,
a d s o r p t i o n by sediments, phot
and a b s o r p t i o n by a l g a e and m o l d s a n d a brief d i s c u s s i
the e x p e c t a t i o n of the i m p o r t a n c e of each of these p r o c e s s e s
for a c e t o n e will be given.
~ective m a s s t r a n s p o r t and d i s p e r s i o n have been d i s c u s s e d in detail p r e v i o u s l y 7, and will be c o n s i d e r e d .
In general,
the i m p o r t a n c e of these two p r o c e s s e s
relative to the other
zesses will d e p e n d on h y d r a u l i c c o n d i t i o n s in the stream; t h e s e c o n d i t i o n s d e t e r m i n e the nsport and d i s p e r s i o n c h a r a c t e r i s t i c s .
Therefore,
because of the wide range of h y d r a u l i c
ditions in s t r e a m s and rivers, a wide range of t r a n s p o r t and d i s p e r s i o n c h a r a c t e r i s t i c s expected.
H y d r o l y s i s and c h e m i c a l r e a c t i o n were c o n s i d e r e d not to have s i g n i f i c a n t effec
Icetone in streams. •t i l i z a t i o n -- V o l a t i l i z a t i o n is the t r a n s f e r of an o r g a n i c c o m p o u n d from the w a t e r acros water-air
i n t e r f a c e into the air as a result of the r a n d o m kinetic m o t i o n s of the m o l e c u
the c o m p o u n d a n d the c o n c e n t r a t i o n d i f f e r e n c e between the w a t e r and air.
This p r o c e s s
is
st orderS, 9 and t h e r e f o r e can be d e s c r i b e d by
dc --= dt
~e K v is the v o l a t i l i z a t i o n c o e f f i c i e n t ,
K v ( C - CE)
(
C is the c o n c e n t r a t i o n of the c o m p o u n d in the
er at time t, a n d C E is the c o n c e n t r a t i o n that the c o m p o u n d w o u l d have in the w a t e r if it • in e q u i l i b r i u m with the p a r t i a l p r e s s u r e of the c o m p o u n d in the air. The t w o - f i l m m o d e l of Lewis and Whitman10 ion of o r g a n i c c o m p o u n d s from water.
is f r e q u e n t l y u s e d to d e s c r i b e the v o l a t i l i -
T h i s model assumes u n i f o r m l y - m i x e d w a t e r and air
ses s e p a r a t e d b y thin films of w a t e r and air in w h i c h m a s s t r a n s p o r t is by m o l e c u l a r fusion.
The e q u a t i o n r e l a t i n g the film c o e f f i c i e n t s of the t w o - f i l m m o d e l is11, 12
I
I
RT
+ KOL
kL
--
(
Hk G
~e K O L is the o v e r a l l m a s s - t r a n s f e r c o e f f i c i e n t based on the liquid phase, k L is the aid-film mass transfer coefficient,
R is the ideal gas constant, T is the a b s o l u t e temper
ce, H is the H e n r y ' s Law constant, and kG is the g a s - f i l m mass t r a n s f e r c o e f f i c i e n t . The v o l a t i l i z a t i o n c o e f f i c i e n t of E q u a t i o n ~quation
(2) are related12,13
by
(I) and the o v e r a l l m a s s - t r a n s f e r c o e f f i c i e n
i0!
KOL = KvY
q
~re Y is the depth of the water phase. Because follows
the r e c i p r o c a l that
I/Ko L in E q u a t i o n
liquid p h a s e ~pectively. 3istance
of a m a s s - t r a n s f e r
and
Analysis
of Equation
in the air
is r e s i s t a n c e
between
~uming s p e c i f i c
into high,
npounds
having
3istance
films d e p e n d s
conditions
low,
to v o l a t i l i z a t i o n
Latilization
is in the air film.
resistance
~ay -I and a k G value Acetone
has b e e n
volatility
film.
to v o l a t i l i z a t i o n .
compound
aqueous
solutions
[m.
Therefore,
3orption
on s e d i m e n t s
depends
the s e d i m e n t :ticle, hural
H values have
are based on a k L value
of 4.~
by Liss and Slater 11. in the high volatilit) Law c o n s t a n t ,
of the solute,
The a c t i v i t y
coefficient
std arm,
is s l i g h t l y
larger
and P
is s and the vapor
respectively, than the
giving
1.2 x 10-5
resistances
will
be i m p o r t a n t
in the volatilizatJ
will
be in the air film.
that b o t h
-- Adsorption
are the p h y s i c a l
the o r g a n i c
:ent of a d s o r p t i o n 17. tendency
of an o r g a n i c
of the sediment
and c h e m i c a l
compound
content
characterisics
The most i m p o r t a n t
property
of the c o m p o u n d
properti~
of the s e d i m e n t
surface
a l s o has a strong
from the water 18.
onto a sediment
Important
of the surface
and the a v a i l a b l e
of the sediment
of the c o m p o u n d
from s o l u t i o n
and of the compound.
sites on the surface,
}
from
but that most of the resistance
on the p r o p e r t i e s
sediments,
having
and air films
is in the air
the type of b i n d i n g
the e s c a p i n g
This value
H to
to v o l a t i l i z a t i o n
it is e x p e c t e d
from water,
~ticle
in std arm.
having
t
s
coefficient
limit at which most of the resistance
acetone
compounds
can be c a l c u l a t e d
at 2 5 ° C from P e r r y 16 are 6.7 and 0.301
H of 3.6 x 10 -5 std a t m m 3 mol -I.
compounds
of
of the r e s i s t a n c e
be c o n s i d e r e d
18 x 10 -6 ~ P
o5
organic
than 95 p e r c e n t
also has an e f f e c t on the Henry's
~re H is in std a r m m 3 mol -I, y is the a c t i v i t y of the pure solute
volatility
both the water
might
Division
Law constant,
For the high v o l a t i l i t y
for the open ocean
and therefore
of a c e t o n e
that th{
in the wate,
Smith et al. 15 d i v i d e d
classes.
These c a l c u l a t i o n s
H =
a t m m 3 mol -I
b a s e d on
significantly.
of the Henry's
For low v o l a t i l i t y
For i n t e r m e d i a t e
shown TM t h a t H for dilute
vapor pressure
transfez
films,
m a y be l a r g e l y
x 10 -3 std atm m 3 mol -I , m o r e
of 720 m day -I e s t i m a t e d
the s o l u b i l i t y
~ssure of a c e t o n e
from w a t e r
films may c o n t r i b u t e
1.2 x 10-5 std a t m m3 mol-1,
is a v o l a t i l e
However,
to mass t r a n s f e r
1.2 x 10 -5 std atm m 3 mol "I, more than 95 p e r c e n t
hween 4.4 x 10-3 and
iss.
compounds
is in the water
than
to m a s s
of the liquid and gas
in the water and air.
larger than 4.4
[ueS s m a l l e r
anificant
resistance
on the m a g n i t u d e
and i n t e r m e d i a t e
H values
is the r e s i s t a n c e
(2) by a number of r e s e a r c h e r s 8 , 14,15 has shown
of o r g a n i c
film, or that b o t h the
mixing
,pounds
is the overall
I/k L and RT/Hk G are the r e s i s t a n c e s
to the v o l a t i l i z a t i o n
[m, l a r g e l y
(2)
coefficient
area 17.
influence
is the f u g a c i t y
Solubility
is o f t e n
For
on the which
used as an
)0
ex of this
fugacity
with
ever,
approach
may not a l w a y s
this
Studies slightly osure
ever,
of the a d s o r p t i o n sorbed
carbon
to a d s o r b
of a c e t o n e
Giusti
are
limited.
but o n l y
of a c e t o n e
et al. 20 studied
was observed.
with montmorillonite.
t adsorption
will c o n t r i b u t e
todecomposition
-- P h o t o d e c o m p o s i t i o n
esult of the a b s o r p t i o n nsfer of e n e r g y
absorption
endent
on the
differ
intensity
which
of the
light,
of c o m p o u n d
processes
from rates
in d i s t i l l e d
the
light
incident
reactions
information
of
light
occurrlng
absorption
of
6
light,
which
is d i r e c t l y
of the c o m p o u n d ,
Photodecomposition
energy
and th~
absorbed.
but are b e l i e v e d
rates
of s u s p e n d e d
occurring
in stream~
The rate of d e c o m p o s i t i o r
per unit of light
water b e c a u s e
on
increa~
it is not e x p e c t e d
is the d e g r a d a t i o n by d i r e c t
I
were a l s o
fate of a c e t o n e
the c o n c e n t r a t i o n
degraded
ketones
diketones
however,
p r o c e s s e s 18.
of n a t u r a l l y
available
a photodecomposition
go to c o m p l e t i o n .
Acetone
erally agreed23
atmosphere
can occur
of
prior
compounds
in natural material
to
waters which
that q u e n c h
or
r e a c t i o n s 9.
is l i m i t e d
ctions 22.
and b e c a u s e
weight
are not as well u n d e r s t o o d ,
considerably
There
shows
of the c o m m o n
a weak
that s u n l i g h t
because
solvents
used
s t u d i e s 2 4 , 2 5 , 26.
rt w i t h
regard
There
energy.
characteristics of ethane
however,
in c y c l o h e x a n e
of acetone.
and c a r b o n
on the p r o d u c t s
at 280 nm,
however,
in p h o t o c h e m i c a l
by a t m o s p h e r i c
studies, suggest
but
gases.
it has b e e n
that a c e t o n e
monoxi
of
the
it is
less than 295 ~, are not t r a n s m l t t e d
and a b s o r p t i o n
These o b s e r v a t i o n s
-- B a c t e r i a l
ource of f o o d a n d / o r
is d i s a g r e e m e n t ,
wavelengths
to p h o t o d e c o m p o s i t i o n
degradation
on the p h o t o c h e m i c a l
at 313 nm with p r o d u c t s
absorption
of s c a t t e r i n g
several
terial
process
or by indirect
incident
and i n d i r e c t
dependence
vapor u n d e r g o e s the
This
compounds
vapor
with w a t e r
as the s o l u b i l i t y
to the
on the rate of a b s o r p t i o n
is the q u a n t i t y
increases.
that a c e t o n e
of a s e r i e s
decreased
Generally,
of o r g a n i c
i n t e n s i t y 18.
the
the a d s o r p t i o n
significantly
on light
enuates sitize
light.
is d e p e n d e n t
reactions
e a similar
of
from a s e n s i t i z e r ,
direct
sitized
G l a e s e r 19 found
Higher-molecular
o r t e d 21 to f o r m c o m p l e x e s on s e d i m e n t s
as the s o l u b i l i t y
if the c l a y was h y d r a t e d
a n d found that the e x t e n t of a d s o r p t i o n
adsorption
ntum yield
decreasing
be v a l i d 18.
by m o n t m o r i l l o n i t e ,
to the a c e t o n e .
ivated
the t e n d e n c y
through
Acetone
is not
used as a sensitiz
is p r o b a b l y
not c o m p l e t
processes.
degradation
This p r o c e s s
is the use of o r g a n i c can be d e s c r i b e d
compounds
by an e q u a t i o n
by b a c t e r i a of the
a
form 17
-Kdt C=Coe
~e C is the c o n c e n t r a t i o n centration radation. bacterial
at time Equation
(5) is a v e r y
degradation
and pH,
compound
zero, and K d is the f i r s t - o r d e r
3ent, all the n e c e s s a r y forms,
of the o r g a n i c
(
to occur, nutrients
temperature,
simplified bacteria
in the w a t e r
representation
acclimated
and trace e l e m e n t s
dissolved
oxygen,
at time t, C O is the
rate c o e f f i c i e n t
for b a c t e r i a l
of a v e r y c o m p l e x
to the o r g a n i c m u s t be p r e s e n t
and the o r g a n i c
compound
process. must
in the p r o p e r
compound
must
be amount
be within
ii(
rain ranges of v a l u e s and c o n c e n t r a t i o n s . radation p r o c e s s ,
Equation
However, despite the c o m p l e x i t y of the
(5) is f r e q u e n t l y used as a first a p p r o x i m a t i o n of the p r o c e s s
T h e r e have been a limited number of studies of the bacterial degradation of acetone. and Agg 27 s u g g e s t e d that a c e t o n e was usually easily d e g r a d a b l e in a biological sewage atment plant. compound.
They
stress, however,
the importance of a c c l i m a t i z a t i o n of the b a c t e r i a to
Abrams et al. 5 s i m i l a r l y c l a s s i f i e d acetone as having low persistence.
Helfg+
al. 28 m e a s u r e d r e f r a c t o r y i n d i c e s for a number of organics where a value of 1.0 indicates dily b i o d e g r a d a b l e a v a l u e of 0.8,
c o m p o u n d s and a value of 0 indicates n o n - d e g r a d a b l e compounds.
i n d i c a t i n g a d e g r a d a b l e compound.
It was expected,
therefore,
Aceton
that
terial d e g r a d a t i o n will c o n t r i b u t e s i g n i f i c a n t l y to the fate of a c e t o n e in streams. 0 r p t i o n by a l g a e and m o l d s -- O r g a n i c compounds in water may be a b s o r b e d by biota within ecological
system.
bon a n d / o r energy,
Once absorbed, excreted,
the compound may be degraded and used as a source of
or s t o r e d by the biota, resulting in b i o a c c u m u l a t i o n .
The
ent of a b s o r p t i o n and b i o a c c u m u l a t i o n depends on the c h a r a c t e r i s t i c s of both the c o m p o u n d the biota. u b i l i t y 17.
The m o s t i m p o r t a n t p r o p e r t i e s of the compound are its stability and S t a b i l i t y in the w a t e r e n v i r o n m e n t is necessary for b i o a c c u m u l a t i o n
the o t h e r hand, umulation
to occur.
if the c o m p o u n d is very soluble In water, then excretion rather than
is m o r e likely.
The m o s t important property of the biota is the surface area
ause a d s o r p t i o n will likely be i n v o l v e d in the absorption process 17. T h e r e are no known s t u d i e s of the a b s o r p t i o n of acetone by biota; however, there have b~ i m i t e d number of s t u d i e s of o t h e r low m o l e c u l a r weight solvents.
Benzene and toluene w e r
nd to have both a s t i m u l a t i n g and an inhibiting effect on the growth of p h y t o p l a n k t o n 2 9 . ed s o l u t i o n s of aromatics,
alkanes, and alkenes resulted in increased rates of photo-
thesis
Also, it was found that several aquatic fungi were c a p a b l e of
in m a r i n e a l g a e 30.
f a d i n g a l k a n e s a n d a l c o h o l s 31. accumulation
Finally, an inverse relation between the l o g a r i t h m of the
factor for C h l o r e l l a fusca and the logarithm of the water solubility was fou
34 s o l v e n t s 32.
All these studies,
however, were for low solubility compounds, and the
a v i o r of a c e t o n e is very likely to be different. erimental Procedures lytical -- A c e t o n e c o n c e n t r a t i o n s
in w a t e r samples were d e t e r m i n e d using a Varian* gas
o m a t o g r a p h with a flame i o n i z a t i o n detector.
For c o n c e n t r a t i o n s in the low m i l l i g r a m - p e r
er range, the a c e t o n e was s e p a r a t e d from the water and pre-concentrated using a strip and p procedure
in w h i c h a 5-~i a l i q u o t of the sample was carried through a Tenax trap by a
eam of h e l i u m gas.
The a c e t o n e was a d s o r b e d on the Tenax at room temperature, and the
er was c a r r i e d on t h r o u g h the trap. o r b e d from the t r a p by h e a t i n g to concentrations
After a 15-minute stripping period, the acetone was
160-180°C, and flushed into the c h r o m a t o g r a p h for analy
in the m i c r o g r a m - p e r - l i t e r
range, a headspace s w e e p i n g and t r a p p i n g
c e d u r e was used in w h i c h the v a p o r a b o v e 20.0 ml of sample at 50°C was swept into a Tenax e use of the b r a n d names in this report is for identification p u r p o s e s only and does not ply e n d o r s e m e n t by the U.S. G e o l o g i c a l Survey.
by a s t r e a m
of h e l i u m
the t r a p by h e a t i n g i s i o n of
gas.
to
rption
plate
describing
The b a t h
conditions
id be c o n s i d e r e d produced
speed
nitrogen
gas,
calculated
were
of E q u a t i o n
was d e s o r b e d
for a n a l y s i s .
2 percent,
Details
and precis
of the technique
given
by R a t h b u n
using
27 m o n t m o r i l l o n i t e
a size
The e x p e r i m e n t a l 10 g w e t w e i g h t to g i v e
er s t o p p e r
ed in a f r e e z e r ared using b a t o r at
were
en as d e s c r i b e d media
erilized
the aJ
for all
ranging
from 0 to
the d i s s o l v e d
oxygen
concentration
Volatilization
coefficier
nonlinear
of the e x p e r i m e n t a l
least
a n d data analysJ
from a small
from Wards
concentration
sediment
was added,
Control
flasks
and all the flasks
then s a m p l e d
at p e r i o d i c
through
vial with
without
were p l a c e d
during
matter
and
of the p u r e flask.
clays
with a
the s e p t u m liquid
the s e d i m e n t s
on a shaker
with a
nitrogen
platform
The e x p e r i m e n t a l
the experiment,
and
were in an and
and the samples
previously. a high
from a small charge
sediment clay
water
stream.
on the clays.
conditions
he m o n t m o r i l l o n i t e
purity
local
were
from
in all e x p e r i m e n t s
In one experiment,
an o r g a n i c
carbon
Milli Q system,
a c t e d as a p e p t i z i n g
The pH was v a r i e d
used
was used.
giving
from a M i l l l p o r e The b u f f e r
content
3.4 to
except
natural of
c
Acetone
flask were m i x e d by shakinc
at one cycle p e r second. intervals
all o r g a n i c
The
Establishmer
the flask was c l o s e d
sample was w i t h d r a w n
analysis.
stream.
Science
in a 250-mi
of the
septum
in a seriE
was used w i t h no processin~
100 m g d r y weight
contents
in a small
local
Natural
in 100 ml of m e d i u m
immediately
was i n v e s t i g a t e d
of Hedges 34 to remove
s e p t u m port,
oscillated
Sterile natural
conditions
the water,
per minute rateg
of time.
sediment
of s u s p e n d i n g
sediment
The p l a t f o r m
the s u r f a c e
riments.
within
to give an initial
on s e d i m e n t s
The natural
a n d an initial
at - 2 0 ° C until
w e r e used,
and water
0.5 ~m.
initial
frozen
30 m min -I,
These
data a n d a t w o - p a r a m e t e r
9 kaolinite
consisted
the same p r o c e d u r e ,
20°C.
flasks
was
of
were of the oxyc
in the water was p r o v i d e d
of s t r i p p i n g
descriptions
a n d a natural
a sampling
one m i n u t e ,
sample
Mixing
acetone
as a function
to the p r o c e d u r e
the d e s i r e d
no m i x i n g
at 21 c y c l e s
consisted
of acetone
a n d no.
less t h a n
procedure
from water
the m e a s u r e m e n t
with r e v o l u t i o n
sufficient
Complete
of the n a t u r a l
containing
ly for a b o u t This
stirrer
the w a t e r
clays
according
fraction
with
a n d Tai 13.
s w e r e no.
e were prepared
with
surface.
which oscillated
-- The a d s o r p t i o n
two p u r e
of a c e t o n e
for all experiments.
because
of the water
procedure
(I).
xperiments
rsed
2 and 4 percent.
f r o m the c o n c e n t r a t i o n - v e r s u s - t i m e
r p t i o n on s e d i m e n t s
Three
than
in a fume hood w i t h a face v e l o c i t y
adding
130 m g 1 -I , a n d s a m p l i n g
er35,
less
the v o l a t i l i z a t i o n
electric
The e x p e r i m e n t a l
with
res a n a l y s i s
rol
the a c e t o n e
into the c h r o m a t o g r a p h
bath simultaneously
conditions
disturbance
and a variable
the w a t e r
nge.
was
as l o w m i x i n g
no v i s i b l e
0 rev m i n -I.
icient
period,
was g e n e r a l l y
in the air were constant
in the b o t t o m of the b a t h
riments
btain
sweeping
flushed
was b e t w e e n
constant-temperature
coefficients.
efore m i x i n g
edures
and
technique
technique
-- C o e f f i c i e n t s
in a large
bout
15-minute
by T a i 3 3 .
tilization ured
a
160-180°C,
the m i l l i g r a m - p e r - l i t e r
he m i c r o g r a m - p e r - l i t e r given
After
11.4
Run 4-35
McIlvaine's agent and
for the where
fulvic acids
the
were added
13 mg 1-1 for the mixture.
ii0
~odecomposition ~xperiments.
-- The p h o t o d e c o m p o s i t i o n
Rhodamine-WT
these e x p e r i m e n t s dispersion
first
procedure
in water,
ppers,
e used r a t h e r
of a c e t o n e
stock
than borosilicate
180 nm w h e r e a s
of the w a v e l e n g t h s
the d i s t i l l e d
8 hours
were
eriment terial
experiments
transferred
repeated
ium,
of
ficient
acetone
1-I.
Samples
il analysis.
test tubes,
experiment.
capped
longer
with
serum
Quartz
tube
to w a v e l e n g t h s than
the atmosphere
300 nm.
Th
is 295 t~. 23 giving
was for 7 hours
one da I
were
the d e s i r e d
cap,
initial
to e q u i l i b r a t e Initial
through frozen
technique.
sewa, wet
alone.
rod shaped and about
I ~m
and G a r d i n e r 37, and an i n o c u l u m
10-day intervals.
hours
A culture
The b a c t e r i a
No effort
the bacteria
in a sterile
medium.
was m a d e
to
were c e n t r i f u
This p r o c e d u r e
of an experiment.
all g l a s s w a r e
and the medium.
filled with the w a s h e d b a c t e r i a
oxygen.
in a serie=
from a p r i m a r y
and finally acetone
typically
to initiation
for several
with d i s s o l v e d
obtained
culture
of s t e r i l i z i n g
then
was i n v e s t i g a t e d
of each experiment,
prior
consisted
w%s s t i r r e d
septum
at about
by a of the
E / B O D respirometer.
and acetone, were
concen-
at the end of the experiment.
source was d e v e l o p e d
and then r e s u s p e n d e d
the b a c t e r i a
as a control.
were
medium
at the b e g i n m i n g
by b a c t e r i a
u s i n g an e n r i c h m e n t of glucose
of acetone
for d e t e r m i n a t i o n
International
that the bacteria
sterile
and a l l o w e d
served
h a teflon-faced
transp
water was used i
is t r a n s p a r e n t
solution
of acetone
to the i n i t i a t i o n
procedure
to give
of the c h a m b e r s
Distilled
in the second
for d e t e r m i n a t i o n
in the m e d i u m of Montgomery
the r e s p i r o m e t e r
the m e d i u m
rd c h a m b e r
showed
to wash
and the m e d i u m
saturate
concentrati~
exposure
in the test tubes
as a sole carbon
plant
grown
Prior
The e x p e r i m e n t a l ee c h a m b e r s
of the desired
to the sunlight.
through
a larger volume
for the stock
remaining
for 30 m i n u t e s
twice
mass
was for about 8 hours per day for 3 days,
u s i n g an O c e a n o g r a p h y
to a fresh,
rev m i n -I
quartz
water experiment,
required
then a m i x t u r e
were
p a pure culture. 2,000
which
use a c e t o n e
treatment
fed g l u c o s e ,
The b a c t e r i a
the convective
o n l y for w a v e l e n g t h s
w i t h a syringe
The d e g r a d a t i o n
ctron p h o t o m i c r o g r a p h s g.
exposure
periodically
--
that w o u l d
from a local
tially
to q u a r t z
for e x p o s u r e
transmitted
In the s t r e a m
solutions in water.
because
is t r a n s p a r e n t
the s o l u t i o n s
degradation
laboratory
tracer 36 was also c o n s i d e r e d
stream was u s e d
transferred
tubes
number
day.
removed
for
and dye
local
in a l i m i t e d
studies.
stock
outdoors
of s u n l i g h t
t e c h n i q u e 36 were m e a s u r e d
and
bacteria
were
glass
experiment,
Dye c o n c e n t r a t i o n s
orometric
ple
glass
23 hours.
the n e x t
Samples tions.
water
of
in water,
and p l a c e d
er limit
in stream
f r o m a small
solutions
to a rack,
get than
al e x p o s u r e
used as a water
of p r e p a r i n g
and dye
and water
of t h e s e attached
is c o m m o n l y
consisted
acetone
experiment
ntities
which
was i n v e s t i g a t e d
this dye was to be used to d e t e r m i n e
characteristics
The g e n e r a l acetone
because
of acetone
to obtain
temperature
suspended
The in th
equilibration
and
One liter of m e d i u m was u s e d in each flask. concentration before
acetone
was then added with a syringe
the initial
concentrations
samples ranged
a septum p o r t with a syringe, immediately
with
liquid
were withdrawn. from
16 to
transferred
nitrogen,
t T
158
to a vial
and stored
at - 2 0 ° C
In s e v e r a l
experiments,
nbers on the n i g h t tone.
Sufficient
~hese c h a m b e r s ~rption series Daena
of
te f l u o r e s c e n t
trol
flasks
eral
and
no a l g a
bacterial
from a small
of the p l a t f o r m
local
to a timer
stream.
as a function
sampled (algal
concentrations
were
flask-shakez
studles
by eight
was use
20-watt
descrlbed
c<
for the
the alga and a c e t o n e
of time.
and
Bristols 38, yeast-
potential) 40 media were used.
reduced
alga
Cladophora
set for a 12-hour cycle.
containing
growth
The
adsorption
the same as that p r e v i o u s l y
were
investigat
the b l u e - g r e e n
was p r o v i d e d
flasks
was
by the green algae
in the s e d l m e n t
wit~
was then add~ previously.
and molds
pyrenoidosa,
Experimental
AGP
as d e s c r i b e d
by algae
dominated
the b a c t e r i a
concentration
was c o n d u c t e d
were c o n n e c t e d
a n d 40 mg 1 -I of s t r e p t o m y c i n
by t r e a t m e n t
with
In
12 mg 1-I of
sulfate.
Discussion
atilization
-- The e x p e r i m e n t a l
tone and t h e a b s o r p t i o n atilization fficient
where
absorption
This
is v a l i d
all the r e s i s t a n c e
from Equation
liquid-film Mixing
are p l o t t e d
the o x y g e n
in the water.
volatilization
coefficients
coefficients
t virtually follows
mold
to the two e×perimenta]
to p r e t r e a t
acetone
Chlorella
described
was b a s i c a l l y
experiments.
experiments,
ditions
tubes
p r o t e o s e - p e p t o n e 39, and
icillin-G ults
procedure
containing
aquatic
were a d d e d
of acetone
green alga
at the s u r f a c e
These
initial
algal p o p u l a t i o n
previously
lumens
tubes.
adsorption
rogen 39,
the
natural
apparatus
The e x p e r i m e n t a l iment
-- The a b s o r p t i o n
a n d an u n i d e n t i f i e d
of 8,860
of a c e t o n e
of an e x p e r i m e n t
and the e x p e r i m e n t
using
a mixed
tform-incubator ~mination
day,
experiments
initiation
to give the d e s i r e d
and molds
flosaquae,
Spirogyra,
to the
acetone
the n e x t
by algae
~ g 1 -I q u a n t i t i e s
prior
(2) t h a t
coefficients
for o x y g e n in Figure
are given
by Equation I.
absorption
has been u s e d as an indicator
of oxygen
absorption
of m i x i n g
p r e v i o u s l y 4 1 , 42
is in the liquid
coefficient
(I) for
The acetone
of the o x y g e n
it has been e s t a b l i s h e d
to the a b s o r p t i o n the o x y g e n
in Table
I as a f u n c t i o n
coefficient because
defined
film;
is v i r t u a l l y
theref¢
identical
t
coefficient.
conditions
can a l s o be d e s c r i b e d
in terms of the s t i r r e r
Reynolds
Number
which
of the s t i r r e r
blade,
and v
i
i n e d 43 as
nL2 Re = - -
re n is t h e r e v o l u t i o n kinematic
viscosity
nt in F i g u r e The e f f e c t ults th of
of R u n s 200 mm.
rate of the stirrer,
of the water.
I, i n d i c a t i n g of w a t e r A-10,
L is the length
The stirrer
the d e p e n d e n c e
Reynolds
d e p t h on the v o l a t i l i z a t i o n
A-14,
and A-15
The s t i r r e r
Number
of both c o e f f i c i e n t s coefficient
for a depth of 267 mm with
Reynolds
Numbers
for these
is shown
next to each dat
on mixing. can be seen by c o m p a r i n g
t~
the result of Run A-2 for a
runs were v i r t u a l l y
identical;
how~
Table
I
E X P E R I M E N T A L V O L A T I L I Z A T I O N C O E F F I C I E N T S FOR ACETONE, AND A B S O R P T I O N COEFFICIENTS FOR O X Y G E N
Run
Stirrer Reynolds Number x 10-4
Water Temp. ("C)
A-I
7.90
25.0
200
2.23
A-2
2.71
25.1
200
1.34
A-3
4.89
25.1
200
1.67
A-4
9.41
25.1
200
2.22
30.1
Water Depth, Y (mm)
Acetone Volatilization Coefficient, K v (day-l)
Oxygen Absorption Coefficient, K o (da~-1)
25.4 4.00 8.62
A-5
5.95
25.0
200
1.68
11.3
A-6
7.00
25.2
200
1.91
14.8
A-7
3.80
25.1
200
1.55
A-8
0
25.1
200
A-9
9.43
25.2
200
A-10
2.69
24.8
267
A-11
1.58
25.1
A-12
0
25.1
A-13
0
A-14
2.70
A-15
2.71
.543 2.31
5.78 1.59 31.1
.995
1.88
267
.917
2.17
267
.683
1.54
24.9
267
.625
1.43
24.9
267
.968
2.45
25.1
267
.982
2.78
O o~
2 QSO
!
I
I
I
,
i
=
a<
Z 0 ~,,,
i 7.00 ® i
2.00
","
3.80 ~ . ~ . . Q / ( 9 ::~"'~ 4.89 fv
0,, p-
1.50
_
M.
/
9.4'1
~
5.95
12.69 / . 1.00"
Zr'J'
2.71
/
0 p-
<
N__
/
i
/
/ (92.71
_ u_ O
9.43
7.90
0.50
L
INDICATES STIRRER REYNOLD S
/ 1.58
NUMBER X 10 -4)
9
I--
< .J
o >
O
0
I
I
]
I
[
I
I
4
8
12
16
20
24
28
32
A B S O R P T I O N C O E F F I C I E N T FOR O X Y G E N ( D A Y S "1)
Figure l°--Volatilization coefficient for acetone as a function of the absorption coefficient for oxygen for various water mixing conditions
ii0
volatilization [ted data
coefficient
suggest
that,
~er should p r o b a b l y Acetone ients,
was a b o u t
to define
contain
volatilization
the water
coefficients
and the v o l a t i l i z a t i o n
In the low m i x i n g
volatilization
in the water
mixing
range would
urred b e c a u s e ing range.
showed m u c h
appear
Therefore,
The v o l a t i l i z a t i o n ing c o n d i t i o n s
for a c o n s t a n t
dition.
ing c o n d i t i o n s
resulting
condition
-- Results
in Table
All the e x p e r i m e n t s
and showed
no s i g n i f i c a n t
sterile
conditions
with natural
Run 4-35,
however,
with n o n s t e r i l e
loss after about
lag p e r i o d
luding the
being
lag period,
This d e v i a t i o n
natural
the i n i t i a t i o n
500 hours.
the f i r s t - o r d e r
in this
in lakes and ponds
for very low
days-1
conditions.
T h e s e measur(
stream
of acetone
for highel
situation. on s e d i m e n t s
and k a o l i n i t e
over
as a low mix~
considerably
for a natural
long time periods.
showed
no s i g n i f i c a n t
sedlment,
showed
significant
and r e s u l t e d
loss was a t t r i b u t e d
rate c o e f f i c i e n t
describing
this
Run 4-~ loss of
loss
in approximatel~
to b a c t e r i a l
to a c c l i m a t e
are
were done und(
similarly
for the b a c t e r i a
ic
from 0.625
of the e x p e r i m e n t
This
the time n e c e s s a r y
may have
water phase.
be i n c r e a s e d
loss of acetone
sediment,
in the
a uniformly-mixed
with m o n t m o r i l l o n i t e
e under
h the
on m i x i n g
was not f u l f i l l e d
of the study of the a d s o r p t i o n
rile c o n d i t i o n s
-percent
would
in the ware
the b e h a v i o r
be a p p l i c a b l e
I ranged
absorptior
0 and 6 days-1
dependence
however,
water p h a s e
in the air phase
on s e d i m e n t s
inning about 90 hours after
model,
of
coef-
o n l y about
conditions
in the air that s h o u l d be c o n s i d e r e d
coefficients
marized
tone.
and the small
to produce
in Table
increased
coefficients
days -I for very high m i x i n g
from winds
Reyno]
conditions
in the o x y g e n
on m i x i n g
with the model.
mixed
of m i x i n g
coefficient
model m a y not always
orption
2.
increase
absorption
of acetone
given
that these
absorption
independent
dependence
is i n s u f f i c i e n t
to 2.31
mixing
It is e x p e c t e d
oxygen
of a u n i f o r m l y
coefficients
in the water
These
than the o x y g e n
volatilization
to be i n c o n s i s t e n t
mixing
smaller
with the t w o - f i l m
the t w o - f i l m
depth.
the stirrer
for a f i v e - f o l d
larger
coefficients
the a s s u m p t i o n
re the rate of v e r t i c a l
ts were
Thus,
are c o n s i s t e n t
for the s h a l l o w e r more precisely,
was r e l a t i v e l y
range b e t w e e n
coefficient
The small v o l a t i l i z a t i o n ditions
were m u c h
from 6 to 30 days -I , the a c e t o n e
percent.
larger
conditions
depth.
coefficient
~he water over m u c h of the range. fficient
36 p e r c e n t
the m i x i n g
degradation,
to the acetone. loss was about
0.(
s-1. todecomposition centration taining
acetone
9 percent ing this
-- Results
exposure
centration
water
exposure
in the a c e t o n e
experiment
showed
o n l y and an 8.6 p e r c e n t period.
no change
decrease
in the acet(
in the tube
The dye c o n c e n t r a t i o n
and dye and dye o n l y solutions,
decreased
respectively,
period.
of the local in either
over a 15-hour
acetone
and dye over a 23-hour
and 24.0 p e r c e n t
Results
of the d i s t i l l e d
in the tube c o n t a i n i n g
stream water e x p e r i m e n t
the tube c o n t a i n i n g
exposure
period.
showed
acetone
no s i g n i f i c a n t
change
only or the tube c o n t a i n i n g
The dye c o n c e n t r a t i o n
decreased
in the aceton( acetone
13.9 p e r c e n t
and
and
16.2
108
Table 2 S U M M A R Y OF S E D I F ~ N T A D S O R P T I O N E X P E R I M E N T S AT 20 ° CELSIUS
Run
Sediment
Medium
pH
Duration of Run (hr)
Initial Acetone Conc. (m@ 1-I)
Results
4-I
Montmorillonite (100 mg)
McIlvaine buffer
7.7
4.67
160
No loss of a c e t o n e
4-11
Montmorillonite (100 mg) F u l v i c Acid
~4zIlvaine buffer
7.7
171
160
No loss of a c e t o n e
3-175
Montmorillonite (100 mg)
McIlvaine buffer
7.7
333
925
Small loss in both exp. and c o n t r o l flasks; all data s c a t t e r e d
4-47
Montmorillonite (100 mg)
Milli Q water
3.4
284
346
No loss of acetone
4-70
Montmorillonite (100 mg)
Milli Q water
8.9
101
38
No loss of a c e t o n e
4-23
Montmorillonite (100 mg)
Milli Q water
8.9
174
160
No loss of a c e t o n e
4-31
Montmorillonite (100 mg)
Milli Q water
11.4
175
160
No loss of a c e t o n e
4-43
Kaolinite (100 mg)
Milli Q water
6.9
503
150
No loss of acetone
4-25
Local stream sediment (2 g wet)
Local stream water
8.4
338
105
No loss of a c e t o n e
4-35
Local stream sediment (10 g wet)
7.3
502
120
Loss of a c e t o n e o c c u r r e d after 90 hours in exp. flasks; ~100 p e r c e n t loss after 500 hours
Local stream water (Not sterile)
=ent in the a c e t o n e
and dye and dye o n l y solutions,
respectively,
d u r i n g this e x p o s u r e
Lod. It was c o n c l u d e d acetone
that s i g n i f i c a n t
d i d not a f f e c t
dye was e x p e c t e d
photodecomposition
significantly
because
of a c e t o n e
the p h o t o d e c o m p o s i t i o n
it has been
reported
did not occur,
of the dye.
in the literature
that
and
that
Decomposition
rhodamine-WT
oJ
degrad~
~ o c h e m i c a l l y 3 6 , 44 . Zerial d e g r a d a t i o n times
-- The e x p e r i m e n t a l
for the b a c t e r i a l
before culated period
the b a c t e r i a from E q u a t i o n excluded
u s e d to o b t a i n
from the data.
s in which
ut 13 hours. hours.
are d i v i d e d
concentration
regression
difference
shows
the
3.
The
lag time
The c o e f f i c i e n t s
as a f u n c t i o n
is th~ were
of time data w i t h
of a log e t r a n s f o r m a t i o n
into two groups,
of
ranged
on w h e t h e r
overnight
significantly
the lag time
importance
depending
of a c e t o n e
the lag time
For runs with p r e t r e a t m e n t ,
This
and the a p p r o x i m a t e
t]
Equation
(~
to the data.
that this p r e t r e a t m e n t
was no p r e t r e a t m e n t ,
in Table
of the acetone.
with a small c o n c e n t r a t i o n
It was found there
Linear
rate c o e f f i c i e n t s
are given
degradation
fit of the e q u a t i o n
results
teria w e r e p r e t r e a t e d
of acetone
begin
(5) and the a c e t o n e
a best
The e x p e r i m e n t a l
experiment.
degradation
actively
first-order
or not the
before
reduced
initiation
the lag time.
from 5 to 19 hours
ranged
of a c c l i m a t i o n
from
and a v e r a g e d
I to 3 hours
of a c u l t u r e
o: FoJ
and averac
of b a c t e r i a
to i
anic s u b s t r a t e . The d e g r a d a t i o n
coefficients
9 to 7.9 days -I and a v e r a g i n g fficient
of v a r i a t i o n
degradation
of v a r i a t i o n
est also
shows
in Table
3 show c o n s i d e r a b l e
scatter,
3.9 days -I for those runs with no p r e t r e a t m e n t .
of these v a l u e s
coefficients
fficient
presented
ranged
from 0.43
of 79 percent.
that the means
was 63 percent.
are s i g n i f i c a n t l y
fr(
The
For those runs with p r e t r e a t m e n t ,
to 3.4 days-1
Comparison
ranging
and a v e r a g e d
of the mean values different
1.4 days-1
with a
using a t w o - t a i l e d
at the 5 percent
level
of
nificance. An e x p l a n a t i o n possible pirometer ium.
chambers
Thus,
acetone,
for the d i f f e r e n c e
explanation
at the b e g i n n i n g
the a c e t o n e
effectively
experiment
was still
reducing
for p r e t r e a t m e n t
s, the e f f e c t
might
tone c o n c e n t r a t i o n s
because
acetone
than e x p e c t e d
of an e x p e r i m e n t
going
K d value.
However,
runs.
than Also,
to have lower K d values
of this effect, A linear
for the no p r e t r e a t m e n t
resulting
regression data
-0.48.
This
coefficient
is s i g n i f i c a n t
at the
endence
of the K d v a l u e s
on the initial
acetone
uniformly
as the b a c t e r i a
shorter
for the p r e t r e a t m e n t
is not r e a d i l y
for the acetone
to become
into s o l u t i o n
the a p p a r e n t
be e x p e c t e d
concentration.
tone c o n c e n t r a t i o n
the m e a n K d values
runs was c o n s i d e r a b l y
w o u l d be g r e a t e r
tone c o n c e n t r a t i o n s
initial
between
is that it took longer
because
runs with
large
of
initial
small
relation
initial
between
Kd
of the initial
3 gave a c o r r e l a t i o n
concentration
degra,
the d u r a t i o n
than runs w i t h
level,
in the
for the no p r e t r e a t m e n t
in an inverse
in Table
mixed
to the
in the m e d i u m
of K d as a function
10 p e r c e n t
apparent.
added
indicating
coefficient
a weak
as hypothesized.
invers,
A linear
Table EXPERIMENTAL BACTERIAL
FIRST-ORDER DEGRADATION
3
RATE
COEFFICIENTS
OF A C E T O N E
FOR THE
AT 25 ° C E L S I U S
No Pretreatment
Initial Acetone Conc. (m 9 1 -I )
Approximate Lag Time (hr)
Degradation Coefficient, Kd ( d a y s -I )
IA
34
19
7.9 7.2
Ru___nn
IB
34
19
2A
35
19
5.8
2B
36
18
6.7
3A
78
6
2.6
3B
146
8
2.6
4A
16
5-10
3.6
4B
39
6-8
2.9
4C
55
8-10
5A
20
16
7.0
5B
37
17
I .3
13
4.8
6A
17
6B
38
.79
15-16
2.3
7A
77
10
I .4
7B
158
10
I .6 Mean
= 3.9
Cv!,/ = 63%
Pretreatment
8A
38
2
8B
53
2
I .2
8C
77
3
9A
20
I
3.4
9B
40
I
I .3
.89 .43
Mean
= 1.4
C I_/ = 79% v
C.I~/ = v
(Standard
deviation/Mean)
x 100%
iii]
~ssion of the p r e t r e a t m e n t ted d a t a ribute
set.
Finally,
ly ideal
olved o x y g e n , coefficients rption molds
are
2, 3-111, 5 with erial
and s u b s t r a t e
by algae
activity.
ribing
-I.
were e x c l u d e d
this o c c u r r e d
either
describing
degradation
studies
th c o n d i t i o n s
were
a long time p e r i o d first-order
of these
nonsterile
in Runs in Run
when
mold
from the local
of a b o u t
significantly
cultures
or a f t e r
long time p e r i o d s had declined.
in the r e s p i r o m e t e r a temperature
of 25=C used
studies.
studies.
the
describing
two factors
of 2 0 a C was u s e d in the a b s o r p t i o n
in the d e g r a d a t i o n
for b a c t e r i a
when
First-order
the c o e f f i c i e n t s At least
algal
was o b s e r v e d .
activity
First,
absorbe.
and a m i x e d
conditions
than
0.25
rate c o e f f i c i e n t s .
Some loss of a c e t o n e
however,
the
rate c o e f f i c i e n t
In Run 4-5 when anti-
was neither
of two u n i a l g a l
stream.
were not s p e c i f i c a l l y
not ideal
was o b s e r v e d
by algae
used to reduce b a c t e r i a l
of a c e t o n e
a r e d w i t h the t e m p e r a t u r e
was o b s e r v e d
rate c o e f f i c i e n t
that acetone
the loss were smaller,
to this difference.
he a b s o r p t i o n
suggest
that d e g r a d a t i o n
were not used to reduce
were used.
with a first-order
f r o m the local under
The
under
bacteria,
of a c e t o n e
In Run 3-149 with an aquatic
when a n t i b i o t i c s
the growth process
of the a n t i b i o t i c s
coefficients bacterial
mold
declined.
also
values.
Some loss of a c e t o n e
in the c a l c u l a t i o n
studies
affect
a n d an a q u a t i c
ributed
0.3 days -I.
of the a b s o r p t i o n
ctiveness
had a p p a r e n t l y
loss was o b s e r v e d
it s i g n i f i c a n t l y
ver,
cultures.
was o b s e r v e d
acclimated
loss of a c e t o n e
in Run 3-119 after
The lag p e r i o d s
lation
No appreciable
of the
would
in the l a b o r a t o r y
of the study of the a b s o r p t i o n
Loss was also o b s e r v e d
loss was about
in the m e d i u m
it is e x p e c t e d
than these
where a n t i b i o t i c s
not used,
Results did
Therefore,
because
3.
concentration,
s t r e a m algal p o p u l a t i o n
am, no loss of a c e t o n e ics w e r e
4.
in Table
meaningful
3 were d e t e r m i n e d
will be smaller
-- Results
of the a n t i b i o t i c s
this
in Table
concentrations.
in T a b l e
to mix r a p i d l y
observed
and trace element
3-127 w i t h u n i a l g a l
the local
ctiveness
given
streams
and molds
summarized and
of the acetone
of n u t r i e n t
in natural
3 was not c o n s i d e r e d
of the results
coefficients
conditions
in Table
failure
to the v a r i a b i l i t y
The d e g r a d a t i o n
data
Second,
made up for g r o w t h of bacteria,
as they were in the d e g r a d a t i o n
stud
the m e d i a
use.
therefore,
studies.
ary and Conclusions Laboratory one
rption s.
of several
and rivers
by sediment,
These esses
important
studies could
were
in d e t e r m i n i n g limited
Consideration
that m i g h t a f f e c t
These
studies
bacterial
that v o l a t i l i z a t i o n
be eliminated.
effects.
of the p r o c e s s e s
were completed.
photodecomposition,
It was c o n c l u d e d
ly to be
tire
studies
in s t r e a m s
degradation,
and bacterial
the fate of acetone
to s i n g l e - p r o c e s s In natural
systems
streams,
of m u l t i p l e - p r o c e s s
included
the c o n c e n t r a t i o n
and a b s o r p t i o n
degradation
of
volatilization, by algae
were the p r o c e s s e s
an mos
in streams. so that i n t e r a c t i o n s
however, systems
interactions was b e y o n d
among
may result
the in non-
the scope of this
studl
112
Table 4
SUMMARY OF ALGAE AND MOLD ABSORPTION EXPERIMENTS AT 20 ° CELSIUS
Run 3-102
Biota Chlorella
Medium Proteose-
Sterilit~
pH
Duration of Run (hr)
Not sterile
7.0
216
Initial Acetone Conc. (m~ 1-I) 400
peptone
Results No loss of acetone
3-111
Chlorella
Bristols
Antibiotics used but not sterile
7.0
264
40
No loss of acetone
]-127
Anabaena
Algal growth potential (5 times normal strength)
Not sterile (Aseptic lab culture)
9.3
451
40
Small loss of acetone; less than 8% in experimental flasks
]-119
Local stream algae
Algal growth potential (5 times normal strength)
Antibiotics used
8.0
672
32
No loss of acetone after 168 hrs; 36% loss after 360 hrs; -100 loss after 672 hrs
3-165
Local stream algae
Algal growth potential (5 times normal strength)
Antibiotics used (except in one expt. series)
8.4
592
40
13% loss in controls; 23% loss in experimentals
|-91
Local Milli Q stream water algal floc (200 mg dry)
Antibiotics used
7.3
93
30
No loss of acetone
)-149
Local stream mold
Yeastnitrogen
Antibiotics used
5.5
574
1.6
No loss of acetone
L-5
Local stream mold
Yeastnitrogen
Sterile 5.4 controls; no antibiotics in expt. series
356
80
No loss in controls; 97% loss in experimentals after 356 hrs
i11
~R/~NCES
W. M. Shackelford and L. H. Keith, "Frequency of Organic Compounds Identified in Water, EPA Report No. 600/4-76-062 (Dec. 1976). Environmental Protection A g e n c y , " P r e l i m i n a r y Assessment of Suspected Carcinogens in Drinking Water," EPA Report No. 560/4-75-005 (Dec. 1975). M. Khare and N. C. Dondero, Environ. Sci. Technol., 11, 814 (1977). E. D. Pellizzari et al., "Identification of Organic Components in Aqueous Effluents frol Energy-Related Processes," ASTM Spec. Tech. Publ. No. 686, p. 256 (1979). E. F. Abrams et al., "Identification of Organic Compounds in Effluents from Industrial Sources," EPA Report No. 560/3-75-002 (April 1975). A. A. Stevens et al., J. Am. Water Works Assoc., 68, 615 (1976). H. B. Fischer et al., Mixin@ in Inland and Coastal Waters (Academic Press, New York, 19 D. Mackay and Y. Cohen, "Prediction of Volatilization Rate of Pollutants in Aqueous Systems," in Program and Abstracts. S~mposium on Nonbiolo@ical Transport and Transformation of Pollutants on Land and Water, NTIS Report PB-257347, p. 122 (May 1976). J. H. Smith et al., "Environmental Pathways of Selected Chemicals in Freshwater Systems Part I.: Background and Experimental Procedures," EPA Report No. 600/7-77-113 (Oct. 1977). W. K. Lewis and W. G. Whitman, Ind. Eng. Chem., 16,
1215 (1924).
P. S. Liss and P. G. Slater, Nature, 247, 181 (1974). D. Mackay and P. J. Leinonen, Environ. Sci. Technol., 9,
1178 (1975).
R. E. Rathbun and D. Y. Tai, Water Res., 15, 243 (1981). D. Mackay, W. Y. Shi11, and R. P. Sutherland, Environ. Sci. Technol., 13, 333 (1979). J. H. Smith, D. C. Bomberger, Jr., and D. L. Haynes, Chemosphere, 10, 281 (1981). J. H. Perry, Ed., Chemical Engineers' Handbook, 3rd Ed. (McGraw-Hill, New York, 1950) p. 670. I. J. Tinsley, Chemical Concepts in Pollutant Behavior (John Wiley and Sons, New York, 1979), p. 14, 19, 139, and 185. G. L. Baughman and R. R. Lassiter, "Prediction of Environmental Pollutant Concentration ASTM Spec. Tech. Publ. No. 657, p. 35 (1978). R. Glaeser, Clay Minerals Bull., ~, 88 (1949). D. M. Giusti, R. A. Conway, and C. T. Lawson, J. Water Poll. Control Fed., 46, 947 (197 L. G. Tensmeyer, R. W. Hoffman, and G. W. Brindley, J. Phys. Chem., 64,
1655 (1960).
J. D. Roberts and M. C. Caserio, Basic Principles of Organic Chemistr~ (W. A. Benjamin, Inc., New York, 1965), p. 41, p. 1065. R. G. Zepp and D. M. Cline, Environ. Sci. Technol., 11, 359 (1977). W. R. Benson et al., J. Agr. Food Chem., 19, 857 (1971). O. G. Crosby and A. S. Wong, J. Agr. Food Chem., 21,
1049 (1973).
D. G. Crosby and A. S. Wong, J. Agr. Food Chem., 21,
1052 (1973).
N. S. Thom and A. R. Agg, Proc. Roy. Soc. London, B189, 347 (1975). T. F. Helfgott, F. L. Hart, and R. G. Bedard, "An Index of Refractory Organics," EPA Report No. 600/2-77-174 (Aug. 1977).
W. M. Dunstan, L. P. Atkinson, and J. Natoli, Marine Biology, 31, 305 (1975). T. R. Parsons, W. K. W. Li, and R. Waters, Hydrobiologia, 51, 85 (1976). J. D. Walker, L. Cofone, Jr., and J. J. Cooney, "Microbial Petroleum Degradation: The Role of C l a d o s p o r i u m resinae," in Prevention and Control of Oil Spills, Conf. Proc., r~rch 13-15, 1973, Wash. D. C., EPA. H. Geyer et al., Chemosphere, 10,
1307 (1981).
D. Y. Tai, "Determination of Acetone and Meth~l Eth~l Ketone in Water, U.S. Geological Survey Water-Resources Investigations 78-123 (Oct. 1978), available from U.S. Dept. of Commerce, National Technical Information Service as Report PB291 151. J. I. Hedges, Geochim. Cosmochimica
Acta, 4~I, 1119 (1977).
Handbook of Chem. and Physics, 31st Ed. (Chem. Rubber Publ. Co., Cleveland,
1949).
J. F. Wilson, Jr., Fluorometeric Procedures for Dye Tracin@, U.S. Geological Survey Tech. of Water-Resources Investigations, Book 3, Chap. A12 (1968). H. A. C. Montgomery and D. K. Gardiner, Water Res., 5, R. C. Starr, Am. J. Botany, 51,
147 (1971).
1013 (1964).
Difco Laboratories, Difco Manual of Dehydrated Culture Media and Reagents, 9th Ed. Labs., Detroit, 1974).
(Di{
P. E. G r e e s o n et al., Methods for Collection and Anal~sis of Aquatic Biological and Microbiological Samples, U.S. Geological Survey Tech. of Water-Resources Investigatlon~ Book 5, Chap. 4. D. Mackay and T. K. Yuen, Water Poll. Research J. of Canada, 15, 83 (1980). J. H. Smith, D. C. Bomberger, Jr., and D. L. Haynes, Environ. Sci. Technol., 14,
(1980). J. T. Davies, Turbulence Phenomena (Academic Press, New York, P. L. Smart and I. M. S. Laidlaw, Water Resources Res., 13,
(Received
in
The
Netherlands
20 August
1982)
1972) p. 149.
15 (1976).
1332