Biochemical Oxygen Demand and Degradation of Lignin in Natural Waters

Author(s): E. W. Raabe
Source: Journal (Water Pollution Control Federation), Vol. 40, No. 5, Research Supplement to:
40, 5, Part II (May, 1968), pp. R145-R150
Published by: Water Environment Federation
Stable URL: http://www.jstor.org/stable/25036349
Accessed: 12/06/2009 04:40
Your use of the JSTOR archive indicates your acceptance of JSTOR's Terms and Conditions of Use, available at
http://www.jstor.org/page/info/about/policies/terms.jsp. JSTOR's Terms and Conditions of Use provides, in part, that unless
you have obtained prior permission, you may not download an entire issue of a journal or multiple copies of articles, and you
may use content in the JSTOR archive only for your personal, non-commercial use.
Please contact the publisher regarding any further use of this work. Publisher contact information may be obtained at
http://www.jstor.org/action/showPublisher?publisherCode=wef.
Each copy of any part of a JSTOR transmission must contain the same copyright notice that appears on the screen or printed
page of such transmission.
JSTOR is a not-for-profit organization founded in 1995 to build trusted digital archives for scholarship. We work with the
scholarly community to preserve their work and the materials they rely upon, and to build a common research platform that
promotes the discovery and use of these resources. For more information about JSTOR, please contact support@jstor.org.

Water Environment Federation is collaborating with JSTOR to digitize, preserve and extend access to Journal
(Water Pollution Control Federation).

http://www.jstor.org

BIOCHEMICAL
OXYGENDEMANDAND
OF LIGNIN IN
DEGRADATION
NATURALWATERS
E. W.

Raabe

of this preliminary
The
purpose
the biochemical
study was to determine
of lignin
in natural
demand
oxygen
waters
and the extent of its degrada
tion under
these conditions,
and to
of
the
BOD
explore
interrelationships
and degradation.
The project was initiated because of
to
to determine
the need
the extent
a
which
chief
constituent
in
lignin,
a
con
mill
is
and
paper
wastes,
pulp
tributor to the long-term BOD exerted
on

the

stream.

Lignin

presents

a wa

ter pollution
and the many
problem
to solve the problem
have
attempts
been only partially
successful.
of mea
various methods
Although
of this type of waste
surement
have
been used, including
short- and long
none has been found that
term BOD's,
over the ex
observations
continued
tended time used in this study.
The plan followed for this work was
to obtain a river sample which
con
tained wastes discharged
from a paper
mill and to determine
the oxygen de
mand at regular
intervals for a period
a portion
of 100 days.
Concurrently,
of the river sample was set up under
the same conditions,
and lignin deter
were made at the same time
minations
intervals as the BOD analyses.
Previous

Work

of liquid wastes
has long
Disposal
been a problem
in the pulp and paper
The Senate Select Commit
industry.
tee on National Water
Resources
(1)
E.
nical
trol

W.

Baabe

Services,

is Chemist,
Division
of Tech
Federal
Water
Pollution
Con

Administration,

Cincinnati,

Ohio.

that in 1954 the water usage

reported
for the pulp and paper mills
of the
United
States was 1,607 bil gal (6.1
bil eu m).
From Besselivre's
data
over
two
it
be
estimated
that
may
(2)
are in
million
tons of lignin products
cluded in the five million
tons of solids
to the nation's
discharged
annually
a
this amount
constitutes
waterways;
on
burden
the
heavy
pollutional
streams.

and Etzel
Woodard
(3) stated that
in the production
of paper the primary
of the pulping
is to
process
objective
cellulose from other constitu
separate
ents of the wood.
The cellulose is used
to make paper while the other constitu
the spent pulping
ents, along with
as waste.
The
chemical, are discharged
are
main
of the waste
constituents
wood sugars and lignin, the lignin rep
30 percent
about
of the
resenting
raw
of
the
material.
original weight
to a stream has a
Lignin discharged
a
effect and introduces
high coloring
The waste
load.
is ob
large organic
jectionable because it reduces the value
of the stream for domestic
and indus
trial use and contributes
to the BOD
exerted on the stream.
Nemerow
(4) states that spent waste
sulfite liquor from digesters
contains
an
sulfur
which
possess
compounds
ac
immediate
demand
that
oxygen
counts for about 11 percent
of the 5
The sugars
day BOD.
(hexoses and
about 65 percent
represent
pentoses)
of the BOD.
Although
lignins account
for over half the solids in this waste,
little to the BOD, ac
they contribute
cording to Nemerow.

R145

R146 JOURNAL WPCF

in a study for the Na
Lawrance,
for Stream
tional Council
Improve
ment
of
(5), found that the discharge
wastes
into a stream places
paper-mill
a rapid oxygen demand
on the water,
because
of
the
chiefly
carbohydrate
content of the waste.
Data
compiled
sources
from different
by the Council
show very definitely
that the lignin has
de
oxygen
only a small biochemical
is a
mand.
Whether
this demand
result of the conversion
of lignin into
to micro
available
organic compounds
as nutrients
or is due to
organisms
other organic
which were
substances
not removed in the purification
process
has yet to be determined.
Considerable
concerning
speculation
the decomposition
of lignins in surface
waters
in the literature.
is contained
Lawrance
that calcium
(5) concluded
contributes
lignosulfonate
little, if at
of spent
demand
all, to the oxygen
no
He
to
evidence
found
pulp liquor.
in
indicate that calcium lignosulfonate
of pure carbohydrate
is
the presence
a
into compounds
converted
having
high BOD.
The hypothesis

et al.
of Woodard
the mecha
to explain
(6) proposed
oxi
in the biological
nisms
involved
dation of lignin as: (a) lignin is re
from solution
moved
by an immedi
ate adsorption
onto the bacterial
cells,
is uti
and (b) the adsorbed
fraction
at a slow, con
lized by the bacteria
stant

rate.

In general, Zobell and Stadler

(7)
the
found that the literature
indicates
on the decomposition
of lig
following
of
nin:
the
microorganisms
(a)
species
lim
that utilize
lignin are relatively
is
ited;
(b) biological
decomposition
very slow and incomplete;
(c) the sus
of lignin to biological
attack
ceptibility
varies with
its source, age, treatment,
chemical nature,
etc.; and (d) higher
and fungi are more capable
organisms
of utilizing
than are bacteria
lignin
and

simple microorganisms.
The extent of biological
degradation
of lignin has been measured
by Wood

1968

May

ard et al. (6) by the oxygen uptake

and reduction
in lignin concentration.
Lawrance
and Sakamoto
(8) found
the microbial
oxidation
of lignin alone
and in the presence
of certain pure
to
be
The
very small.
carbohydrates
of the sugars, with
the
5-day BOD's
un
of xylose, were usually
exception
affected by the presence of lignin.
The
bacterial
of lignin
oxidation
is unaf
fected
by the cellulose
degradation
but the BOD of butyric and
products,
lactic acids and their calcium salts was
lower when
The
lignin was present.
BOD may be due to impurities
in the
of a por
sample or to the oxidation
tion of the lignin.
Pearl
(9) noted
lignin
that, when
even under
is subjected
to oxidation,
mild
conditions,
complete
disruption
of the molecule
takes place and simple
are obtained.
degradation
products

Eldridge

(10) found that the BOD

curves
for sulfate
liquor and white
water from paper mills show quite dif
ferent rates, with an apparent
transi
tional stage for the former in 5 days
and a slow transition
for the latter in
12 days.
and Moggio
Holderby
(11) found
that the BOD of spent sulfite liquor is
variable
and is controlled
largely by
the sugar content.
West
(12) states
that the k rate for rapidly
oxidized
wastes
like sugars is greater than 0.20.
little is known about the
Apparently
of lignin in natural bio
decomposition
Even
less is known
logical processes.
of
about the biological
decomposition
industrial
forms of lignin in streams
these wastes.
receiving
Laboratory
Experimental

Work

Procedure

sample was collected approx

6
miles
(9.6 km) below the
imately
waste discharge
point of a paper mill
The
Kraft
the
using
pulping process.
in the laboratory
sample was received
two days after collection and a portion
was diluted
to five percent with
for
"C"
water
mula
for BOD
dilution
A river

Vol. 40, No. 5, Part 2

LIGNIN DEGRADATION R147

standard
BOD
The
as fol
procedure
(13) was modified
lows: (a) dissolved
oxygen
(DO) de
were made
terminations
of
by means
the dropping
mercury
electrode;
(b)
in place of the conventional
BOD bot
125-ml
with
bottles
reagent
tle,
glass
stoppers were used, since the polaro
of sample;
graph uses small amounts
(c) when the DO approached
depletion
a reaeration
technique was used; and
were
(d) duplicate DO determinations
made up to and including
100 days.
as BOD
in milli
Results were plotted
grams per liter vs. time in days.
determinations.

acids?so
lignosulfonic
superior-grade
were run as a
dium salts.
Standards
part of the routine
lignin determina
as lig
tion.
The results were plotted
nin concentration
in milligrams
per
liter vs. time in days.
The BOD reaction rates were calcu
lated by the "daily difference method''
The
(14).
suggested
by Tsivoglou
ac
demands were
ultimate
calculated
?
?
to
Y
the
formula
cording
L{\
10-kt).

Results
of the first stage
The fast component
of the BOD progressed
at a fast rate
=
demand
and the ultimate
(fc
0.455)
was 33 mg/1.
A slower decomposition
for the
rate (k = 0.072) was calculated
of the first stage, with
slow component
an ultimate
A
of 65 mg/1.
demand
after about 23
second stage beginning
rate
had a reaction
incubation
days
=
k
of
0.080 and an ultimate
demand
of 103 mg/1.
de
observed
The
experimentally
mand
for the 100-day BOD was 210

with the BOD deter

Simultaneously
the river sample for lignin
minations,
ex
was set up under
determinations
same
the
conditions
actly
(5-percent
125-ml glass stoppered bottles
dilution,
in a 20 ?C incuba
stored under water
a DO determination
for
tor). When
a simultaneous
the BOD was made,
was made using
lignin determination
the "Tannin
method
de
and Lignin''
Methods"
scribed in "Standard
(13).
from
standards were prepared
Lignin
280

i?r

i?i?i?i

260
240
220

LONG TERM B.O.D.

Y=
[33(l-IO-?455t)]

[65(l-IO-?072t)]

[l03(l-IO-?080t)]

200
180
<v
=
160
s?
en

^
Q
O

140
2nd STAGE k=0.080, L=103

st STAGE-SLOW
COMPONENT
k=0.072, L=65
iiiiiiiiiiiHiiiiiiiiiiiiiiiMiiniiiiiiiiiiiMiiiiiiii.mm.i.iiiiiiiiiiiiiiiiiii]
1st STAGE-FASTCOMPONENTk=0.455, L=33 _
/
lll.^iiiiiiiiiiiiiiiiiiuiiiiiiiiiiiiiii^iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii<iiiiiiiiiiiiiiiiiiiiiiiiiiiiitiiiiiiiiiiiitiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii

J_I_I_L/J_L
15
5
10

20

25

30

35

40

45

50

55

60

65

70

75

TIME, days
FIGURE

1.?Long-term

BOD

over

100-day

period.

80

85

90

95

100

May 1968

JOURNAL WPCF

R148

T~"T

FIGURE

10

20

2.?Long-term

30

"T"T

BLD

over

50

40

T"l

100-day

period.

60

70

over

100-day

80

TIME,days
FIGURE

3.?Degradation

of

lignin

TT

period.

90

100

Vol. 40, No. 5, Part 2

LIGNIN DEGRADATION R149

to the calculated
ulti
compared
of 201 mg/1.
demand
The 100
in Figure
is illustrated
1.
day BOD
was calcu
The lignin decomposition
lated from the lignin data as a bio
chemical lignin demand
(BLD), using
as for the BOD,
so
the same method
that a comparison
between the k and L
values of the BOD and BLD could be
determined.
The overall reaction rate for the lig
was calculated
nin decomposition
to be
k = 0.027.
for
The ultimate
demand
to be 85.5
the BLD was
calculated
to the experimentally
compared
mg/1
BLD
of 84 mg/1.
observed
100-day
The 100-day BLD is illustrated
in Fig
ure 2.
The
is
lignin decomposition
shown in Figure
3.
of
The data show that 51.6 percent
the lignin
origi
present
compounds
nally were not oxidized after 100 days
of incubation
at 20?C.

mg/1
mate

Discussion
have
Previous
sug
investigators
gested that the first stage of the BOD
of paper mill wastes
the
represents
of wood
oxidation
sugars and other
Neme
readily decomposable
organics.
row (4) found that in the 5-day BOD
of spent sulfite liquor from digesters,
the sugars (hexoses and pentoses)
rep
resented about 65 percent of the BOD,
to the fast component
corresponding
?
in this
of the first stage
0.455)
(k
This
fast
study.
component
(presum
about 47 per
ably sugars) represented
In this study
cent of the 5-day BOD.
a sulfate waste from the Kraft pulping
process

was

used,

whereas

on spent sulfite
reported
The curve (Figure 1)
the 5-day BOD is related
concentration
hydrate
the long-term BOD
while
of an oxidizable
fraction
as any
as well
pounds,

Nemerow

waste

liquor.
that
suggests
to the carbo
of the waste
is indicative
of lignin com
other slowly
in the
present
organics
decomposable
93
In
50
percent of the
days,
sample.
de
been
fractions
had
oxidizable
of the total
88 percent
stroyed, while
BOD had been satisfied.

curves for sulfate

The BOD
liquor
and white water
from paper mills de
scribed by Bldridge
(10) showed an
transition
apparent
stage at 5 and 12
In this study the
days, respectively.
transition
in about 7
stages occurred
and 23 days, respectively.
confirms
This study
the results
of
Kroner
and Moore
which
showed
(15),
that 41 to 46 percent of the lignin re
mained
after about 20 wk, whereas
in
this experiment
about 51 percent
of
15 wk.
after
about
lignin remained
The slight difference
in results may be
due to the difference
in the type of
or to difference
in
lignin compounds
the
incubation
since
temperatures,
Kroner's
samples were held at room
20 ?C was main
while
temperature
tained in this study.
Additional

Work

This study has shown that paper

mill waste decomposition
has a multi
curve
BOD
that the
and
component
50
less
than
lignin decomposes
percent
in 100 days.
Since the fast component
of the first stage is related primarily
to the concentration
of the carbohy
a
on pure lig
BOD
long-term
drates,
nin compounds
should help to identify
the portions of the curve due to lignin.
in
Further
investigation
might
clude:
long-term
(a)
determining
BOD
of pure lignin compounds,
(b)
BOD and lignin degrada
determining
raw
with
tion in a stream polluted
the
effect
of
Kraft waste,
(c) studying
on BOD
time of passage
character
istics of a polluted
stream, and
(d)
studying BOD and lignin degradation
of waste
treatment.
after biological
Conclusions
1. This study shows that the BOD
of a stream polluted with Kraft mill
wastes apparently
is related to the con
the frac
of carbohydrates,
centration
oxidizable
tion of lignin
compounds
to other
in 100 days,
and possibly
organics.
slowly decomposable
of the first
2. The fast component
of the
is indicative
stage of the BOD

R150JOURNAL WPCF
of wood

oxidation

sugars and other

The
materials.
readily
decomposable
reaction rate is very rapid (k = 0.455).
3. The slow component
of the first
stage, and the second stage of the BOD
= 0.072 and
are
(k
0.080, respectively)
of
the
of
the
suggestive
decomposition
and other
lignin and its by-products
organics.

decomposable

4. Over a period
of 100 days,
less
than 50 percent
com
of the lignin
under
pounds present were oxidizable
test conditions.
5. The
at an
lignin
decomposed
overall slow rate of k ? 0.027.

The author wishes

to acknowledge
the assistance
of Alfred W. West,
Sani
Technical
tary Engineer,
Advisory
and Investigations
Division
Activities,
of Technical
Federal Water
Services,
Pollution
Control Administration,
De
of the Interior,
in the calcu
partment
lation of the k and L values
for the
long-term BOD.
Bibliography
1. TJ. S.

Senate

on National
Comm.
Select
"
Future
Water
Re
Resources,
of Principal
Water
quirements
Using
Industries."
Print
Committee
No.
8,
U.
S. Govt.
Printing
Office, Washing
ton, D. C. (1961).
"
2. Besselievre,
E.
Industrial
Waste
B.,
Treatment."
McGraw
Hill,
Inc., New
N. Y.
York,
(1952).
3. Woodard,
P. E.,
and Etzel,
J. E., "Co
acervation
and
Chemical
Coagulation
Water

of

from

Lignin

Liquor."

This

(July 1965).

Pulp

Journal,

4. Nemerow,
tices
ment.

N.
of
''

"
and Prac
Theories
L.,
Industrial
Waste
Treat

Addison-Wesley
Publishing
Mass
Inc., Reading,
(1963).
5. Lawrance,
W. A., "The
Microbial
Oxida
tion of Pure
in the Pres
Carbohydrate
''
ence of Calcium
Na
Lignosulfonate.
tional
Council
for
Stream
Improve
Tech. Bull. No.
80.
ment,
6. Woodard,
F. E.,
O. J., and At
Sproul,
P.
"The
kins,
F.,
Jr.,
Biological
of
from
Degradation
Lignin
Pulp
Mill
Black
This
Liquor.''
Journal,
36, 11, 1401
(Nov.
1964).
7. Zobell,
C. E.,
and
"The
Stadler,
J.,
Co.,

of Lignin
Oxidation
Ponds
and Lakes.''

(Germany),
8. Lawrance,
W.
"Microbial

Acknowledgments

Mill
37,

Black
7,

990

1968

May

from
by Bacteria
Arch.
Itydrobiol.

37, 163

(1940).

and
A.,
Oxidation

and Lactic
Butyric
of Calcium
Lignosulf

42, 93 (1959).

Sakamoto,
W.,
of
Cellobiose,
in Presence
Acids
''
onate.
TAPPI,

9. Pearl,
I. A.,
Chem.
"Lignin
Chemistry.''
Eng.
News,
42, 81 (1964).
10. Eldridge,
E. F., "Studies
of Biochemical
Demand
of Trade
Wastes."
Oxygen
Sew.
Works
Jour,
[abs.]
2, 4, 503
(Oct.
1930).
11. Holderby,
J. M.,
and Moggio,
W.
A.,
"Utilization
of Spent
Sulfite
Liquor."
This
Journal,
32, 2, 171 (Feb.
1960).
12. West,
A. W.,
"Useful
for
Information
Stream
Pollution
and Evalu
Surveys
"
ations.
(Unpublished
memorandum.)
13. "Standard
Methods
for
the Examina
''
tion of Water
and Wastewater.
12th
Amer.
Pub.
Health
New
Ed.,
Assn.,

York

14.

(1965).

E. C,
Tsivoglou,
in
Streams."
Robert

A.

"Oxygen
Tech.

Relationships
Rept.
W58-2,

Taft
Sanitary
Engineering
Ohio
Cincinnati,
(1958).
15. Kroner,
R. C,
and Moore,
W.
A., "The
Persistence
of Lignin
in River
Wa
ters."
8th
Proc.
Ind. Wastes
Conf.,
Purdue
Univ.
Ext.
Ser. 83, 122 (1953).
Center,