-,
i .REPORT
-
HMSC
HMSC
TD
888
.P8
B8
cop. 2
cop.2
FEE
t
PROGRESS,
PROGRESS
REPORT
V/P_)24
GRANTWP-524
RESEARCHGRANT
RESEARCH
ADMINISTRATION
rATER POLLUTION
VATER
POLLUTION CONTROL
CONTROL ADMINISTRATION
UNIVERSITY
STATEUNIVERSITY
OREGON STATE
OREGON
Engineering
Civil Engineering
\flildlife
Fisheriesand Wildlife
Fisheries
1966
March31,
March
3r, 1966
W
t'tll5fr
I'J,it' EbBtfifttlltlEStlEllSE
W
W
Raport
Progrcer Report
Progress
PULP
PULP I.|ILL
MILL T{A818
WASTE
IN I{ANINE
DEGRADATION
IN
MARINE WATERS
WATERS
DEORADATION
1966
31' 1966
through March
March 31,
April 1,
Aprtl
1, 1964
1964 through
Research
WP-524
Research Grant llP-524
Adnlnlctration
Control
Pollutlon
lfater
Federal Water Pollution Control Administration
Inveettgator
Prtnclpel
Principal Investigator
Burgeee
Fred 3.
J. Burgess
Fred
Englneerlng
of Civil
Clvll Engineering
Professor
Profecaor of
Co-Invegtlgator
Co-Investigator
E. Dimick
Dlmlck
Roland E.
Roland
Flcherlea
of Fisheries
Professor of
Proferaor
Conducted Ttrrough
Through
Conducted
Expertncnt Statton
Engineering
Station
Englneertng Experiment
Engtneerlng
Gtvtl Engineering
Dept. Civil
Agricultural
Experiment
Station
ExPerlment Stetto!
Agrlcultural
lltldltfe
end Wildlife
Dept. Fisheries
Fl.sherlea and
Unl.vcratty
Stete University
Oregon
Oregon State
Oregon
Corvallis,
Conral1l.e, Oregon
1966
March 31, 1966
Harch
ST'I.{MARY
SUMMARY
progresa report
Ttrle progress
report describes
descrlbea research
This
pulp m{l1
mill \raste
waste
reaearch conducted,
conducted on pulp
degradatlon
ln marlne
grant
during the
the first
20 months of
degradation in
marine waters
waters during
20
first
of research
research grant
l{P-524. the
WP-524.
ls an interdisciplinary
by engineers
lnterdlacipllnary
btoloThe proJect
project is
effort
effort by
engtneers and
and biologlets to
to assess the
the effect
effect of
of kraft
kraft mill
gists
mlll effluents
upon the
effluente upon
the marine
marine environenvlronment. It
ment.
ie further
It is
further sought
aought to
determine the
to determine
the effectiveness
effectlveness of
of several
several
treatment
frorn both
blologlcal
treatment methoda
methods from
both a biological
and engineering
engineerlng viewpoint.
vlewpolnt.
EngtEngineering
lnvestlgatlons
durlng this
yeara have
thts first
flrat one
one and
and one-half
one-half years
have cenneering investigations
during
cen(a) treatment
tered upon
treatment of
(b) foam
of rntll
waetee by
by dilution;
tered
upon (a)
mill wastes
(b)
dilutlon;
foam separation
eeparatton
of strong
(c) treatment
strong wastes
rastes and
and (c)
treatment of
of
of evaporator
by carbon
evaporator condensates
condensates by
adcarbon adeorptlon.
Biologlcal
sorption.
studlee
have
been
wlth
bloconcerned with development
development of
of bioBiological studies
been concerned
aseays suitable
euitable for
for assessing
aesessing the
pulp mill
the effect
effect of
of pulp
assays
mtll effluent
effluent on
the
on the
marlne
envlronment and
and for
for evaluating
marine environment
eval.uating waste
rragte treatment
treatmenc methods.
methodg.
Bloaseay development
devetopment has been a contlnuatlon
Bioassay
continuation of
of earller
earlier work
work of
of R,
R E.
E
Dfuaick
l{.
Breese
and
P.
involvlng
bay
qgg.tlg"
rhethe bay
Dimick and W.P. Breese involvingthe
the
embryo
mussel
(Ujs
ernbryo
of of
musaet
pdu.tis),
paclflc oyster
(Carassostrea el.ggg),
the pacific
oyster (Carassostrea
1is), the
tilottrer
igi), in
other
in addition
addition to
wlth the
(@g-EEtyel!:-1p.),
the marine
marine algae
work with
(1
algae
the three
rhree spine
sptne stickleback
srtclcleback
shiiTisp ), the
and the
the common
cormon salt
guppy. Research with
salt water
water guppy.
wlth M!tilus.
hae
edulis embryo
embryo has
Mytilue eCylls
ehown
a
of correlation
correlatlon
between abnormal
shown a htgh
high degree of
between
abnormal embryo
embryo development
d&elopment and
and
itaste concentration.
concentratlon.
waste
test proved to
The
valuable tool
The test
to be a valuable
tool for
for evaluating
evalustlng
the effectiveness
of treatment
treatment methods
methods in
the
effectiveness of
in terms
terms of
of toxicity
toxlclty reduction.
reductlon.
spectflc
flndlngs are reported
reported in
in the
the chapter
chapter on
on bioassay
bioassay methods.
Specific findings
rnethode.
The degradation
degradatlon of
The
of kraft
kraft puLplng
pulping wastes
wastes in
marine waters
waters has
has been
in marine
conducted
under circumstances
circumstances approximating
approximating dilution
conducted under
dilutlon subsequent
dissubsequent to
to discharge in
ln the
the sea
sea or
or in
ln estuarine
estuarine waters.
watere.
These
etudtes indicate
These studies
tndlcate that
that
degradation
follows first
flrst order
order reaction
reactl.on kinetics
kl,netlcs but
but that
degradation follows
that reaction
reactlon rates
retes
are higher
hlgher for
for dilute
are
dilute solutions.
solutions.
It
It waa
was further
further found that
that the
the toxicity
toxlcity
of kraft
kraft waste
waete as
as measured
measurea by
Uy bioassays
bioassays on
of
on the
bay mussel
biodegradabl.e.
the bay
mussel is
is biodegradable.
However,
there is
is no
no apparent
apparent correlation
correl.ation between
However, there
between the
Ehe degradation
degradatlon of
of BOD,
fOD,
PBI and'
PBI
toxicity.
and toxlclty.
In addition
additton, the
the degradation
degradation of
BODappears
In
of BOD
appears independent
independent
of salinity
sallnlty
the change
of
and the
change in
rate constants
constants wlth
with temperature
in rate
temperature are higher
hlgher
than
for domestic
domestlc sewage.
than for
Be\rage.
Expertments on treatment
treatment by
Experiments
by foam separation
revealed that
separation revealed
that a foaming
foarnlng
was necessary
necessary for
agent was
for reliable
rellable foam
foam formation.
forratlon.
BODreductions
BOD
reductlons from
from 15.8
15.8
to 35.2
percent and
and COD
CODreductions
to
35.2 percent
reductions up
up to
percent were
20.2 percent
to 20.2
lrere obtained.
obtained.
Toxlclty
reductlon factors
factors up to
Toxicity reduction
to 2.3
2.3 were
were obtained.
obtained.
These exploratory
exploratory
These
tests indicated
lndicated that
that foam
foem separation
promislng method
eeparation is
tests
not aa promising
ls not
meEhodbut
but may
may
have limited
llmlted application
appLlcatlon as a method
have
method of
reducing
toxicity
to
marine
of reducing toxlcity
to marine
organiems.
organisms.
Studles on the
the treatment
treatment of
of kraft
Studies
evaporator condensates by activated
kraft evaporator
activated
carbon
that up to
Eo 75 percent
the organlc
carbon revealed
revealed that
percent of
of the
organic materlala
materials could
could be
removed
thts method
rnethod with
wlth aa toxicity
removed by this
toxlcity reduction
percent.
of 80
reductton of
80 percent.
An estiAn
eetlmated
eost of
of $0.23
per 1000,
1000 gallons
prellmlnary basis.,
mated cost
gallons ts
is indicated
lndicated on
on aa preliminary
basis.
$0.23 per
Toxlclty
factors of
Toxicity reductlon
reduction factors
of as much
much as 17 were
were observed
observed on batch tests.
teste.
Thle
to hold
This method
method appeara
appears to
hold Bome
some promlee
promise for
of apeciflc
specific waste
waste
for treatment
treatment of
streams
lf the
the process
streams if
process economice
economics can
can be improved
by coupllng
coupling the
lmproved by
the treatment
treatment
wlth
blologtcal
processes or
with biological processes
or other
oEher methods.
methods.
Speclflc details
detalle of
theae related
related research
reeearch efforts
Specific
efforts wtl1
will be found in
of these
ln the
the
body of
of this
thia report.
report,
sT{FrrNc
STAFFING
Percentl/
Percentl/
Personnel
Personnel
of Activity
ActlvttJ
Pertod of
Period
Burgeca'/
F. J.
J. Burgess2/
F.
Investl.SsBor
Principal
Prtnc tpal Investigator
Englneertng
of Civil
Clvtl Engineering
Professor
Profeaaor of
1.5
15
- prceent
present
4lLl64 4/1/64
Dlnick
B. Dimick
R. E.
Flaherles
of, Fisheries
Professor of
25
25
praecnt
4ll,l64 -- present
4/1/64
LO
10
present
41U64 -- prerent
4/1/64
25
25
prerent
411164-- present
4/1/64
100
100
present
4lLl64 -- preecnt
4/1/64
6t
i,
Phllllpett
D.C. Phillips2'
D.C.
Englnecrlng
Prof. Civil
Ctvtl Engineering
Assoc.
Acsoc. Prof.
Breege
l{.P. Breese
W.P.
Engtncarlng
Prof. Civil
Cl.vtl Engineering
Asst.
Aest. Prof.
CourBrl.ght
R. C. Courtright
Blology
Pollutlon Biology
Asat.
ln lilater
Asst, in
Water Pollution
tl
8130165
elll64 -- 8/30/65
9/1/64
Hansen2l
S.P. Ilengen-'
S.P
tl
3/
4l3Ll66
slll64 -- 4/31/66
9/1/64
tt
olNeal-'
G
. L . O'Neal2'
G.L.
3
3/l
hltl.l66
hlLl64 -- 4/31/66
4/1/64
tl
lazter-'
J . L . Biazier2
3.L.
Student
Greduate Student
Graduate
,t
L
1/1 Based
bealc
upon 12
Eonth basis
12 month
Baeed upon
2/l Supported from
2
Sourceg
othcr Sources
fron other
top{c
31
3/ Approximately
theele topic
al thesis
used raaQarch
research as
302 -- used
Approxlnately 307.
THESES
ANDTHESES
PUBLICATIONS
PUBLICATIONSAND
Publlcatlons
Publications
rrBay Mueeel Embryo
Bloaseayrn
Embryo Bioassay,"
Breeee lt.P.r
Dimick R.8.3
RE.; Breese
WP., "Bay Mussel
Dlnlck
l{alte
Waste
Industrlal
Northuest
Paclflc
Proceedings
1965,
Pacific
Northwest
Industrial
1965,
Proceedlnge
1965'
November
1965,
November
tfaehlngton,
of
Conference,
University
of
Washington,
Conferenc-, Unlverelty
p p 165-175.
165-175.
pp
Ttreeag
Theses
ln
"The Degradatlon
Degradation of
of Kraft
Kraft Pulplng
Pulping lfartcr
Wastes in
G.L. ttTtre
OtNeal, C.L.
O'Neal,
UnlverrltYt
Sttte
oregon
TlrerLa,
tlatarr.fr
Ph.D.
Estuarine
Waters."
Ph.D.
Thesis,
Oregon
State
University,
Estuerlne
1966.
1966.
t?oam Separatlon of
Toxlc
and Toxic
Organtc and
of Organic
Blazl.er, J,L.
Blazier,
JL. "Foam Separation
ftreetst
!1,S.
Materials
Kraft u111
Mill Effluents.n
Effluents." M.S. Thesis,
tn Kraft
Haterlala in
1966.
UnlvereltY' 1966.
Strt€ University,
Oregon State
Oregon
rhppllcatlon of
to the
thc
Carbon to
Activated Carbon
of Actlvstcd
S.P.1 "Application
Haneen,
Hansen, S.P.,
l{.S.
Condensates."
M.S.
Evaporator condensltGt.rt
Krafl-M111
Treatment
Mill Evaporator
of Kraft
Treatnent of
1966,
Unlverclty' 1966.
State University,
Oregon State
Thesis,
Ttreels, Oregon
OF CONTENTS
CONTENTS
TABLEOF
TABLE
Watere
& Harlne
pingl{asteg
Wastes
& Marine
Kraft Pulplng
Waters ------------------ 11
Pulplng
Procees Process ------------------------ 22
The
Kraft
Pulping
lhe Kraft
4
ChemicalRecovery
Chenlcal Recovery ProcesaProcess --------------------- 4
- p
Nature of
of lfagte
Sources and Nature
Waste -- -- - -------------------U111
Georgia
Pacific
Mill ----------------------Georgl.a Paclfic
5
5
77
- - - - 1
11l
B
Bioassay
loaseayliethod
Method ---------------------------1
1
layHueeelB
loaeeay-BayMussel
Bioassay
' - - L 4 14
Embryonic
----------------------E r n l r y o n t c D e v eDevelopment
lopnrent-- ' L 7 17
Examples
Bioassay
E x a n p l e a o f Bof
loae
s a y R e a u l t sResults --------------------
------------------------ 11
---19
-Exploratory
-------------------------E x p l o r a t o r y S t u d l e sStudies
19
20
lfeterg Waters ----------- 20
wasteg
1n llarl.ne
Kraft
U111Mill
Degradation
Kraft
Wastes
in Marine
Degradatlon of of
20
Degradatlon
Evaluatlng
Methodsforfor
Evaluating
Degradation ----------------- 20
llethodg
22
Procedure
Experimental
Procedure ---------------------- 22
Experllnental
24
?eet
Test Resulte
Results -. --------------------------- 24
t7
of Reeultc
Discussion
of Results ------------------------ 37
Dtecuesion
FoamSeparetlon
Separation
of Kraft
of
Foam
of
Study
Method
42
Utll lfaetaa
Kraft
Mill- Wastes
------------------- 42
Method of Study --------------------------
42
42
GarbonCarbon -------by Acttvated
TreatmentofofEvaporator
Evaporator
Condensates
by Activated
Condensates
TreaEment
General
l{aatee Wastes ---------Condeneate
Characteristics
Evaporator
Condensate
of of
Evaporator
Characterlattce
Activated
Carbon
Treatment --------------------Treatment
ActlvaEed Carbon
of Analysls
Method
of Analysis -------------------------Method
Experimental
Procedure ---------------------Experlmentel Procedure
Research
Findings ------------------------Research Findings
- - ------------------------ -'
Evaluatlon
Economic
Evaluation
Economlc
54
54
45
Results------------------------------45
Reeul.ts
5t+
General------------------------------ 54
----83
Bibliography
-----------------------------Blbllography-- Appendlx
Appendix
--------------------------------
54
54
57
57
58
58
51
61
64
64
78
78
83
88
A-1
Retention
Studies -------------------------- AA1
Retentlon Studiee
-25
Synthetic
-----------------S y n t h e t l c s a l t wSaltwater
a t e r D e v e l o p ' uDevelopment
ent--
A-25
PI'LPIXq
OF KRAFT
KRAFT PULPING
THE
DECRADA?IONOF
TIIE DEGRADATION
$TASTESIN
ESN'ARINE I{ATERS
WASTES
WATERS
IN ESTUARINE
baeed to
to
ls based
Northweot is
Paclflc Northwest
the Pacific
of the
lltre economy
Nature
econmy of
the Problem
Problen -- The
Nature of
of the
and
foreets
abundant
forests
and
abundant
nanely
resource8;
maJor
a
large
extent
upon
two
major
resources;
namely
@o
power
for power
prlnclpally for
Water
used principally
tJater is
la used
are available.
avallable.
whl.chare
water supplies
suppltes which
commercial
comnerclal
consumptlonr
and
nuntclpal
generation, recreation,
industrial
and
municipal
consumption,
generatlon,
recreation, lndustrlal
proproducts are
ereproA
of products
A variety
varlety of
lrrlgatlon.
and irrigation.
fishing, transportation
transPortatlon and
flshlng,
of
As
a
result
of
rle
a
result
wood.
of
utlltzatlon
upon
tha
duced
by
industries
based
upon
the
utilization
of
wood.
duced Uy lnduatrlee baaed
the
maintain
the
matntaln
to
dtfftcult
becoore
tncreasl.ngty
these actlvltlee,
activities, it
has become increasingly difficult to
lt hag
thege
marl'ne.
and marine.
both fresh
frech and
quellty
water, both
quality of
of the
the water,
quallty effects,
effectet
water quality
lrhlch create
create water
baecd industries
lnduatrles
Of the
which
the forest
foreet based
Of
In
the
problem.
In the
problem.
dtfflcult
moet difficult
presente the
the most
paper industry
lnduetry presents
the
pulp and paper
the pulp
and
the
Oeean
the
Pacific
Ocean
and
the
Pacific
the
between
lylng between
area of
Washington, lying
of- Oregon
Oregon and
ind t{ashlnglon,
area
Cascades,
approximately
C a e c a d e a ,there
t h e r e aare.42
r e . @ n l 1pulp
1 s p rand
o d u cpaper
l n g a p mills
p r o x l n producing
ate1y
by
increase by
to increase
pulp daily.
le expected to
tong of
sf pulp
16,000
16.000 tons
mctton This production is
ere
pulplng
variety of
of pulping processes
2000' A varlety
ear 2000.
Processes are
a factor of four by the year
proc€s8€8o
mechanlcal processes.
and mechanical
seml-chemlcal, and
kraft,
kraft, 8emi-chemical,
sulflte,
used including
lncludlng sulfite,
of
type of
of
the
but regardless
regardless of the type
predomlnate, but
plante predominate,
pulptng plants
The
ltre chemical
ehemlcal pulping
wasteof
volumes
of
wastelarge volumea
and large
uged and
are used
weter are
frech water
mill,
of fresh
volumee of
n111, large
large volumes
satlefactory
ln aa satisfactory
ltastes in
Treatment and disposal
of these
these wastes
dlsposal. of
Treatment
water result.
result.
water
industry.
pulp and paper industry.
the pulp
faclng the
problens facing
maJor problems
manner is
of the
the major
manner
te one of
pulplng
of pulping
dtaposal of
ln the
the disposal
prlnary concern
concern in
For many
many years
years the
tha primary
For
problem
The
major
problem
maJor
Ttle
streame.
freahwater
upon
the
wastes
was
their
effect
upon
the
freshwater
streams.
wastes wae thetr effect
to
preto
necessary
levele
oxygen
Prebeing
maintenance
of
minimum
dissolved
oxygen
levels
necessary
dlaaolved
mlnl.mum
belng malntenance of
migrated
they
varieties,
as
they
migrated
as
varietlesr
prlmarlly
anadromous
the
serve
fish
life,
primarily
the
anadromous
fteh l.lfe,
,"nri
yearst howhowIn the
1O-15 years,
laet 10-15
the last
In
pollutlon.
through zones of
pollution.
of industrial
lnduetrlal
through
mllle
newer
Many
of
the
newer
mills
have
the
of
Many
arisen.
problem area
ever, another problem
area has arisen.
everr-another
These
These
coaet.
open coast.
or the
the open
estuarleg or
been constructed
tl.dal estuaries
near tidal
or near
constructed on or
already
were
which
already
whlch
n{lls
older
of
the
added
to
problems
created
by
many
of
the
older
mills
nany
added to problems created
Wlth
With
area.
Sound
area,
Sound
Puget
the
tn
located
marine waters,
waters, Parttcularly
particularly in the Puget
located on marine
onest
older
ones,
older
the
productlon
ln
lncreased production in the
this
of nerl
new mllte
mills and increased
tnflux of
thls influx
The
The
waters.
marl'ne waters.
to marine
betng released
released to
significant volumea
volumes of
waste were being
of waete
algnlflcant
aB
estimated
as
beea
ectimated
have
mllle
Northnest mills have been
combined
Paclftc Northwest
lrastes of
of the
the Pacific
comblned wastes
people.
people.
nllllon
20 million
frorn 20
of that
that from
having
populatlon in
fa excess
excees of
wbgte population
havlng raw wiste
oxygen'
dissolved
oxygen,
dlasolved
ln
problem is
reductlon in
le reduction
While
the main
matn problem
fregh water
watei the
While in
tn fresh
toxLc
problems
are
toxic
are
problems
prlmary
the primary
that the
in
marine waters
waters indications
are
ere that
lndlcatlono
tn marlne
concentrations.
permleslble concentrations.
on permissible
agreement on
effects,
but
agreement
ll.ttle
but there
le little
there is
effects,
blologlet.
the biologist.
ptoblen
of the
prirnartly the
the problem of
ie primarily
Establishment
levela is
of these
these levels
Eetabllatment of
overall
influence
lnfluence
ovcrall
the
determlne the
to determine
however, to
It
the engineer,
engLneer, however,
to the
falls to
It falls
processes
treahent
varloue treatment
evaluate various
Processcg
qualtty and
to evaluate
and to
of
wastes on water
water quality
of the
the wastea
qualfty.
ltater
to improve
lmprove water quality.
which
order to
be applied
ln order
applled in
ntght be
wtrlch might
Le aa particurLvers is
pollutlon
and rivers
ltaters and
Pertl'cushore waters
Pollution
of
near shore
or near
of estuarine
eetuarlne or
these
water
water
resources
resource8
these
slnce
Northweet since
larly aerlous
serious problen
problem in
Paclflc Northwest
the Pacific
ln the
larly
nell
region
as
well
as
the reglon
of the
part of
economy of
form
part
of the
the economy
lntegral
auch an integral
form such
-2-2upon
baced upon
people. Tourism
Tourlsm based
their
recreational and
to the
thc people.
and esthetic
eethetlc value to
thetr recreatlonal.
Sports
and
and
Sporta
8tate.
ln the
the state.
recreation
thl.rd largest
lnduatry in
is the
the third
largert industry
recreatlon is
recrcand recrethe economic
econourlc and
commercial
of the
aspect of
naJor aspect:
conblned form
foru aa major
ftehtng combined
conmerclal fishing
vlth the
thc
uses combined
conblned with
above uses
Ttre above
ational
resource. The
valuea of
of the
the water resource.
atlonal values
perbe permethodabe
that methods
other
tt essential
of water make
nake it
eseenttal that
valuee of
other important
lmportant values
wlthbe accomplished
acconpltshed withprovlde jobs
can be
fected
whereby industrial
to provide
fected whereby
lnduatrlal growth to
Jobe can
out despoiling
deapolltng the
the environment.
envlronment.
THE
PROCESS
PTTLPINCIPROCESS
rHE KRAFT
KRAFTPULPING
process,
kraft process,
proceas, more
the kraft
Generalknownas
ae the
Gqneral- The
Ttre sulfate
more commonly
co'nmonlyknown
sulfate process,
Although this
thla
involves
pulping of
wood in
an alkaline
alkallne solution.
eolutfon.
lnvolvee the pulplng
of wood
Ln an
the
states untll
L907, the
process was
was not
United States
until 1907,
lnto the un{ted
not introduced
lntroduced into
process and
and
produced today
pulp produced
derlved from
fronr this
thts process
majority
rnaJorl.ty of
of the
the pulp
today is
lc derived
World l{ar
been of
most
War II
moet of
of the
the mills
nllle constructed
constructed since
eLnce World
II have
have been
of, this
thls type.
ttpGo
chtpa.
The
the procese
process te
is the
the dlgeetlon
digestion of
of the wood
wood chips.
flrst step,
otep. lnin the
lhe first
wlth the
chemtcal
placed in
pressure vessel
along with.
the chemical
veceel along
The chlpe
chips are placed
The
ln aa large
large pressure
p.s.L..
The
Ttre
pressure is
to about
about 100
100p.s.i..
cooking
cooktng liquor
and the
the pressure
lo increased
lncreased to
llquor and
dlgearhe digespressure and
pressure
of the
and the duration
duratlon of
and temperature
dlgestor and
temperrture in
ln the
the digestor
perlod are controlled
belng used
used and
and the
the
wood being
tion
by the
of wood
tlon period
controlled by
the type
type of
gases
perlod,
ln the
the
During
the
digestion
period,
the
gases
in
pulp
quallty
the
quality of
pulp
desired.
dlgeetl.on
of
deslred. Durtng
rrtall
recovery
digestor
are
intermittently
removed
and
sent
to
"tall
oil"
recovery
to
a
oll[
dlgeator are lntermlttentty
removed and sent
of separator.
separator.
by some
type of
This
un{t.
followed by
sometype
unit.
conslsts of
of aa condenser
Ttris consists
condenser followed
the internal
Lnternal
allowlng the
At the
the end
of the
the cook,
cook, the
the digestor
dlgeetor is
le emptied by allowing
end of
ftblow tanks"
pressure to
blow the dlgeetton
digestion mlxture
mixture into
where the
the pulp
pulp
tanksfr where
to bl.ow
Lnto "blow
waahera.
is
dral.ned before being
betng sent
ls drained
to the
the washers.
sent to
groups of
wood.
tn wood.
of components,
componentsr in
There
or groups
Ttrere are three
three major
maJor components,
components, or
(1952)
Casey (1952)
hemlcellulogeg. Casey
These
ere cellulose,
cel.lulose, lignin,
and the
the hemicelluloses.
Ttreee are
llgnln, and
glvea
pereentage compositions
follows:
as follows:
gives the
the approximate
approxfinate percentage
couposltlona as
Cellulose
Gellutose
Lignin
Ltgnin
}lemicelluloses
llenlcelluloees
607
607.
17-327.
17-327.
l5l87
15-187.
!ta:xeo'
fata, waxes,
resLne, fats,
amounts of
of resins,
In
are smaller
In addition
addttlon to
to these,
theee, there
there'are
smaller amounts
tyPe
dependlng uPon
the type
and other
materials preaent,
present, the
amount depending
upon the
the anount
other trace
trace matertala
pulped.
betng pulped.
of
wood being
of wood
the
whtch holds
holde the
blndlng agent
agent 'which
The
fractlon serves
aB the
the binding
Ttre lignin
llgnin fraction
serves as
The
not
hae not
of lignin
llgnin has
structure of
chenlcal structure
cellulose
celluloee fibers
flbere together.
together.
Ttre chemical
been determined
since
very complex molecule
molecule and
ls a very
deteruriaed definitely
deftnltely
cl.nce it
lt is
wood.
of wood.
appears
species
vary between
between different
dlfferent
specles of
appeare to
to vary
glucoce and has the
eeme
polymer of
the same
The
fraction
of glucose
fractl.on is
Ttre cellulose
cellulose
le a polymer
polymer
hydrolyzed
The
cellulose
polymer
is
hydrolyzed
ls
ccllulose
composition
regardless
of
source.
the
cornposltlon regardlees of source.
frorn the
the
permlte the
separated from
only
with difficulty,
which permits
whlch
ftber to
to be separated
the fiber
only wlth
dlfflculty,
other
wood
components
during
digestion.
other wood componeftts durlng dlgestlon.
-3-3-
wood is
the hemicelluloses.
herntcellul.oeea,
Ttre
fractlon of
of the
the wood
ls the
The other
other naJor
major fraction
group of
polymerlc substances
nhlch
lheee are
ere aa group
of easily
substancea which
easlly hydrolyzed
hydrolyzed polymeric
These
glucoee. Compounde
zyloaet
as zylose,
Compounds such
conteln other
other sugar
unlta besides
beeidee glucose.
sugsr units
euch as
contain
galactose, mannoae,
been found
found in
ln
uronic acids
have been
arablnoae,
and uronic
aclds have
arabinose, galactose,
mannose, and
(Stansrand
L953).
and Harris,
Harrls, 1953).
extracts
of the hemicelluloge
hemtcellulose fraction
fractlon (Stamm
extracts of
codirm
chemlcala: sodium
followtng chemicals'
the following
contalna the
The
llquor contains
Ttre cooking
cooklng liquor
(Na2CO3)'
(NaZS), sodium
carbonate (Na2CO3),
(NaOHi, sodium
aodiun carbonate
sulflde (Na2S),
hydroxide (NaOH),
adat.* sulfide
hydroxlde
(Na2S2O3). The
NaOH
The NaOH
(NaZSOA),and
thioeulfate (Na2S2O3).
and sodium
sodl.un thiosulfate
sodium sulfate
eulfata (Na2SO4),
sodlum
preaent
are present
three are
the latter
latter three
chemlcale; the
and
cooklng chemicals;
the active
actlve cooking
and Na2S
Na2$ are the
go
not go
do not
ltquor do
cooklng liquor
the cooking
used to
to prepare
only btcauee
because the reactions
reactlons used
only
Prepare the
typlof aa typi(l9t+7r, the
content of
Na2SO4
the Na2SO4
content
to Grant
Crant (1947),
Aceordlng to
to iompletton.
to
completion. According
pet22 perabout 22
Na2Sabout
percent' the
the Na2S
seven percent,
wlll approximate
approxl.mateseven
cal
l.lquor will
cook.tng liquor
cal cooking
The
The
eolution.
ln solution.
sollds in
percent of
the total
total solids
of the
40-45 percent
NaOH40-45
cent,
and the
ihe NaOH
cent, and
prlmarllY
Na2CO3.
te
remainder
remainder is primarily Na2CO3.
essenttally
are essentially
place in
dlgeatore are
the digestors
ln the
The
take place
fhat take
reactlona that
lhe reactions
eonstitucnta
ml.nor
and
rnaJor
all
to
This
applies
to
all
major
and
minor
constituents
applles
reactl.ona. Ttrte
hydrolysle reactions.
hydrolysis
detalle
gme
The
The
exact
details
cellulose.
€xtent
to some extent cellulose.
mentioned
lnc.ludlng to
above including
mentioned above
general
deacrtpa
la
The
following
is
a
general
descripfollowtng
The
not known.
known.
are not
reacttons are
all. the
the reactions
of all
of
digestlon:
durlng
fractlons
varLous fractions during digestion
to the
the various
tion
happens to
tton of
of what happens
Ltgnlne -Lignins
grouPs are
thought
are thought
The
phenolic hydroxyl
hydroxyl groups
Ttre phenolic
hydrolythe
in
prtnarlly involved
lnvolved in the hydrolyto
be primarily
to b€
the
ls split,
eplltr the
moleeule is
Oncethe
the molecule
sia. Once
sis,
solualkall
producta
are
decomposition
alkali soludeconposltion products
removed.
be removed.
can be
ble
ble and
and can
Hemicelluloses
Henlcellulosea --
hydrolyzed
easlty hydrolyzed
The polynrers
polymers are easily
Ttre
ln alkali.
alkall.
and
producta are
are soluble
oolubl'e in
the products
and the
Reelng -Resins
aclds,
organlc acids,
weak organic
are weak
The
reslns are
Ttre resins
to
NaOHto
wlth NaOH
readlly with
react readily
and
auch react
and as such
These
salts
pl.ue water.
$eter.
Ttreeesalts
glve the
give
the salt
ealt plus
reeasl'ly reare easily
and are
are quite
qulte soluble
aoluble and
moved.
moved.
Fats
Fats and lfaxeg
Waxes --
saponlfled
readily saponified
These compounds
compounds are readily
lheee
wlth
by reaction
reactlon with
and rendered soluble
coluble by
and
NaOIl.
NaOH
dlgestlon
the digestion
la the
reactlons in
and reactions
components and
In
main components
the maln
to the
addltlon to
In addition
preeent
The
sulfur
present
eulfur
reacttong.
of
side
reactions.
of
al.de
wide
varlaty
process, there
are aa
process,
variety
there are
_Ttre
effect
little
effect
on
have
llttle
whlch
reactlona
of
nuuber
gives rise
to a large
large number of reactions which have
r1ge to
itrre"
reactl'on
followlng
of
the
The
products
of
the
following
reaction
products
pulp.
qualtty of
of the
the pulp. lhe
the
ihe quality
odor and
the characteristlc
characteristic kraft
kraft odor
of the
source of
sequence are
major source
the taJorare the
""q,r"o""
materlal:
toxlc
of
toxic
material
of
aa aa source
aource
luportance as
may
aleo have importance
may also
hydrolyels
hydrolysis
Lignin
----------Llgnin
CH3O}I
CII3OH
Na2S
CII3OH* +
CH3OH
Na2S -------CH3SH* +
NeON -------NaOH
CH3SII
(ClI3Sll)
methyl
mercaptan (CH3SH)
methyl mercaptan
Na2S'
dime thyl eulflde
sulfide +* Na2
S.
dlmethyl
-4-4-
be discussed
later.
w111 he
dlscueeed later.
Ttre toxic
toxlc effects
of methyl mercaptan
The
effecta of
nercaptan will
of
blow tank,
tank, most
moat of
the blow
pulp ia
lnto the
blown from
the digestor
dlgeator into
Ag the
from the
As
the pulp
la blown
Ttre
ta
and is removed.
removed. The
out and
black liquor,
dralne out
or weak
ltquor, drains
the cooklng
cooking liquor,
weak black
the
itq,ror, or
percent-.
Some
from 10-20
10-20 percent. Some
normally from
of the liquor
ltquor varfes
aollds
solids content
content of
varies normally
ls
remalnder is
the remainder
and the
pulp washers,
washera, and
the pulp
to the
ls sent
seit to
of the weak
weak liquor
llquor is
of
chem{cals.
cooklng
of
the
cooking
chemicals.
of
for regeneration
operrtlon for
to the
the recovery operation
cent to
sent
"egeterttton
guLthe sulof the
advantagee of
maJor advantages
the major
of the
One of
The
Process -- One
Reeovery Process
Cheqlcal Recovery
Ttre Chemical
not
wag
this
If
this
was
not
chemlcale. If
the cooking
cooktng chemicals.
of the
fate process is the recovery of
recovery
the
be uneconomical.
uneconoml.cal. The
would be
whole would
process as
as aa whole
possible, the
pooe1ble,
the process
present in
la
lnorganLcs present
and inorganics
organtce and
the organics
of the
separatton of
prn""""
process requires
requires a separation
proceca.,
conrbustion process.
through aa combustion
This
accompllshed through
lg accomplished
biack liquor.
llquor.
Ttrls is
the
the weak
weak black
blaek
neak black
the weak
of the
concentratlon of
lnvolves concentration
The first
ln recovery
recovery involves
flrst step
etep in
Ttre
From
combustlon. Fron
to support
suPPort combustion.
suffictent to
concentratlon sufficient
eolids concentration
liquor
to a solids
llquor to
tncreased
le
solids
concentration
is
increased
concentratl'on
percent,
sollda
the
value
of
10-20
an
of 10-20 percent, the
an initial
lnltlal
by means
mesni
out by
carrled out
usually carried
This concentratlon
concentration is
ts usually
percent. Ttris
up to
30-50 percent.
to 30-50
evaporatlon.
of
of nultlple-effect
multiple-effect evaporation.
ln aa recovery
reeovery
burned in
ls burned
llquor is
Following
bl.ack liquor
the black
concentratlon, the
Follorrlng concentration,
followlng
polnt.
Ttre
The
following
at
thls
addedat this point.
are added
chemlcale are
l,lake-upchemicals
furnace. Make-up
furnace.
furnace:
recovery furnace:
ln the recovery
occur in
whlch occur
are
major reactions
reactlons which
the maJor
are the
1.
1.
CO2.
lnto CO2.
carbon into
organlc carbon
of the
the organic
Conversion
Converslon of
Co2
C * o 2 ---------- - CO2
C+02
3.
3.
NaOH.
free NaOH.
Reaction of
with any free
the CO2
CO2 wlth
of the
Reactlon
N a 2 C O+3 +H20
1120
CO2
------- Na2CO3
C O Z *+
2 N2NaOH
aOIt
derlved
comPounds
Reaction of
of CO2
CO2 wlth
with sodlum
sodium compounds derived from
from
Reactl.on
dlgestlon.
digestion.
Na2CO3
CO2
---------- Na2CO3
C O 2 *.+
N a 2Na20
O-
4.
4.
le
and is
gulfate is
chemlcal and
Sodium
ae aa make-up chemical
added as
ls added
Sodlrrn sulfate
react,ion.
step reaction.
ln aa two
two step
converted
Na2CO3in
to Na2CO3
converted to
2,
2.
2CO2
Na2s
Na2SO4* +2C2C ------- Na2S
+ +2CO2
- ----- Na2CO3
ll2S
Na2CO3+f H2S
Na2S *+ CO2
Na2S
CO2* +Hzo
1120
Na2CO!
the Na2CO3
whlch the
ln which
Le caustlcizat,l.on,
the procees
The
next step
process is
causticization, in
ln the
atep in
lhe'next
wlth
Ca(OH)2.
by
reactLon with
is converted
converted to
NaOH
reaction
to NaOH
la
2NaOE
CaCO3
Ca(OH)2
Na2CO3 ----- CaCO3
+ *2NaO}1
Ca(On)2 * +Na2CO3
aupernatant
The supernatant
mud. The
ee aI mud.
rernoved as
ls removed
The
and is
lnsoluble and
water insoluble
is water
CaCO3is
lhe CaCO3
ls
The Ca(OtI)2
Ca(OH)2 is
operatlon.
dlgeetlon operation.
the digestion
to the
liquor is
recycled to
then recycled
li then
llquor
and
then
then
CO2
off the
the CO2
drlve off
to drive
CaCO3to
regenerated
by first
the CaCO3
heatlng the
ftret heating
tej"n"t"ted
llme.
rcsultlng lime.
by slaking
the resulting
slaklng the
process has
kraft process
the kraft
of the
general outline
outllne of
In
above, a general
sections above,
In the
the sections
wlthln
waate within
of waste
the sources
eources of
In the
eubeectLon, the
followlng subsection,
preeented.
the following
In
been presented.
been
dlscueaed.
are discussed.
characterlatlce
thelr characteristics
the
process and their
are
the proccsa
-5-
-5--
- Two
waste sources
of waste
source8
general classifications
claaalflcatlona
Sourcee
of lfagte
tro general
Sources and Nature
Nature of
Waste of
of
a
are
pertalns
whtch
piocesa.
to
those
The
first
pertains
to
those
which
are
of
a
flrst
Ttre
iriiC from
tiom this
CtrlJ process.
arise
lhe other
other
etC.n The
spLlle, etc.,
nature, such
as Leaks,
such as
leaks, spills,
more or
or less
temporary nature,
leos temporary
oPeratlon
part
the
dally
of
permanent
are aa
refers to
which are
part of the daily operation
to those
thoee sources
aources whtch
refere
be made
made in
ln the
the
w111 be
pulp mills.
between these
dtgtl"nction between
thege will
n111e. A distinction
of
of moet
most pulp
f ol.Loulng discussion.
dLscusalon.
following
waatea
of wastes
procecs, the
sources of
portlon of
naln sources
the main
the process,
In
dlgestlon portion
of the
In the
the digestion
occurrences
these occurrences
through these
Ttre materlal
lost through
The
material lost
and/or spills.
spllle.
are leaks
leakg and/or
are
waate.
etrong waste.
whlch is
ls aa strong
dlgcussed earlier,
liquor discussed
eartier,
is
weak black
black liquor
which
ts the
the weak
(B.O.D.) and
and is
ls
OxygenDemand
Demand.(B.O.D.)
Blochernlcal Oxygen
matertal has
hag ae very
vary high
hlgh Biochemical
ThLs material
This
out of
of the
the
cooked out
organlca cooked
of the
the organics
htghly colored
colored since
lt contains
contalng most of
highly
elnce it
proportton of
of the
the proln this
thle portion
The only
only permanent sources
waste in
wood. Ttre
sources of
of waate
underseparator undergasea from
the separator
bLon tank
and the
the blow
tank and
are the
the condensed
fron the
cess are
condensed gases
although
dtscharge, although
unlt.
The
Ttre latter
latter discharge,
ftow from the
the turpentine
recovery unit.
flow
turpentlne recovery
dlnethyL sulfide.
sulftde.
and dimethyl
B.O.D., nethyl
tn B.O.D.,
smal.l,
small, is
very high
high in
methyl mercaPtan,
mercaptan, and
le very
trend
but the
the current
current trend
be severed,
theee sources
sources may
may be
sewered, but
The
material from
frm these
Ttre matertal
portlon of
operation.
of the
the operation.
thls water
Ln some
some other
other portion
is
reuse this
water in
le to
to reuse
contrlbuflrst
really èigniflcant
algnlficant
the first
operatton makes
The
washing operation
makes the
really
contribultre wEehlng
portLon
of the
the
thls
Included
in
this
portion
of
ln
from
the
n111.
Included
tlon
to
waste
the
load
tion to the
load from the mill.
the
concentrates the
whlch concentrates
process are
pulp washers
waehere and
and the
the thickener
thtckener which
are the
process
the pulp
depende
the saste
of the
pul.p
prlor to
actual source
waste depends
source of
to storage.
storage.
The actuat
stock prior
pulp stock
there is
le aa
proceduree, but
but in
mille there
rnogt mills
ln most
equipment and operating
upon equl.pment
operattng procedures,
of
dllute
conbisting
this
waste
from
of liquid
ltqutd waste coming
comlng from this conèisting of dilute
significant
amount
significant
amount of
black liquor.
llquor.
black
the evapoevaPopulplng process
ls the
The
waste in
the pulping
source of
of waete
{n the
remalning source
lhe remaining
Process is
in
nultlple
btack liquor
Ls concentrated
concentrated in multiple
As the
llquor is
the black
rator
rator condensates.
condengates.
per cent
up to
to approximately
aPproxlmately
cent solids
sollde up
from about
about 15
15 per
effect
effect evaporators
evaporators from
ls
materlal is
organlc material
per cent,
volatlle
of water
and volatile
cent, a large
water and
organic
amount of
50 per
large amount
is
a
evaPorator is a
rnultiple-effect
from
evaporator
from a multiple-effect
effluent
removed. The
Ttre final
final effluent
B.O.D.
l h e B.O.D.
B . O , D . . The
milky-colored,
foul-smelling
w l t h aa high
h l g h B.O.D..
t i q u i d with
n
llky-colored,
f o u l - s m e l l l n g liquid
the total
total
of the
cent of
contributed by this
may amount
amount to
to 75
75 per
eource may
thls source
contrlbuted
Per cent
to be toxic
toxlc
shosn to
This materlal
material hae
has also
aleo been shown
B.O.D.
of the
n111.
Thle
B.O.D. load
load of
the mill.
organisms.
to
to aquatic
aquatic organisms.
and
mlll' and
wlth aa paper
Most pulp
ln conjunction
pulp mills
operated in
conJunctl.on with
srllls are
are operated
Peper mill,
pulp
the pulp
In
preparing the
wagte.
In preparing
of waste.
maJor source
eource of
this leads
to the
the third
third major
thie
leads to
storage
from its
lts storage
pulp stock
dl.luted from
process, the
for
papernaklng process,
stock is
is diluted
the pulp
for the
the papermaking
pulp stock
the pulp
atock
As the
and refining.
refl.nlng.
handl,lng and
facllltate
density
handling
denelty in
in order
order to
to facilitate
to
from
lt
water
{s
paPer
the
removed
is
spread
on
the
paper
machine,
the
water
is
removed
from
it
to
permit
machtne,
spread
the
ls
Permlt
ltater or
or
This water,
water, called
machine water
called machlne
sheet.
this
formatton
of the
the paper sheet.
formation of
anount
large amount
but contains
relatlvely
B.O.D. but
contalng aa relatively
white
large
whlte water,
water, has
has aa low
low B.O.D.
dllute the
the incomincourto dilute
water is
reueed to
ls reused
Most of
of this
this water
wood fiber.
fiber.
of
of short
ahort wood
maJor
contrl.buthe
one
of
thie
to
make
ing
stock,
but
enough
is
wasted
to
make
this
one
of
the
major
contribubut
la
waated
lng atock,
enough
the total
tors
tors to
to the
total effluent.
effluent.
procesa which
whleh
paper-making process
waste from
froo the
the paper-making
Another aspect
of the
Another
the waste
aspect of
rtsllmlcideg.r
Ilue
Due
of
should
be
considered,
and
that
that
is
le
the
the
effect
effect
of
"slimicides."
consldered,
ahould
for
a
tendency
pulp
there
ls
stock,
to
presence
presence
of
wood
sugars
in
the
the
pulp
stock,
there
is
a
tendency
for
wood
eugars
ln
of
to
parte
of
other
grolt
and
ln
machlne
biological
slimes
to
grow
on
the
paper
machine
and
in
other
parts
of
on
the
btologtcal
sllnes to
PePer
quallty and
and an
an inplant
tnplant
paper quality
proceas.
of paper
This
to aa reduction
reductLon of
ltrlg leads
leads to
the
the process.
-6-6-
growth, chemical
the
are added
added to
to the
nutsance. To
chentcal slimicides
el{mictdee are
thls growth,
To prevent
prevent this
nuisance.
are
pulp stock
waters. These
Ttrese agents
agents are
and will
w111.appear
nachlne waters.
etock and
appear in
{n the
the machine
pulp
under
that under
It is
ls thought that
It
very
to all
all forms
of aquatic
aquatlc life.
llfe.
toxlc to
forme of
very toxic
present is
la insufficient
lnsufflclent
nornal operation
amountgof
of these
operatlon the
the amounts
these agents
agents present
normal
problema. Spills
falluree, however,
however,
operatlonal failures,
to
any problems.
Sptlla or other
other operational
to cause
cause any
potenttally dangerous
cooof these
theee comamountsof
dangeroueamounts
to the
the loss
of potentially
lead to
losa of
could lead
pounds.
pounds.
tn
aourcee, but in
lndtvldual sources,
the individual
to the
the above
above discussion
dtscusston pertains
fire
Pertatns to
effluentt
tot8l
the
or
of
these,
or
the
total
effluent,
of
thece,
all
of
the combination
cornblnattonof all
ls the
most
cages it
lt is
most cases
upon auch
such
dependlng upon
This affluent
effluent can vary
vary wldely
widely depending
concero! Ttrta
of concern.
uhlch
ls of
which is
The
The
oPeratlon.
quallty
operation.
of
and
wood, process,
of wood,
variables
type of
as type
varlables as
Proce6a, and quality of
nornally
paPer nil'l
lg normally
mill is
pulp and
and paper
kraft pulp
unbleached kraft
from an
an unbleached
whole
waste from
whole waste
chtpe'
undlgested
undigested
chips,
flber,
of
smounts of fiber,
varytng amounts
coffee-colored
contalnc varying
and contains
coffee-colored and
properttes
of
the
some
of
gtves a listing
Table 1
llctlng of some of the properties
L gives
bark, etc..
pleces of
etc..
pieces
of bark,
that
out that
polnted out
be pointed
ahould be
lt should
table, it
itrie table,
examlntng this
In examining
ltastes. In
kraft wastes.
of kraft
of
exceed
Any
mill
could
exceed
Any
n111
figuree.
absolute figures.
not absolute
are not
the
maximums and
minimums are
and minlmums
the maxlmums
characterlstice.
operattng characteristics.
uPon its
tts operating
dependlng upon
these
theee limits,
llrntte, depending
TABLE
TABLE 11
(after Nemerow,
1963)
Nemerow,1963)
Kraft Hill
Characterists
Mill Wastes
Wastes (after
of I(raft
Characterista of
Characteristics
pH
pH
Total alkallnttlr
alkalinity, PPm
ppm
Total
Phenol
ppm
alkallnltlr
Phenol alkalinity,
PPm
Total
solids,
ppm
sollder
Total
Ppmn
%
s o l l d s , 7.
Volatile
V o l a t l l e solids,
soltder
Total
suspended
solids,
ppm
Total suspended
PPm
%
e
o
l
l
d
e
,
Volatile
V
o l a t l l e solids, 7.
pm
B.0.D.,
ppm
B . O . D . , 5-day,
S-day' p
ppm
Color,
Color, ppm
Maximum
9
.5
9.5
300
300
50
50
2000
2000
75
75
300
300
90
90
350
350
500
500
Minimum
7.6
7.6
100
100
0
0
800
800
60
60
7
755
80
80
100
100
100
100
Average
8.2
8.2
t75
175
00
1200
1200
65
65
150
150
85
85
L75
175
250
250
functlon
dlrect function
are aa direct
effluent are
tot81 effluent
tbe total
of the
The
strength of
Ttre volume and strength
run
efflelently,
is
If
the
mill
is
run
efficiently,
If the m111
rni}l.
io the
the mill.
consumptlon in
of
water consumption
of the
the water
streaors
potential
waste streams
of the
the potential
wtll be mlnlmlzed
water
minimized and many
many of
losaes will
Tater losses
and
volume
both
the
This
will
reduce
both
the
volume
and
proceee.
Ttris w111
the process.
wlthtn the
will be reused
reused within
wlll
consumpltaBer
hlgher
for higher water consumpThe
true for
18 true
reverte is
The reverse
waste.
of the
the waste.
the strength
strength Of
the
to as
a8
uP to
gallons up
201000 gallons
fro'n 20,000
range from
pulp may
may range
of pulp
per ton
ton of
use per
lfater use
tion.
tLon. Water
gal'lons.
60-70'000 gallons.
as 60-70,000
high
hlgh as
cooperacloae cooperathe close
- The
reeelved the
haa
untveralty
Ttre University
Georgia-Pacific
Pulp
Mill has received
Pulp Mill
Georgta-Pactflc
paPef
lnduepulp and
and paper indusother pulp
lc Corporatt'on
tion of the Georgia Pacific
Corporation and other
yeara.
thts
This
many
studies
for
many
years.
for
studlee
acl.entlflc
ln
aseoclitl.ons
tries
and
associations
in
scientific
trles
problen
tha problem
for the
concern
concern for
Lndustrles
the industries
from the
atemed from
hae stemmed
cooperative effort
has
effort
cooperatLve
be
found'
rnust be found.
control must
of control
means of
an effective
effectLve means
that an
and
reallaatl.on that
the realization
and the
-7-7-
lhe Georgia-Pacific
Georgta-Pactflc Pulp
Pulp Mill
lltll at
been used
at Toledo,
Toledo, Oregon,
Oregon, has
has been
uged for
for
The
of
thts
purposes
of
this
study.
atudy.
lfaste
baalc
aamples, basic data
ilata and
full access
Waste samples,
and full
accesa to
to
PurPosea
thl.a mlll
provlded by
been provided
by the
the company.
this
mill have
have been
company.
ye8 constructed
The Georgia
Georgla Pacific
Paclflc Mill
tllll at
at Toledo
Toledo was
conscructed in
ln the
the early
early
The
1950ta.
In order
1950's. In
order to
to m{nlnlze
pollutlon of
of the
the Yaquina
Yaquina Bay
Bay estuary
e3tuary
minimize pollution
strong
frm the
the mlll
pumpedthrough
plpeLlne to
are pumped
through aa pipeline
strong waetea
wastes from
mill are
to the
the
Paclftc
gl.x mi1es.
near Newport,
Nenport, Oregon,
Oregon, a8 distance
dlstance of
of approximately
approxlnately six
Pacific Ocean
Ocean near
utler.
-
TIGURE11
FIGURE
Georgla Pacific
Pactflc Mill
l{111
Georgia
Oregon
Toledo, Oregon
Early in
ln the
the operation
operatlon of
of this
problems of
Early
thla mill
nlll problems
of odors
odora near
near the
the
baach developed.
developed. To
beach
problenr, surface
thlc problem,
To counter
counter this
surface aerators
eerators were
rere installed
lnetalled
on
thc strong
strong saste
plant which
lagoon at
at the
the plant
on the
waste lagoon
rtrlch also
alao serves
purpose
aenrec the
the purpose
of
coollng and
and equalizing
of cooling
equallzlng flow.
flow.
Ftgure
2 preeente
flow diagram
dlagranr of
Figure 2
presents a flow
of the
the study
atudy mill.
mlll.
Basl.c data
date for
for the
the mill,
n111, in
addttton to
Basic
tn addition
to information
lnforuatlon on
on waste
ragte flows,
flore,
etrength and
productlon are
and production
provlded by
are provided
by the
strength
thc company.
glvec
company. Table
Tabla 22 gives
typlcal data
data for
for the
the month
typical
nonth of
of June
June 1965.
1965.
7Zirpef me
ip
!6
e€ ,$x
t/)
$'$
paraho,,
i
r* I
Wc
)i O8t
8B
;s
per
€
!
{
tr)
Slack L,auor
bBt
S
:'
-6
dt
a
r
tu
S
.Uh :$
-d\
r,3
\v
p*
\x: \
\l
,
u$e
;FA
a)l{
orlt
Recovery
FQrnaca
Vapot-
{,
.8
s
UJ
{
t
$
F
x
D
\
o
qJ
o
I
t
I
I
t$
iT
rt
rs H$
I3
t9B
Utu
\t{
t,
r$
Jii
(")
tus
NSIF
u-5v
to
t, sti o
;'$I s
a8s$
lt{
\
E
{
\)
Flow DIAGRAM
TOLEOO, OREGOW
v,
o\
FqJ
Lime
.|'
.c\
,e7lter
U
Lirn
k7Th
(\
Stack
Lime
n
'tr
KRAFr MILL
Mr
Washer
/
II
GEORGIA PACIFIC
s
rSme
iapor
W't Li
Caa1icizi'9i 'br7k.S
{q
Evapcmt
bs
sfi.
j otc'
Evaporator
Clarifier
Rejett
5a ker
S/a ker
F
C code
rg
--
€
Q of Sh-eam
I
lr
Conak ad Lcas
7Laocr 3Q% '5frcom
.P
M,/t,-Effect
/ P
Say
\.
To La9
r-
Th
{d
Tower
0xoti
Ss
/0 Laqoon
L
C/oar Wfrer Waite
c/m9 Water
O
$ra
Cjrr
Ot
A,r
r
.1,
Mace
a
Woher
Ore
c
7 Lon 5 %
5/ow
Thrk
I
(Mrifier
so/v/9
":o
Slow at-SI
Dige5fer
£hiteuor7
-B-
r4
c
.(
q,
F
f,
.a
U
Service Water to Yaguina
Flow
Suspended
5-Day
MGD
B.OID. Solids/#fDay
-9-
4,104
ln
n
|f1
..i
7.5
(\|
@' nl
ro
\o
a.r
F
.
F
\O
.
F!
tn
-'
7,063
\t
(t\
fa
t\
F.
t
\t
3,640
7,736
rn
.
Fr
\t
..r
\g
O
5.589
,l"l; tl
url
3,580
EtlO ol
qllO.El
Fl o+t1
\o o
\t
5,394
IN
olo 8l
513*l o
o
tlc!\l
O
r
rn
F.
o\
'ld El ,'i ;
rn
e
c
@
rn
.d .d ,i
6.2
8.5
6
a
6.516
o\
6.981
olo(.,l
5.969
+{l
blchn|f|dc
\o
klBal
6.035
oltn El
5.915
6.5
rl
cl6
Fl? 9l
2.5
Ll
gl o,dl
u1
a
€
F
t-{
.
rn
9,136
o
3
@
o
0\ * o
S
161
lO ol
lETll
16+{l
ItF{l
\o \o
o
rn
9,396
I
I
I
I
F{
.
o
6'l
o
\g
.
6l
F,
2,436
O
g
O
o
@
5,150
GEORGIA PACIFIC CORPORATION
PAPER DIVISION - TOLEDO
z
O
HO
l{A
<Ft
12,760
I'o8l
g I l€El
o
I
lgl\l
30,180
Effluent and Storage Lagoon Data
June. 1965
Effluent to Ocean
Suflides
Suspended
5-Day
Bromine
No.
Solids/#fDay
B.O.D.
IN
m
\t
.
o.l
oi
ctt
.
c
320
90
248
216
164
H I I*;I
I
l
I
175
276
g
S R
F{ F' :
"n
"n
o
(,
o
d
cco
Ol.
EO
12.822
u'l
arl
(t\
O
I
@
ctr
or
6'l
F.
'
N
.
799.93
12.787
12.130
o
N
u1
F
t\
.
.+
A
co
860.59
(
@
F
.
N
t
EO
OF
ql. { o
€.d
H
or,
r|c
oo
o
FaL
o orl{
!0
tro
B.'{
o
EgO
ts
ql
ct l.
27
1
20
rro
c>
a<
lrl
Fr\tNOF
6lF.Nal
ol
.
F.
804.70
N
.
@
€
F
F
O
12
Date
ol
711.02
N
oi{lNa.tFoc
O
A rQl
o
+a =t\.1
r{
- cUol .oCl l
'-r
F
iol
bl
788.23
Tons/Day
Fle|FaFat{
d
F\
sl r .
(,
11.874
N
.n
.
rt
,i
752.97
tlr\Ff.tfFO
F.
I OAI
1..r
6tri9l
.
C
- -C
= I' lE I
(\
;
13.323
-;
5.934
8.668
3.206
5.829
5.408
4.743
ldtl
12.312
Flow
MCD
lEEl s 3 s R 3
Prod.
E
F
t.
laroo\\g@
-ts|l
Data shown selected from monthly record.
Average is for entire record.
8o"
I lx'il
.,
d I l8;l
208
Et E
g l'l
4
g
1
F{ H
:AFo
fi fi
128
CrO
HH
Raw
Water
MCD
tsl
Ff
,l l3l
ol
l"o8
ctrl 16 G,l
C F .ll tOll O Z l
k
llrlg
I
8
.
t
l
,
l
j
g
l
',516l:El €
S
gl
E
"
r
l
,
t
l
,
cr lHl Fol
Machine
TABLE 2
HH
o . 8 'z
150
Sd S lrl'81
-- 1100(1965) of
approxluately
of approximately
productlon capacity
capacLty (1965)
a production
Briefly this
mill has a
Brlefly
th{c nlll
gallona
10'400
averege
watt€3
The
strong
wastes
average
10,400
gallons
day.
The
pulp per
per day.
strong
of pulp
800
800 tons of
(B.o,D.)
200 ngll
of
Demand
(B.O.D.)
of
200
mg/i
D,amand
oxygen
llochenleal Oxygen
putp-rrith
per ton
with aa Biochemical
ton of
or pulp
pulp.
The
of
The
lbs/ton
of
pulp.
lbs/ton
of
11
loga of 11
aollds loss
(range 150-i0Qi
150-300) end
and a euepended
suspended solids
lrang"
gallonc/ton
a
wtth
gallons/ton
with
a
81350
to the eatuary
weak
wastes discharged
estuary everage
average 8,350
dlscharged to
weak wagtet
lbe/ton
of
7
of
7
lbs/ton
eollda
(ringe 2 to
euependedsolids
aad aa suspended
to 10)
10) and
B.0.D. of
mg/i (range
of 6 ng/l
B.O.D.
quallty at
at the
the
uPon their
baeed upon
thclr quality
wagtea is
Ls based
weak wastes
pulp. Data
for weak
Data for
of pulp.
of
lagoon.
perlod of
tn aa lagoon.
of storage
atorage in
point
polnt of
efter aa period
d{seharge after
of discharge
--111.1BIOASSAYUETIIOD
BIOASSAY
METHOD
of
the effects
effecta of
assesalng the
for assessing
methods for
bloaaaay methods
of bioassay
General
Developmentof
General -- Development
a
been
contlnulng
continuing
has
environment
the
marl.ne
on
industrial
effluents
on
the
marine
environment
has
been
a
effluents
li,lffifal
hls
and his
l{P -- 524) and
(Go-investlgator WP
Dlmlck (Co-investigator
R. E.
B. Dimick
effort
of Professor
Profesgor R.
cffort of
been
aupported
have
years.
These
efforts
have
been
supported
efforts
These
10
more
fpr more than
than 10 years.
associates fpr
aeeoclates
the
of the
Improvement of
Stream Improvement
for Stream
Counctl for
Natlonal Council
Univerelty, the
the National
by the University,
grantc.
Reeearch
Research
reeearch
pollutton
by
lrater
paper industry
pulp
and by water pollution research grants.
putp and
ana paper
lniuatry and
these efforts
efforte
of these
of support
support of
source of
been the
maJor source
the major
tfP -- 524
hae been
Grant
524 has
brtnt VP
bloaasays
of
development
tncluded development of bioassays
reeearch included
Elologtcal research
!964. Biological
since
al.nce 1964.
Paclflc
the Pacific
(Myttlus edults),
edulla), the
bey mussel
mussel (Mytilus
involving the
the enbryo
embryo of
of the
thebay
lnvolving
marlne'
the
use
of
the
of
the
use
of
the
marine
of
glgas), and
(caraseoatrea gigaá),
exploratlon
and exploration
oyster
oyster (carassostrea
end
eurvlval
upon
the
based
are based upon the survival and
The
(raonochrycfs sp.).
tests are
6e embryo
enUryo tests
spl).
algae (monochrysts
to
exposed
to
"igr"
exposed
of
embryo
davelopment of embryo
the abnormal
Ebnormal development
and the
growth of
griuth
of the embryo
tnbryo- and
productl'on. In
pulp production.
process of
of pulp
kraft mill
mlll process
different
wastes from the
the kraft
dlfferont wastes
and
stlokleback and
aplne stickleback
tte three
three spine
involving the
addition bioassay
b1oaseay techniques
technlquea involving
addltlon
a
form
do
noE
although
they
do
not
form
a
they
employed alChough
the comnon
common guppy
guppy are also
also belng
being employed
used to
to
are used
developed are
The bioassay
bloaeaay techniques
technlquee developed
proJect. Ttre
part
of this
thle project.
part of
engl'neerlng
evaluate efftency
effiency of
of treatment
treatment methods
methods Lnveatlgated
investigated ln
in the engineering
evatuate
the
staff, the
funds and
and staff,
proJect funds
of project
Because of
of
llnitations
of the limitations
reeeerch. Becauge
research.
bay
the bay
use of
of the
to the
the use
prlmarlly to
been limited
llnited primarily
bioassay
work to
has been
date has
to date
bloassay work
L.
Mytllus edulls
mussel, l4ytilus
edulis L.
mussel,
Ij.
edulis L.
MYFtlus.edulis
musael, Mytilus
Bay mussel,
cotmtonBay
lAe common
Bioassal -- The
Bay Musssl
Mussel Embryo
Egbrlg Bioassay
Bay
and
that
its
embryos
and
embryos
its
that
suggest
whlch
possesses certain
unique features which suggest
possesses
certaiilTiT,ffiEeatures
leboretory
routine laboratory
ln routine
advantageously in
be employed
employed advantageously
larvae
might be
also mlght
i"r.r." also
that
guppy
-that guppy
ltays
satne
the
much
I'n
bioassays
made
in
saltwater
samples
much
in
the
same
ways
eamples
bloaasays made |n salt$ater
test
used
as
("water-fleas")
are
used
as
test
(rbater-fleegtt)
Daphnla
the crustaceans,
crugtaceana, 'Daphnia
fish and
and the
fleh
stations.
freehwater stations.
orgaüisms
at some
somefreshwater
organisms at
bioassay
u8e as
a8 aa bloaeaay
for use
Bay mussel
nussel for
Favorable factors
of the
the Bay
cupport of
ln support
factors in
Favorable
arei
tnverBebrate are:
marine
marl,ne invertebrate
of
zones of
lntertldat
the intertidal
tn the
dlstributlon
Its wlde
wide geographtc
geographic distribution
in
Its
provldes
co11mon
provides
a
common
ateas
ehore areas
ocean shore
estuaries, bays,
some ocean
baye, and
and on some
estuarLes,
partlculocated
located particustationa
at many
test organicm
organism available
available at
many marl.ne
marine stations
test
Paclfl'ct
north
tn the
the north Pacific,
It
occure in
It occurs
hemlaphere.
north6rn hemisphere.
fn the
*re northern
larly in
larly
as
south
as
eouth
far
and as
as far
BaJa, California
Callfornl'a and
from
Arctic Ocean
Ocean into
lnto Baja,
Cha Arctlc
from the
Amerlca
of
North
North
America
coaet of
eastern coast
on the
the eastern
CoacC; on
Japan on the
Aslatic Coast;
the Asiatic
from
Europe, from
ln Europe,
and in
Carollna; and
North Carolina;
Hatteras,
from
Greenland to
North
to Cape
CaPe Hatteras,
from Greenland
It is
le
It
Afrtca.
northern Africa.
and northern
the Medtterranean
the
White Sea
Mediterranean and
Sea to
to the
the Whlte
frm
AroerLca; and from
South America;
of lower
lower South
eoaate of
also
reported from
both coasts
from both
also reported
1955).
(Soot-Ryen 1955).
Zealand.
New Zealand.
and New
Australia
Auatrall.a and
1.
1.
meane; and
by chemical
chemlcal means;
stlmulated by
Spawning
readtly stimulated
Spawnlng can be readily
tt
arear at
ot!' area,
Ln oiz
Leaat in
at least
avallable,
(eggs and sperm)
are available,
ganrete (eggs
aperm) are
gamete
at
year.
of the
the year.
all times
all
tlmes of
2.
2.
documented
the muesel
The embryology
embryology of
of the
mussel {a
is well
well known
known and documented
Ttre
(Rattenburg
(Rattenburg
lanree
and
enbryoe
ebnormal
the
(Field
as
are
the
abnormal
embryos
and
larvae
(Fteld 1922)
a"
Lg22,
1954). "te
and Berg 1954).
3.
3.
-L2-12of
by aa wide
wlde variety
variety of
The
affected by
lntmically affected
Ttre embryos
embryos are
are inimically
factorr
perhapa by
by differences
tn ecological
ecologtcal factors
chemical
dlfferenceg in
and perhaps
chemlcal compounds
compoundaand
tn saltwater.
seltrtetcr.
occurring
and experimentally
experlmentally in
natural.ly in
{n saltwater
aaltwater and
occurrlng naturally
4.
4.
frou ar
resulted from
f,or testing
teatfng purposes
enbryoe for
Use of
of the
mussel embryos
Bay muarcl
Uee
the Bay
Purposea resulted
of
the reactions
reacttone of
obsenlng the
In 1958,
while observing
195E, wtrlle
laboratory happening.
happcntng. In
chance
chence laboratory
salteeltln ae strong
rtrong
(oyatera, clams,
muesels) in
clamr, and
and mussels)
several kl.ndc
kinds of
btvllves (oysters,
of bivalves
several
(KME), it
that
notlced that
lt res
eftluent (KNE),
water
mill effluent
was noticed
of Kraft
Kraft u111
rater concentration
concentratlon of
(Breeae,
end
Mlllemenn and
end sperm
apenn (Breese, Millemann
eggc and
several of
of the
mussels discharged
dt.echarged eggs
the mpsels
reveral
apaun.
to spawn.
not stimulated
sttuulated to
were not
clasu were
and clams
Dimick
oyetera and
ntrtle the
the oysters
1963) while
Dlnlck 1963)
qera
ripe") adults
(fraexually rlpa[)
adultg were
grevld ("sexually
that gravid
dlscovered that
Then, later,
was discovered
later, it
Lt rag
Ttren,
embryoc
year. Thus,
Thua, mussel embryos
of the
the year.
bay at
eeaeonaof
present
preeent in
et all
alL seasons
ln the
the bay
needed.
when
time
when
needed.
t{me
et
any
purpoees
btoassay
obtainable
for
bioassay
purposes
at
any
for
obteinable
were readily
reedtly
(2
aolutlong
ln
ealtrrater
KcL
Subsequently,
it
was
found
the
the
ICCL
(2
gr/liter)
in
saltwater
solutions
found
it
wae
Suboequently,
$|ttt,ar)
vlablc
ln viable
ganetee which
reculted in
whtch resulted
of gametes
also
vigorous spawning
apawrrLngof
also caused
c'auaed vtgorous
nor:nal larvae.
lanrae.
embryos and
and normal
embryos
thc
of expoalng
conatsta of
bloaeaay essentially
eaeentlally consists
Method
exposing the
mrgsel embryo
enbryo bioassay
A mussel
Hethod -- A
of
concentratlone
different
concentrations
of
dlfferent
to
eaaul.ng embryos
embryoa to
eggs and sperm
and the
the ensuing
spetra and
E'ffiTna
tlnet
of this
thla time,
the end
end of
hours. At the
for 48
48 hours.
particular
substances
paitt",rtar
ln seawater
seawater for
subgtances in
abnormal
abnormal
and
larvae
(ahelled-etralght
htnged) larvae and
the nunUerc
numbers of
of normal (shelled-straight hinged)
ihe
the
of the
eash of
ln each
counted in
(nonshelled
or imperfectly
are counted
(nonahelled or
larvae are
ahelled) larvae
lmperfectly shelled)
ere counted
counted
eggs are
fertlltzed
In sore
some bloaasaya,
bioassays, the fertilized
eggs
ln
test
te.Bt solutions.
Bolutiong.
of
gurvfvlng larvae
the termination
ternlnetlon of
at the
larvae at
of surviving
and then related
numbers of
related to
to numbers
and
the tests.
teatg.
the
ln
I'r in
clams is
and clams
oysters and
uelng oysters
bloaaeay using
blvalve bioassay
This
ganeral type
of bivalve
type of
Ttrla general
Each
has
Eaeh
her
lnvectlgators.
by several
eeveral investigators.
been employed
enployed by
but has
hag been
way original
but
orti{nal
no wey
dl'sA
A thorough
thorough discondltlona.
and conditions.
needg and
added
modifications to
epeclflc needs
flt specific
to fit
addedmodlilcatl.ong
particularly
pertaining
to
the
Pertalnlng to thc
cuss ion of
of laboratory
laboratory proeedureg
procedures lnvolved,
involved, partlcularly
cuse1on
Woelke
by Charles
Charles lloelke
preaented by
been presented
has been
Pacific oyster
oyster and
andsome
clanr, has
aomeclams,
Pactflc
ttBioaseay -- The
Tool.rl
Iarvae Tool."
Blvalve Larvae
the Bivalve
(1960)
(1960) in
entitled "Bioassay
ln- a paper entltled
are everywhere
everyetrere
sperm are
and sperm
Adult
obtalnlng eggs
egge and
used for
for obtaining
mrussels used
Adult mussels
prevall
patterns
sallnlty patterns prevail
nhere adequate
adequate salinity
abundant
bays where
of our
our bays
ln most
moet of
abundaut in
ftoatat
to
They
are
normally
found
attached
to
floats,
Ttrey are normally found attached
throughout the
cycle.
the life
lLfe cycle.
lnterttdal
ln the
the intertidal
ueually in
piling,
structures, usually
plllng, rocks,
other solid
and other
eolld structures,
rocko, and
zone.
zone.
barnaclelt
ae barnacles,
euch as
materl.al such
of extraneous
extraneoue material
The mrcrela
mussels are first
flrat cleaned of
Ttre
inmterced
lmerced
dishee
etaeklng
ptaced
lndivLdual
They
are
then
placed
in
individual
stacking
dishes
ln
then
ltey
debris,
etc.
debrla, etc.
30
within 30
epawnlng slthtn
start spawning
normally start
llales normally
KCL. Males
contalnlng KCL.
in
Ln seawater
searater containing
rinsed
rl'nscd
thoroughly
ls
mussel
the
As
soon
as
spawning
is
noted,
the
is
thoroughly
noted,
ls
soon aa iparntng
minutes.
m1nutee.
(Flgure 3).
In this
thle
3). In
aeawater (Figure
dtluent seawater
of diluent
beaker of
and
ln a separate beaker
and placed in
and
separate
mussels
may
be
kept
separate
and
be
kept
nay
muasele
from individual
lndlvlduat,
way,
sperm from
and sperm
fafr eggs
cgge and
tnhcrent
ehould inherent
be identified
ldenttfted should
enbryos may
thus tha
the perentagc
parentage of
of regultlng
resulting embryos
may be
ttrug
guestlon.
a
bccomc
viability
of
and larvae
trarvec become a question.
of embryos
embryos and
v{ablllty
adJuated
watcr adjusted
Bay water
Yaqulna Bay
golutlonr are
froo Yaquina
Test
usually from
prcprred usually
arG prepared
Teet solutions
cprtng
uncontaminated
spring
uncontaml'nated
p.g.t.
wlth
when necessary
necessary to
to aa aallntty
salinity of
of 25
25 pp.t. with
wlren
- ltght
light
ultra-vl'olct
to ultra-violet
exposed to
La exposed
water is
tegt rlter
dlluent test
thc diluent
Oenerelly, the
water. Generally,
ratGr.
Test
centrifuglng.
g@ettnea subjected
to continuous-flow
contlnuous-flory centrifuging.
eubJectcd to
and it
1g sometimes
end
lt is
u8ually
rangcsr
conc€ntr8tlon
rlthln effective
affcctlve concentration ranges, usually
solutions
arc then
then prepared within
colutlona are
-13-13predctenDlned by
Measured
of eggs
volune of
eggr
predetermined
by ae screening
test.
Dlaarurcd saltwater
saltwatcr volume
rcrecning test.
glaee teat
way,
In this
dlahes, In
thl.r way,
and
end sperm
lnto the
thc glass
spcrm are
erc introduced
tntroduced into
test dishes.
phce ifl
teat solutions.
fertilization, if
tlr the
thc test
solutlotg.
takcr place
fertlllzetLon,
lf not
not inhibited,
Lnhlbl.tcd, takes
rooos and/or
and/or
Then
Then the
the dishes
dleher are transferred
to constant
constant temperature
tcqaratur€ rooms
tranrferrcd to
incubators,
lncubatorr.
-
*
FIGURE
FICINE 33
mrcgcls
Spawning
male and female
of nalc
female mussels
Sparwnlng of
(Cloudy dishes
of sperm)
cpctn)
(Cloudy
dlshes indicate
lndl.cete emission
eml,aelon of
-14-14-
y
ZR
TIGUNB44
FIGURE
blorlray
of incubating
lncubattng bioassay
dlrhca of
tert dishes
Stacked
Stecked test
bloaeaey
of, ae bioassay
bcfore termination
tcrninrtlon of
Approximately
or two
ta6 before
hour or
an hour
Approxlortely an
I'r
dlrtllled
Ln
eteln in distilled reter
(46
tro of
(46 to
to 47 houra)
hours) a drop or
or two
of ncutrel
neutral stain
water is
of
dlffcrcntlatlon
leter differentiation of
in
ln the
thc later
t!rl.t!
dtrh. This
thlr assists
to each
cach test
teet dish.
added to
edded
of
fcrtllltlne
thc
Forty-eight
hours
from
the
time
of
fertiliForty-clght hourr frou
lewrc.
fron normal
nornel larvae.
abnormal from
ebnornel
lenrec
ebnornat larvae
end abnormal
of normal
nornel and
end numbers
nunberl of
zation
killed and
rrc ltlllcd
lanrec are
zatlon the
thc larvae
of 150
150
Sample
sizes
Sarylc elzcr of
concentrition.
tolutton concentration.
are
tegt solution
for each
each test
ere recorded
rccordcd for
recorded
er.
recordcd
count3 are
occarlonalty counts
(abnornel and
nadc and
rnd occasionally
arc made
larvae
nornel) are
and normal)
lenrac (abnormal
ln incuI'ncuspece in
Replications are
unlcrr space
trc employed
cnployed unless
RepltcetLoar
raryles.
for dupllcats
duplicate samples.
for
normal
of normal
rarutta, percentages
In
reporting test
teet results,
In reportlng
betorg is
tg limited.
ltutted.
Pcrccntegeg of
bators
bioreveral bloof several
reaultr of
larvae ere
are ugcd
used end
and relatlvc
relative percantager
percentages rhen
when results
lenrec
lledlan
the Median
groupr. For comparison,
couparlconr, the
re combined
conblned groups.
assays
arsayr are considered
conaldercd as
producc
goiutLon which
to produce
ls expected
crpectad to
rtrlch is
Effective
of test
tect solution
Concentratlon of
Effectlve Concentration
lanree).
norual larvae).
percant normal
(or conversely
5O percent
csuvcrecly 50
50
percent abnormal
lanac (or
abnornel larvae
50 percent
en
follcu
noruelly follows
develop,uent normally
Enbryonlc development
Embryonic
an
l!,evelopment -- Embryonic
Enbrvontc Development
time periods
orderly
pattern
of
structural
changes
occurring
at
specific
@ructura1ehengeroccurr|'ngetepeclf1ctlreper1ods
approxtnatelt
lt approximately
tchcduls ii
lanra schedule
(Fleld
darclop,nental larva
tha developmental
At 20°
2Oo CC the
(Field 1922).
tbZD.
ac
follms:
as follows:
rhen discharged
digcharged
[n shape
rhape when
ovel in
The
at first
flret somewhat
emertret oval
le at
Ttrc egg
cgg is
nicrong
(approxfioatcly
70 microns
goon changes
ehepc
but
to
nearly
round
shape
(approximately
70
ncarlt
to
but soon
changce
nctaphalc
the
to
dcvelopmnt
in
diameter)
and
rapidly
starts
development
to
the
metaphase
rep[dly
rtrltt
end
ln dl.anctcr)
(Flgurc 5)
3)
of development.
dcvelopoenE. (Figure
stage of
ltegc
1.
1.
- 15-15-
the egg
minutes after
penetrates the
llLthtn about
20 ninutcs
aftot the
thc sperm
aperu Pen€tntsc
2.
2. Within
.bout 20
follorcd by ae
poler body
1r followed
body appears.
membrane,
eppcars. This
Itrlr is
tho first
flrrt polar
mubrme, the
(Flgurc 6)
polrr body
6)
(Figure
second
body in
10 minutes.
ntnutcr.
recond polar
tn about
abouc 10
poler lobe
rnd second
recond
rnd first
flrrt and
Then
bcaomr evident
lhen a
e polar
lobc becomes
cvtdcnc and
perlod
follorlng
nlnute
cleavages
durlng the
thc 50
to 90
90 minute period following
clcrvagcr occur during
50 to
(Flgurc 1)
Lnremlnatlon.
7)
insemination.
(Figure
3.
3.
(theny cclledrr)
rtrc 44 1/2
The
celled") become
at the
bccoec free
free swiiauing
eslmlng aB
blmturl ('!many
Tlrc blàstual
U2
pcrlod.
to
to 5-hour
5-hour period.
4.
1,
Gas
trulation teke,
takes plecc
place end
and ra hrvel
larval foru
form (unehellcd)
(unshelled) crllcd
called
Gertruletlon
the
houn after
rftcr fertilization.
fertlllzetlon.
20 hours
trochophorc appears
rppGrrr about 20
the trochophore
5.
5.
Shells
(velver) begin
rppeerlng in
ln
bogtn appearing
Shcllr (valves)
then
called vcltgcr,
veliger, rtrlch
which
lenac, callcd
thsn the
the larvae,
(D shape)
hinges
occut. from
fron 43
hlnger shells
rhellr (D
rhapc) occurs
43
(Ftgure 8)
(Figure
8)
after fertilization.
eftsr
f,crttllzetlon.
6.
6.
end
about 40
43 hours
hourr and
to 43
40 to
rell-forud
.trtlthtposses
well-formed
straightPotr.t
tlm
hourr elapsed
elrprod time
to
to 45
45 hours
I
*
I
FIGURE
TICURB55
t
--16-.
16-
:i'
ritl: .:
;;
"rt,
:
,
r
FIGURE 6
FIGIJRB
FIGURE 7
rrcm8
7
., :
-t7 -17-
n
8
FIGTIRE
FIGURE 8
tfornrl and
and abnormal
rbnoruel larvae
lervac'
Normal
bloeecayr
fron five
flvc typical
typlcal bioassay.
Bloetaay Results
Resultc -- The
rerultt from
Examlee of
of Bioassay
ftre results
Examples
la bclng
hor the
tcst is
were
illustrate how
mussel-embryo test
being eoployed
employed
weiC selected
the nussel-cobryo
Eel,icEad to
tolllurtrete
preaented deals
wlth results
rerultr
dealg with
The
at our Yaquina
Bay Laboratory.
leboratory.
Ttre example
exaryle presented
at
lequlna Bay
stagct
undergoes successive
euccelelve stages
froo
the waetc
from a alnrlated
simulated cctuary
estuary in
which the
waste undergoes
ln wtrlch
of degradation.
degradatl.on.
of
trstrong waste"
(nlnue wash
rash and
and service
servlce
Composite 7-day
racten (minus
of Ustrong
Co,4orlte
aaqplee of
7-day samples
type of
of mill.
nLll.
non-bleech type
treekly intervals
frou aa non-bleach
waters)
watcra) were
sere collected
at weekly
lntervale from
collected at
aPparatuc
pasaed through
ctablll.aatlon apparatus
were passed
through aa stabilization
Seven
Seven of
of these
theac samples
sanples were
18 liters.
ll'tera.
glaaa jars,
holdlng 18
each holding
whlch
serl.ec of
of glass
which incorporated
lncorporated aa series
Jara, each
lnto the
thc
punrpedfrom
from aa reservoir
reservoLr into
percent by
!ra8 pumped
by volume, was
Diluted
Kl{Er.25
Dlluted KNE,
25 percent
gravlty
succeaglve
by
each
was
lnto
flow
first
jar;
and
from
there
the
flow
was
by
gravity
into
each
successive
end
thcre
thc
flrgt Jer;
fron
retentton in
ln
2-day retention
at approximately
w€r€ maintained
matnteLned at
approxlnately 2-day
jar.
Flon rates
retea were
Jar, Flow
before
the
provlded
reservolr
sas provided in
ln the
the reservoir before the
Mild aeration
aeratlon was
each
each jar.
Jer. l,llld
an
and an
mlxlng and
eomplete mixing
to assure
assure complete
diluted sample
entered the first
flret jar
dlluted
aanple entcred
Jar to
glnulated
passege
rasPectsr
ln
eome
Such
a
passage
system,
in
some
respects,
simulated
Such
system,
aerobic
aerobl.c environment.
ernrlroment.
10-day
paaclng down
durlng aa 10-day
downan
an estuary
estuary during
a travel
an effluent
efflucnt passing
route of
of an
travel route
perlod.
retention
retentlon period.
seParetc
of seven
seven separate
racults of
the composite
conpoe{tc results
An
of table
table 33 shows
ahorn the
An inspection
lnapectlon of
geven-day
rnean
relatlvc
ln
and expressed
expreeged in mean relative
bioassay.
Lntenlals and
bl.oaeaayc made
nradeat
at seven-day intervals
groups ranged
frm 85
85
ranged from
percentager or
coatrol groups
The seven
sevcn control
norual larvae.
larvEe. The
or normal
percentages
The
median
percent.
nedl.an
Ttre
of 95
95 percent.
to
percent notmal
normal larvae
with a mean
mean of
lanrae wlth
to 99 percent
of the
the KME
KllE
(EC 50)
percent by
by volume
voltrun of
ln percent
Effective
vglues in
50) values
Effectlve Concentration
Concentretton (EC
end
pereant
larvae
produce 50
abnormel larvae and
50 percent abnormal
are the
to produce
amounts estimated
are
the amounts
cstlmated to
hand column.
column.
the right
rlght hand
these
estimates are
tn the
tecotded in
ars recorded
theee €sttmates
Estimated
EC 50
% KME
-18-
81
8.2
74
138
312
265
45.6
420
582
61.1
67].
761
743
798
888
904
aaaaaa
FITiFFOO
!'p
qt
7.2
131
323
57 0
77.6
!nFFINF{N
r0
E()trl
7 1
29 4
.t
57
40
15
cro
rr rn
37.2
E
trlbt
KME Stabilization Results from 10 Day Retention Samples
Mean relative percentages of normal larvae based on seven bioassays
o
t\
(6
o
'@
.tt
14
o
o€
o)
F{C
oio
8.3
fndN!n
11
HB
.no
aaaa
@
6
€
90
0, rd.
+Jo
o
& a(ll)
Percent normal larvae
o
h
>
qlH
6
r{
r{
(tl
EE
gl
825
84.5
98 3
..lI
6 day retention
8 day retention
\Ct
.if
F1
co oc
rlU
+JH
(dO
Ng
{;
FIO
1
05
947 722
r{>
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rtt +J
lJ ql
cO F.l
o
c)
5
4 day retention
2 day retention
ccccc
ooooo
."{t{ddt{
urrlJut,
ol
EI
5l
I(ME %
Fll
beol
>l
rrl
I
=
>|
gol
trtrc!
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o
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l.
trtr
O
t
h
qt
r,
h
irl
E
h
cl
t
h
r0
t
<rt
.s
\o
@
10 day retention
:l;
E ord
Original
samples
HK
90.5
+J
943
c,
103
H
356
1u,
oo
c'@
3
r{
dd
-l;
u
tr
o
o
2
fi sr
0
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o
5
6
Bb
r+{ gi
by volume
TABLE 3
Fl
E
7
}|
F{
FI
aaaa
.ttcNrnN
('l
N
tll
o(U
o
.'I
l
o.c.vl\oo
9
+'(u
655
tro
o
.r{
('f
F{
F{(.}N
O
l.
h
rrt
€
I
-L9-19ghonn in
9.
Flgure 9.
Results
Reeultc of
typlcal bioassay
bloaeeay are
are shown
ln Figure
of this
thls typical
CHANGES
IN
CHANGES
IN NORMAL
NORMAL LARVAE
LARVAEPRODUCED
PRODUCED
DURINGBIOLOGICAL
BIOLOGICAL
DURING
MODIFICATION
MODIFICATION
OF KME
OF
KME
IN A
A SIMULATED
IN
MARINE
ENVIRONMENT
SIMULATED
MARINE
ENVIRONME
NT
EC50
I?
PERCET{T
PERCENT
NORMAL LARVAE
NORMAL
LARVAE
FIGURE 9
FICT'RB
The reader
reader is
directed to
to nBay
"Bay llucsel
Mussel Btoacaeyo
Bioassay" by
by R.
R. E.
E. Dtnlck
Dimick
lhe
le dlrected
Paetflc Northwest
NorttrweatIndustrial
Industrlal
Breege, Proceedings
and
V. P.
P, Breese,
Proceadtnge of
of the
the 12th
12th Pacific
and l{.
deacrlptlon
detalled description
for a detailed
Waste
Washington, for
lfagte Conference,
Untveralty of
Conf,erence, University
of lfaahlngton,
procedures.
of
of test
teat procedures.
EXPLORATORY
STUDIES
EI(PLORAr{'RYSTUDIES
- Exploratory
General were undertaken
undertaken in
basis for
for
1954 as a baeLr
Ln 1964
Exploratory studies
studles rerc
qulckly
forn
been
to
The
objective
of
these
studies
to
quickly
form
has
of
ensuing
work.
work.
obJectlve
these
studl,es
Ttre
Cniutng
quidelines
that
might ba
be encountered ln
in
quldellnes and
that rntght
determlne difficulties
dlfflcultles
and determine
aature.
detatled nature.
subsequent investigations
more detailed
of ae morc
lnvectlgatlonr of
eubaequent
wlth
waatee treated
treatad with
on wastes
In
btoacaayc were
were conducted
conducted on
In these studies
studl.eg bioassays
Statc
Oregon
8t
graduate
various
methods
by
graduate
students
in
engineering
at
Oregon
State
Ln
englneerlng
atudents
varlous methods
studleg
Retention studies
In addltlon,
addition, Stetlc
Static and
Seml-dynanrlc Retention
and Semi-dynamic
In
University.
Unl.veraity.
CentGr.
Scl,ence
Harlne
at
the
with
strong
kraft
wastes
were
conducted
at
the
Marine
Science
Center.
rester
rere
conducted
wlth strong kraft
blologlcal
phyclcal
and
of
the
This
resulted
in
the
evaluation
of
some
of
the
physical
and
biological
of
some
Thlr reautted ln the evaluetlon
Pearl
llenend, Pearl
OxygenDemand,
properties, based
Blologtcal Oxygen
propertlec,
baeed on
of Biological
on ae comparison
cmparlcon of
have
Exploratory
bioassays
have
bloaeaaya
Bxploratory
Bay mussel
bloaaaay.
Benson Index
and the
muesel bioassay.
Beneon
lodex and
thc Bay
fl.ah,
saltrater
been run
run rlth
with the
amphipod, Corophl.um,
Corophium, the
the Stlclclebech
Stickleback fish, saltwater
been
the anphlpod,
-20-
been centered
centered
haa been
gupplec, and
emphael,ehas
Howevar, emphasis
and the
oyater. However,
the oyster.
conditioned
condltloned guppies,
reflne
bloaaray, to
to refine
8ay mussel
nuaael bioassay,
of the
on
the Bay
devElopnent and
and evaluation
cvaluatlon of
on the development
the animal.
anlmal.
of the
blology of
the biology
the technLques
techniques end
and to
better undsratend
understand the
to batter
thc
study wer
recearch, aa study
dlrectly to
to the research,
In eddttlon
addition to
work relatcd
related directly
was
In
to rork
uee in
ln
for use
saltwatGr for
for synthetic
undertaken to
eynthetlc saltwater
develop a formula
fornnrla for
to develop
of kraft
Certain cxperlnental
experimental treatments
kraft wastas
wastes
bloaseaya. Cert[ln
treetments of
marine
narlne bioassays.
the
of the
btologlcal level
level of
to the
the biological
demanded
be raised
raised to
aallnlty be
thst the
the salinity
dananded that
toxt'cent.
of
thc
the
concentratlon
wlthout
organism
being
tested
without
changing
the
concentration
of
the
toxicant.
betng
changlng
testcd
organtsn
tostLng
eel.twatcr
e
reproduelble
to
formrlate
Also,
it
was
necessary
to
formulate
a
reproducible
saltwater
testing
Alao, Lt was n€cessary
nottal embryonic
enbryonlc
so that
that normal
medium
blologlcally acceptable
eal.ta, so
acccpteble salts,
wtth biologically
uedlum with
torards
to
recearch
This
necessity
led
to
research
towards
led
neccnslty
therel.n. lhle
development mey
may occur therein.
developoent
rratandardtr
medlum.
testLng
salt$teter testing medium.
of a "standard" synthetic
cynthetlc saltwater
the
development of
the development
ln
been included
lncluded in
have been
studl€s have
The
of these
thece exploratory
axploratory studies
The results
reoultr of
of this
thle report.
report.
the appendix
appendix of
WASTES
OF
DEGRADATION
OF KRArT
KRAFT MILL
ITECRApATION
EILL WASTES
IIATERS
ESl'ttARIt{EWATERS
IN ESTUARINE
wastee in
Ln estuarine
ectuartne
mlll wastes
of kraft
kraft mill
General -- Studies
Studles of
of the
the degradation
degrcdetlon of
General
problem of
llr. 0G. L.
of Dr.
part, as
reaearch problem
ea the
the research
waters
were conducted,
Ln part,
cOnducted, in
watera were
progress report
r.port
the progress
of the
eectlon of
progrem of
Ttrls section
of study.
atudy. This
hls program
O'Neal
ln his
Orlleal in
phase of
of the
the study.
study'
thie phase
summarizes the
research undartaken
undertaken on this
thc reeearch
sumarl.aes
Methods Selected
Evaluating Pegrgdatls-n
Degradation -- l,leacuremente
Measurements of
of tha
the oxygen
oxygen
for Evaluatlng
Selected for
Uethods
conbackbone of
of pollution
e backbone
demand of the waste or polluted water are the
Pollutton conthe
of
evaluatl.on
Without
these
measurements,
an
accurate
evaluation
of
the
an
eccurate
measurementa,
lllthout
th€se
trol
work.
work.
trol
Oxygen
The Blochemlcal
Biochemical Oxygen
lhe
lmposclble.
le impossible.
system is
oxygen resources
resources wlthln
within the system
oxygen
lnformietl'on.
obtaln
thla
uged
to
Demand
test
is
the
method
most
commonly
used
to
obtain
this
information.
co'monly
uoet
tbmand teet La the nethod
oxygan
the oxygen
whtch the
at which
rate at
the rate
The most accurate
of the
determinatlon of
Eccurate determination
Ttre
B.O.D.
B.O.D.
ul'tlnate
ln
uae
of
the
change
demand
is
consumed
is
obtained
by
use
of
the
change
in
ultimate
demandLa coneumedls obtelned
maxlnuo
represents
the
maximum
B.Q.D.
B.O.D.
rePrecente
period.
ultlnate
This
Ttrls ultimate
over a time
tl.me period.
over
Eo
tlne taken
takea to
of the
the time
gtven sample,
Lrrespectl.ve of
oxygen
aauple, irrespective
of aa given
demandof
oxygen demand
ul'tlnate
tn
the
change
For
a
variety
of
reasons,
the
change
in
ultimate
varlety of reacona,
demend.
achieve this
thls demand.
achleve
which
teetO whleh
Inatead, tests
etudles. Instead,
ueed for
for rate
rate studies.
rarely used
method is
le rarely
B.0.D. method
B.O.D.
The
ueed.
the
are
used.
B.O.D.
ultlnete_B.O.D.
proportlon of
the ultimate
of the
give some
glve
fractl.onal proportion
aooe fractional
whlch
test,
which
testt
B.O.D,
20oC B.O.I!,
flve-day 20°C
le the five-day
most
methods is
of these
theee nethodc
noat common
comon of
gerLee of
of experiments.
expcrlnente.
was
thls series
dn this
ueed in
wag used
wastes.
uost wastes.
for most
wlthln limits,
llnite,
Tests
for
be true,
true, within
to be
thle to
have shown
shorn this
Teets have
B.O.D. represents
rGPresentt
flve-day B.O.D.
ln five-day
chenge in
prcctaely true,
the change
trua, the
Even
lt is
lt not precisely
tf it
Even if
For this
thLl
B.O.I)..
B.O.D..
ultlmate
ln ultimate
of change
change in
a
of the
the rate
rate of
good approximation
approxlnatton of
a good
thle
and
incubator
space,
this
of time
tftne and Lncubetor sPacet
reason, as
as considerations
well as
conclderatlons of
ls well
"caeoo, wag
study.
the study.
method
was selected
durlng the
eelected during
method
tcmparature
le aa temperature
The btologtcal
biological degradation
material is
of organic
organlc matcaltl
degradatlon of
Ttre
to mathematically
Dathemattcally
bcen done
done to
haa been
great deal of
of work has
proceec. A
A great
dependent process.
dependent
formracocptedforinuemonly accepted
most commonly
Ttre most
dependency. The
evaluate
thta temperature
tenperaturo dependency.
eviluate this
ghorrn below:
belor:
lation
Ls shown
latlon is
-2L-21(T1
tk1/k2
r/ttr.o(T1
zl
-- T
T2)
where:
where:
' reaction rate
tt
reta at
kl """"tr'on
at
reaction rate
rrtc at
k2 . reactl.on
k2
T1
tenPcrature Ti
temperature
T2
t€mPGreture T2
temperature
coefftctent
temPerature coefficient
e -r temperature
9
by Arrhentus
Atrhenlur
developed by
retrtlonahtp -developed
of the
thc relationship
verrlon of
rlnpllfled
ta aa simplified
This
version
Ttrte is
In these
therc
In
tcmperaturG.
end
and
temperature.
a chenrlcel
sf a
which
chemical reactl.on
reaction
valoclty of
relatcr velocity
whtch relates
equrtl'on'
thlr equation.
uelng this
evaluatcd using
studies
was evaluated
rtudtca 90 waa
tost
B'O.D. test
TAc B.O.D.
l{aterlela -- The
lc Materials
l n OOrganic
of Reduction
Reduct
Direct Measurement of
in
a
present
ln
degradable
material
present
in
a
le nCterfal
measures the amount of
of btologlcatly
biologically degr
ffit
dlrect
glve
r
which
give
a
direct
however, whlch
arc available,
avallable, however,
methods are
other nethoda
system. Other
organlcr present.
the organica
of
"irt"r.
of the
all,
Present'
or
of
eorne,
amount
evaluation
of
the
amount
of
some,
or
all,
of
the
evaluatton
content
organlc content
measurement
of
organic
of,
m€asurement
dtrect
icr
nethodt
of
theae
3rro
Initially,
two
of
these
methods
far
direct
Inlttally,
(C'O'D')1
test
Demandtest (C.O.D.),
Oxygen Demand
Chemlcat Oxygen
These vere
ware the Chemical
conaldcred. Ttreee
ware considered.
were
tect.
Pearl-Bengon test.
the Pearl-Benson
and
and the
an
tn an
organlcs in
the organics
of the
oxldatlon of
chemlcal oxidation
tnvolvea chemical
test involves
The G.O.D.
C.O.D. test
Tlre
frm
tnterference from
to interference
aubJcct to
fu subject
The
test is
Ttre test
eolutton.
acid-dichromate solution.
actd-dtchromate
ugc
the use
the
prohlbtted
paat,
thte
In
the
past,
this
prohibited
In
the
oxldlzed.
algo oxidized.
chlorides which
ictr are also
;hi;"i;;;-rt
howevcrr -nodifl'caRecently,
modificaRccently, however,
colutlons.
chlorlde solutions.
hlgh chloride
ln high
of
method in
thls method
of this
other
and
water
in
sea
water
and
other
use
tn
for
propoaed
bean proposed for use
tions
of the
method have been
the nethod
tlonr of
a great
study,
a
atudy'
phaac
of
thts
Sreat
priltuLnary
In
preliminary
phase
of
this
a
In
high
chloride solutions.
ilit-"tiorfie
tn
meehod
attempting
to
use
use
this
thl'a
method
in
"of"tions.
to
attenptlng
ln
spent in
deal of
of time
was spent
effort wes
and effort
tlne and
deal
the
the
of
meaaurlng
mcthod
Since
other
method
of
measuring
no
other
8ucce88' Slnce
sea
water rlthout
without success.
see wetor
rtudy
of the
the study
portton of
thle portion
aval.lable, this
readLly available,
fractl.on wae
soluble
was readily
earbon fraction
eoluble carbon
be abandoned.
abandoned.
had to
to be
had
followfor follownethod for
the method
ao the
(P.B.I) was
wae selected
eelected as
The
Indax (P.B.I)
Pearl-Beneon Index
Ttre Pearl-Benson
at
the
developedThis
test,
developed
at
the
tegt,
Ttrls
degradatlon.
llgnln degradation.
the lignth
of the
ing the course of
Lng
the
designed
to
indicate
the
presence
lndlcate
to
Pretencc
ortg1nally deatgned
University of
of llashlngton,
Washington, tae
was originally
Unlverelty
cpraed
eince spread
have since
uges heve
Its uses
eetuarln" tat""s.
in estuarine
ltquor in
of sulfite
waters. Its
eulflte waste liquor
of
Lr
test
is
thla
Northrect'
In
the
Northwest,
this
test
w88te8' In
kreft wastes.
of kraft
to
detectlon of
lnclude detection
to include
of
indicator
of
pollution,
lndicator
Pollutton'
used quite
control agenciac
agencies as-an
as an
qul.te frequently
frequently by control
ured
B'O'I)'
P.B'I' 1 B.O.D.
betreen P.B.I.,
the relatl'on
relation between
on
avatlablc
1g
yet
no
information
is
available
on
y"t
oo
tnfornaiton
'and
celeeted.
waa
selected.
nethod was
thls method
For this
reaaon, this
thle reason,
toxtclty.
and toxicity.
to
uaed to
The third nrethod
method used
ltues?l --.The_thlrd
BaI Mussel
the- Bay
to the
Reduction
ln Toxicity
Toxlcltv to
Reductlon in
change
the
ls
in
marine
waters
is
the
change
ttaters
evaluate
of kraft wastess ln marlne
ae
tne degradation
evaluate the
greet
a
toxicity
indicated,
a
great
lndlcated-,
dtacugal'on on
As the
on toxiclty
ttre earlier
earller discussion
ei
in toxicity.
toxtclty.
[n
lt
mekcg
This
makes
it
Thla
test8.
toxlclty tests.
ueed in
ln toxicity
been used
have been
variety
of animals
antnale have
vartety of
a
la
There
is
a
Ihere
tegts.
betrreen tests.
the resulta
results between
compare the
to compare
very difficult
to
Aitflcult
anfnal
teat animal
the test
toxicity
for
which the
whlch
for
of
toxlelty
tect
unlforn
a
definite
need
for
a
uniform
test
of
for
defl.nlte need
oregon
rt Oregon
Wildlife
at
tiltldltfe
and
Flsherles and
of Fisheries
D,eparrmenrof
The Department
is
readily available. The
i"-i.iirri-ivarlauto.
I'n
uee
for
test
of developing
ruch a test for use in
developlng such
ptocasg of
the process
ln the
State University
lc in
untverolty 'ft"is
ststc
bay
nucael
the
comeon
bay
mussel
ie tha co'mon
tegt is
thla test
ln this
oriantan in
i""t organism
waterso The test
marine waters.
marlnc
bloessay
work
thle bioassay
uaed this
work used
thlr
for
t€sts
All
toxicity
tests
for
this
tixlctty
tll
l.i.
(Mytilue
iUyUf"" edulis L.).
peraonncl.
FleherLee personnel.
by Fisheries
out by
method
were carried out
ffiarrlcdand"a"ffr
-22-22- Ttre
test objectiveo
the test
Experimental Dcglgn
Design The eveluatton
evaluation of
of the
objectives was
was carrled
carried
Experlurcntal
encountered
in an
out
f f i r eunder
P r e E econditions
n t a t 1 v e o f wrepresentative
h a t n 1 g h t b e e nof
c o uwhat
n t e r might
e d 1 n gbe
n
saste
coocentratLong
cnd'threc
eallnttea,
Two
temperatures,
two
salinites,
and
three
waste
concentrations
&ro tcoparatur€a, tno
eaturry.
estuary.
raete concentraconcentraand waste
aellnlty and
of salinity
sere used.
uacd. Six
Slx different
dtfferent combinations
co,nbtnatlona of
were
run in
Ln
wer
comblnatl.on
each combination was run
and each
tegt runs
rune and
all of
of the
the test
tion
were used
uged in
ln all
tlon rrre
eccll'uated
be
10
ul
was erbttrtrlly
arbitrarily choeen
chosen to
to be 10 ml acclimated
lcvel rar
dupllcate.
the seeding
accdlng level
duplicate. The
proto prostl.rred to
The test
were stirred
rolutlonr wGrc
Ttre
test solutions
rolutton.
of test
aaed/l,ttcr
test solution.
seed/liter of
glver
gurfsc€
tha
Table
Teblc 4 gives the
prevcnt settling.
aettllng.
and prevent
rGrcratlon and
vide surface reaeration
vlde
tertg.
organl,zrtlon of
of the
the teats.
detailed
detellcd organization
TABLE44
TABLE
Gondltlonr
Test Conditions
Serlcr
Series
Test #
TQlrt
2
, 3 6&4&
2,3
1 , 1laa
1,
2 , 2a
2t
2,
3,
3,
4
4,,
5,
5,
5,
6,
516
5,6
3a
3a
4e
4a
5e
5a
6a
6a
Ternp.
Temp.
oC
°C
-
2ooc
20°C
tl
r
"
tl
"
"
tl
It
$allnlty
Salinity
ppt
PPt
lfactc
Conc.
Waste Conc.
bY vol.
vol.
%
7 by
25
25
15
15
25
25
t5
15
25
25
15
15
l0
10
tf
'I
7
1
r
N
33
n
U
12oC
tcnperaturc . 12°C
Sauc
Sa
ne cxcept
except temperature
thc verlour
In
various comblnetl.onr
combinations of
of condltl'onr
conditions
teoti, the
s€tting up the tests,
In setting
and 4 rstre
Series 2,
were
2, 3 and
to test
test containers.
contgl.ner3. Serlee
were
were randomly
asalgned to
randmly assigned
daya,
for ebout
17 days.
6 for
tested
period of
of 15
and gerlea
Series 5 and
and 6
about 17
15 days, and
testod over a perlod
Expertmentel
Experimental Procedure
- The
fron
obtatned from
ttudy was
for this
thle study
The eaote
Source
Waste waste for
was obtained
of llastc
Source and
and Sampling
$arnpllng of
ls
a
This
is
a
Ttrle
Corporatl'on.
Weatern
Kraft
the Western ICraft Corporation.
the Albany, Oregon, mill of the
a prevloue
la a
glnllar in
deacrl.bed in
thet described
to that
kraft nlll
mill very
very similar
previous
operatl.on to
ln operation
kraft
proend pronetcrtale
at
rarr
flr
The
mill
uses
chips
of
Douglas
fir
as
raw
materials
and
Ttre nlll uscr chl.pa of Douglao
section.
aectlon.
llnarbolrd.
end
kraft
of kraft paper
duces
430 tons/day
tona/day of
duces approximately
approxlnately 430
PePer and linerboard.
uaual
Ttre usual
4oC. The
tt 6°C.
and refrigerated
rcfrlgcrated
Composite
at
wera taken
taken and
eamplec were
GoupocLte samples
3.6
ePProxlnately
the eaopllng
sampling perlod
period wag
was 15 hours
hours and the
sampling rate
rate approximately 3.6
raryltng
tha
srncollact
to
prsp
used
was used to collect the sampoaittve displacement
dlaplaeement pump ras
A positive
lttire/fiour,
liters/hour.
of
of
gono
strength
the
relatfve
of the relative strength
tndlcetl.on of
In
obtain some indication
plca.
order to
to obteln
In order
ples.
determined.
pll of
the raw
waste, the
of all
all canplet
samples were
were determined.
end p11
C.O.D. and
the C.O.D.
rar wa8tG,
urtng
dctetrl'ncd using
rras determined
Denand was
Orygan Demand
Analytical
Analytlcal Methods
llethode -- The
lhc Chemical
Ghemlcal Oxygen
gdttlon
thc
for
Methode
the method described in
in the
the llth
11th Edition of
of standard
Standard Methods for the
ffid
(1960).
lulfetc
Ttre silver
ellvcr sulfate
lfastowater (1960). The
Examination of
Water and
tnd Wastewater
of lfater
Exanrlnetton
flltercd
were filtered
A11 samples
eanplet were
determlnatlona. All
for these
theac determinations.
catalyst war
was added
added for
catalyct
prlor to
to dilution.
dllutl.on.
glass wool prior
through glase
-23-23Converalonr
hydronetetra. Conversions
wlth hydrometers.
rere made
nede with
All salinity
deterntnatl.onr were
A11
callnlty determinations
tables
reductton
denslty
by
uec
of
density to
were nada
made by use of density reduction tableg
to salinity
ealtnl.ty werc
from denelty
neerert
the
to
Ta3
uelsurcd
was meisured to the nearest
(zerbe and
Ths salinity
rrllnlty
and Taylor,
1953). The
taylor, 1953).
(Zerbe
ppt.
0 . 1 ppt.
0.1
rnadc
werc made
B.O.D. test
tcst were
for the
the B.0.D.
The dissolved
measurements for
dlcrolved oxygen
oxygcn msaurements
ttrc
ln
outll'ncd
ae outlined in
}lethod as
Winkler Method
thc Winkler
using
of the
t{odlflcetlon of
thc Alsterberg
Alcterberg Modification
uslng the
tcstl consisted
conelgtcd
f,or the
the teats
The dilution
(1060). Tte
dllutlon water for
Standard l{achodr
Standard
Methods (1960).
No
wetGr. llo
wlth fresh
frcah water.
ppt salinity
ppt and
eallnLty with
and 25
25 ppt
of sea
water diluted
15 ppt
dlluted to
to 15
of,
seq 1r€tcr
sceded.
r'as not
not seeded.
weter was
dltutlon water
lhe dilution
supplemental
iaaea and
ana the
wera- added
nutrlents were
rupplenental nutrients
bared upon
uPon the
thc
were based
the calculations
calculatlona were
ueed in
tn the
The blank
Utank corrections
correctlona used
ftiwetsr.
ln the
the sea
aea water.
organisms
already present in
organlcma already
flnsl rata
For each
condition, the
thc final
rate obtelned
obtained lc
is bsced
based upon
upon dete
data
each test
test cond{t!.on,
all.oryable
strongest
were
the
uaed
The
dilutions
used
were
the
strongest
allowable
dllutl,one
dtlutlon.
Ttre
one
from one dilution.
folloring
The
bottles.
the following
oxygen in
ln the
the bottles.
consistent
wlth the
ths available
avatlable oxygen
conclstant with
percent
wattG
ten
l4
for
the
ten
percent
waste
for
the
114
be
eatlafactoryr
found to
to be satisfactory:
dilutions were
were found
dllut1ons
three
and
1:1'for
eatte;
concentration;
1:3
for
seven
percent
waste;
and
1:1
for
three
percent
Percent
concentratlonl 1t3 for s€ven Percent
wa3te.
waste.
llgnlnr
of lignins
concentratlon of
the concentration
for estimating
ectlmat{ng the
The Pearl-Beneon
Pearl-Benson nethod
method for
Tfre
phenollc
type
are
derlvetlvea
and its
lts derivatives are phenolic type
llgnln and
is
based on the fact
fact that
that lignin
Lg based
eolutlon
acldlc
ln
aitrlte
groupa
wl.th
reEct with nitrite in acidic solution
phenollc groups react
Ttrese phenolic
substances.
subatances. These
a raore
alkaltae, a
nade alkaline,
When this
more htghly
highly
t{hen
1g made
thlc is
derlvatlve.
nitrooo derivative.
forn ae nitroso
to
to form
reprels reprecolor
thls
In
dilute
solution,
this
color
is
formed. In dllute eolutton,
l,s formed.
derLvatlve is
colored derivative
colored
proeedurc
preeent.
The
Ttre procedure
derlvatlver present.
llgnln derivatives
of lignin
amount of
sentative
of the
the amount
lcntetlve of
used
(1963).
Bioassays
used
Btoaaeaya
by Barnes,
Bernos, $
followed wes
was that
recommended by
et al.
thet recormrended
foLlowed
9!. (1963).
ln
eooperatlng in
by biologists
biologlctc cooperating
perforued by
were performed
phace of
work were
of the
the work
in
th[e phase
ln this
report.
thla
ln this report.
preeented earlier
earller in
upon material
the proJect
project and
and are based
based upon
material presented
the
contaLnere
of square
square containers
cone{eted of
thta work
The apparatua
apparatus used
used in
work consisted
ln this
Tfre
and
cguare and
were 18
18 inches
tnches square
top. They
Ttrey were
at the
the top.
ptlifgUee
and open
oPen at
made
and
of plexiglass
made of
lttere
the 55
55 liters
whea the
that when
The dimensions
Bo that
choaan so
dlnenelona were chosen
aeep. The
one
one foot
foot deep.
retio
volume ratio
to volume
aree to
place, the
the surface
aurface area
wera in
of
tn place,
solutton were
of test
teat solution
nlxLng
the mixing
were provided
provtded to
to enhance
cnhence the
Baffleg were
e minimum.
nlntnum. Baffles
approached a
approached
characterlstlce.
characteristics.
mechanLan.
mechanism.
the stirriág
stlrrlig
contalnera wae
part of
test containers
An
was the
of the
thc test
An integral
lntegral part
were
operatad
operated
sttrrera
all
uaed
wea
and
For
simplicity,
a
rope
drive
was
used
and
all
stirrers
were
e roPe drlve
For alnpltclty,
on
retre oounted
The stirring
mounted on
ahafts were
ct[rrlng shafts
polter source.
source. he
ltngtc power
from a single
get.
Ttre
The
bean
had
bearlnga
thc
aluminum
channel
sections
into
which
the
bearings
had
been
set.
whlch
alumlnum ctrannet aectlona lnto
reducer,
apeed
varlable
a
motor,
drive
consisted of
of an eleetrle
electric motor, a variable speed
drive train
traln consl.gted
the
placed in
ln the
pulley was
waa placed
A floating
gear drive.
A
floatlng pulley
drlve.
and a right-angle
rlght-angle gear
and
adequate
and
maintain
adequate
malnteln
and
belt
of the
tha belt
uP any
any elongation
system
elongatlon of
to take
takg up
system to
tenslon.
tension,
corrin
ln aa conlmrsed
nerc immersed
contalners were
teet containers
the test
To
tenperature the
control temperature
To control
neceagltatcd
Gontainera
test
of the test containers necessitated
The size
slze of
beth. Ttre
rit"r bath.
stant temperature water
stent
rraa 12
12
bath was
the bath
The
main tank
of the
tank of
fha maln
unit.
large unit.
of ae rather
rather large
construction
construction of
at
provided
punp
wae
A
pump
was
provided
at
A
daep.
foot deep.
one foot
and one
feet wlde,
feet
wide, and
four feet
feet long,
long, four
wet
The
temperature was
Ttre temperature
reclrculcted.
one
water sas.conatantly
was constantly recirculated.
and the
the water
one end
end and
water.
water.
taP
colder
lntroductl.on of
level by introduction
maintained at
of colder tap
deelred level
at the
the desired
natntalned
trtrlch
teuperature controllcr
This waa
was controlled
controlled by a ges
gas erpanelon
expansion temperature
controller which
Ttrls
tt wae
lftth
systemr
With
this
system,
it
was
thtg
water inlet.
t'nlet.
the water
on the
actuated
valve on
colenol.d valve
ectuated a solehoid
level.
level.
deslred
of
the
possible to
maintain temperatures
within + O.toC
0.1°C of the desired
posalble
teqeretures wlthln
to nalntsln
--2424- Data was
Test Rcrulta
Results was obtel.ned
obtained from
three test
test runs
runs et
at 20oC
20°C and trro
two
frm three
Tect
wcre
tenpcrature were
at each
each temperature
tests
fron all
tcsts at
runs at l2OC. The
Tte data
deta from
all similar
rtntlrr
EffiTXf€.
In
the results
reaultr
to compare
compare the
plottlng and
In order
order to
superimposed
for plotting
and analysis.
analyala.
rupcrlnpoged for
la terms
teros
1r reported
reported in
from
various test
degradation is
the vartoua
the.degradatton
fron the
condtttona, the
test conditions,
uclng
Fitting of
was done
done using
of the data wae
of
percent Initial
B.O.lr. Consumed.
Consumod, Pltttng
of pcrcent
Inltl.al B.O.D.
(f960).
temperature coefficient
coefflcfent
the
method propoced
proposed by
by Trtvoglou
Tsivolou (1960).
The
The temperature
the nethod
(Tj '- Til,
T2), rhlch
which estimates
varlatlon
the variation
O
0 for
thc equation
€stlmates the
for the
equatton k1/k2 r Q(T1
for
Taa
cmputed
B.O.D.
of
the
E.O.D.
rate
constant
with
temperature,
was
computed
for each
wlth
of tha
temperature,
rate consttnt
for this
thls
and
analyzed
In
total
12
curves
were
developed
and
analyzed
for
were
developed
test
condltl,on. In total 12 cuwea
test condition.
gtve
rePreoentatlv€
Figures
10
through
13
give
representative
portlon
13
portion of
of the
the research,
reeearch. Flgurcs 10 through
ppt respectively.
reepectlvely.
and 15
results at
end salinities
of 25
25 and
15 ppt
et 20°C
20oC and
and 12°C
eallnlttea of
regulte
t2oC and
glver the
obtalnsd
rate constants
constantr obtained
Rate
rate
Rate Constants
Conatanta -- Table
thc first-order
flrat-ord€r
Tablc 35 gives
from
various combinations
of test
varl.ables.
frm the
the varloue
conblnatlona of
tcst variables.
TABLE
TABLE55
First-Order
Firrt-Order Rate
Rate Constants
Conrttntr
Temp.
Tenp.
oC
°C
Waste
lfagte Conc.
conc.
vol.
1 by vol.
la
la
2a
2a
3a
3a
4a
4t
5*e
5
6a
6a
20°C
200c
10
l0
10
l0
1,
1 , 1*
1r
2,
2 , 2a
2a
3,
3*r
3, 3
12°C
12oc
Series
Serlcc
Tests
Teatg
2,
2 1 33,
r& &
4
4
1,
1,
2,
2,
3,
3,
4,
4,
5,,
5
6,
6,
5
5 &&66
4,4a
4,
4a
5,
5 , 5*
5a
6,
6, 6*
6a
tl
"
tl
"
tl
"
ff
"
tf
ll
"
tl
It
tl
"
it
"
Salinity
Sal.tnlty
ppt
Ppt
7
7
7
7
3
3
3
3
10
10
10
10
7
7
7
7
3
3
3
3
k
k1
1
25
25
15
t5
25
25
15
15
25
25
15
15
0.114
0.114
0.094
0.094
0.126
0.126
0.125
0,125
0.210
0.210
0.173
0.173
25
25
15
15
25
25
15
l5
25
25
l5
15
0.034
0.034
0.036
0.036
0.039
0.039
0.043
0.043
0.076
0.076
0.092
0,092
- Trble
the temperature
tempcreturG coeffl.clenta
Temperature
Coefficients Table 6 gtvee
gives the
coefficients
Temperature Coefflclente
of
teat
condittonl.
computed
for
the
six
combinations
of
test
conditions.
conputed for the alx conblnetl.ons
TABLE 6
5
IABLE
Temperature Gocf
Coefficients
fl.clcntr
Terycrrturc
Tests
Teatr
1,
1,
2,,
2
3,,
3
4,
4,
5,,
5
6,
6,
1*
la
2*
2e
3*
3e
4*
4t
3aa
5
6*
6r
ppt
Salinity,
3a11nlty. ppt
25
25
15
l5
25
25
15
15
25
25
15
15
Waste Conc.,
vol.
l{aeta
Concr, 7.
Z by vol.
10
10
10
10
7
7
7
7
3
3
3
3
-!@Temp. Coeff. 0
1.163
1
.163
1.127
L.L27
1.158
1
.158
1.143
1
.143
1.135
1
.135
1.082
082
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Pearl-Benson
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Pearl-Benson Indax
1dex data
Peerl-Bencon Tegta
all
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The
data
for
all
similar
6
et 12°C.
and 6 at
l2oc. Tlre
serler 55 and
3
m and 4 at 20°C and Series
Detat
Data,
for plotting.
rar.
rupert4oged for
tests
at cech
each temperature
were superimposed
tcrycrrturc
te3t, et
Plotttng.
Ftgurce
{n
erc shown
ahownin Figures
plotted as
pcrcont Initial
P.B.I. Consumed,
Contuned, are
plotted
tr percent
Inltlel P.B.I.
14, 15,
15, 16
16 and
eld 17.
17.
14,
- Bioassay
for all
ell experimental
experlncntrl
narc conducted
DLoarery tests
testf were
conductcd for
Toxicity tcrte
Tests Toxtcltv
thc results
rceulta
betwc€n test
ta.t runs,
runst the
ln the
tho data
deta between
varl.rtlonr in
iEilec.--Ee
to the
the variations
series. Due to
of
everage of
the average
lftthln each
run, the
Within
preaented separately.
crch run,
reperrtely,
of each
run are
ere presented
of
crch run
thc
of the
purposeer The
plottlng purposes.
ltc results
rcrulta of
ueed for
for plotting
tro duplicates
dupllcatee is
lr used
the
the two
ere
concentrltlonl
reven p€rcent
tests urlng
using tGn
ten pcrc€nt
percent and
and seven
percent waetc
waste concentrations
are
te3t!
plot of
of the
thc TI,5,
TI5, expresred
shown
expressed at
as ra Peroent.Sc
percentage of,
of kraft
kraft rsstet
waste,
ea aa plot
ehorm as
percent waste
conwast€ conurlng the
the three
threc percent
dayr. For the
thc tests
tlnc in
tcrtr using
ln days.
versus time
peroentegc of
notnal larvae
lanae
of normal
plotted as
as the
the percentage
centration, the
rcaultr are
rr€ plotted
ccntrltlon,
thc results
of these
theae
The results
resul,tr of
undl.luted sample.
aarlplc. Tlre
tert using
uelng the
the undiluted
counted in
ln a test
tabul8tlon
A complete
2!. A
conplete tabulation
through 22.
ln Figures
16 through
bloaeeay
arc shown
Ftgures 16
bioassay tests
teata are
rhmn in
B.
Appendlx B.
bc found
ln Appendix
found in
bloaeeay test
tcat can
can be
of the
the bioassay
of
of, the
the results
rcaults of
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u
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'37-37- Baeed
been
had been
by others,
t't had
others, it
done by
of worlr
analyolc of
Based upon
upon analysis
work done
Discussion
Qlqcuqg:Lo_q
Ttre
The
neture.
be of
two-comPonentnature,
of aI two-component
would be
anticipated that
the curves
cunrea would
ii,EGffid
that the
rate
and the
the slower
slffier rate
fracttOn and
to the sugar fraction
fastest
rate muld
would pertstn
pertain to
faetect rate
flrct-ordcr
thet aa first-order
chow, however, that
The
cunree show,
llgnln fraction.
f,ractlon.
Ttre curves
to the
the lignin
to
degradetl.on
that lignin
llgn{n degradation
glvee the
data indicating
bcat fit
lndtcettng that
flt of
of the
tha data
the best
curve
cunre gives
thc
curr/€r
did
the
of
not
effect
ehape
did not effect the shape of the curve.
perlod exists.
Ttrtr
This
exlsta.
no lag
lag period
lndlceta no
20oC teats
for the
the 200C
terte indicate
Ttre curves
curvec for
The
the
In
In
the
lag.
a
evol.d
to
wag
choeen
level
seedlng level was chosen to avoid a lag.
was expected since
raa
the seeding
alnce the
tetts
of
of
the
the
tests
perlod
for
eone
oecurred
lag
the 12°C
12oC runs,
run8, aa small
case
caee of
of the
anall lag period occurred for some
It is
not knonn
known whether
whether
ts not
eame. It
the same.
aeedlng level
level remained
remal.ned the
the seeding
even though the
Gven
8ona
or
organiamr
populatlon of
of seed
seed organisms or some
decresae in
ln the
the population
this
due to
to a decrease
thie is
lg due
factor.
other
other factor.
descendlng
ln descending
obcerved arranged
ananged in
rate constants
conrtantc observed
ahows the
the rate
Table 7 shows
order of
of magnitude.
uagnltude.
order
TABLE77
TABLE
Rate Constants
Conrtents
of, Rate
Rearrangenent
Rearrangement of
Temp.
og
°C
Waste Conc.
3
3
3
3
7
7
Serlea
Series
Teetc
Tests
2r3r&
4
4
5
5,,
6
6.,
3,
3,
4,
4,
1,
1,
2
2,,
5
5aa
6a
6a
3a
3a
4a
4a
Ia
1a
2a
2a
2ooc
20°C
6,
6,
6a
6a
5aa
5
4t
4a
3a
3a
2a
2a
la
1a
12°C
120C
5 &&6 6
5
5,,
4,
4,
3
3,,
2,
2,
I,
1,
tt
"
ll
tf
"
tt
"
It
"
tl
"
ll
It
"
t,
"
It
"
by vol.
vol.
Z. by
7
7
10
10
L0
10
3
3
3
3
7
7
7
7
10
10
10
10
lnlty
Salinity
ppt
PPt
k1
25
25
15
15
25
25
15
15
25
25
15
15
0.210
0.210
0.173
0
.173
0.126
0.126
0.125
0.125
0.114
0.114
0.094
0.094
15
15
25
25
15
15
25
25
0.092
0.092
0.076
0,076
0.043
0.043
0.039
0.039
0.036
0.036
0.034
0.034
15
15
25
25
alonet
tteote concentration
coneentretl.on alone,
to waste
reepect to
Considering this
with respect
this sequence with
Conglder[ng
to the
the
corresponde to
constent corresponds
rate constant
largest rate
20oC the
the largest
it
can be seen
at 20°C
that at
aeen that
tt cen
one
One
noted.
trend is
is noted.
At
aarne trend
the same
At 12°C,
12oC, the
rast€ concentration.
concentration.
weakest
weakeat waste
or toxic
toxlc
be inhibitory
tnhlbltory
may be
there may
possible
for
or
that there
thle is
ls that
poaatble explanation
for this
explanatlon
Slnce an
Since
action.
bacterlel
the bacterial
retard the
substances
waste wtrtch
which retard
action.
the wa8t€
ln the
lubctanceg in
of
acclimated
seed
was uged
used to
to Lnnoculate
innoculate the
the test
test contaLnera,
containers, an
an effcct
effect of
aeed waa
acclloated
the
ln the
lndlcated in
trenda indicated
Due
the trends
Ihe to
to the
bc expected.
not be
expected.
would not
this
thls type
type would
be considered.
cons{dered.
poeelblllty
uuat be
data,
must
horever, this
thla possibility
data, however,
Table
ln tablc
Rate Congtents
Constants as
Function of
of Saltnlty
Salinity -- If
If the
the rate
rate cotrBtaotB
constants in
aa a FunctLon
Rate
pl'cture is
is
picture
dlfferent
alone, aa different
-ttntty
7 are examined with respect to salinity
alone,
fastet rate
rate
the faster
20oC, the
al 20°C,
concertritlon
For a glven
given weate
waste concentration
at
preccnted.
presented. Fotr
horever,
The
three
highest
rates,
ratett
however,
hlghaot
three
Ttre
callnlty.
the
hlghcr
corresponds
to
the
higher
salinity.
to
cotr""poods
ppt salinity.
sallnlty.
25 ppt
havlng 25
teet conditions
condltlone
threc test
do not,
not correrpond
correspond to
having
to the
tha three
-38-38rate
the fastest
fsstctt rate
Here the
be true.
to be
tru€. Here
aPP€ars to
the reverse
At 12°C
rev€rse appears
12oC just
Juat the
sall'nlty.
the lower
lower salinity.
to the
for a glven
given concontratlon
concentration correepondc
corresponds to
for
on the
thc
be explained
nlght be
explatned on
20oC runs
for the
rune might
The
lndlcated for
tha 20°C
trend indicated
Ttrc trend
erplanatl'on
This
explanation
watet.
TtrLo
Ln
the
sea
the
nutrL€nt
concenttatLon
baaLs
of
basis of
nutrient concentration in the sea water.
Ihe
rune. The
the 12°C
12oGruns.
from the
recults from
for the
the results
would not
hold, however, for
not hold,
belor.
dlscucsed
are
pooatble effects
nutrl.ent
of
changes
possible
of
nutrient
changes
are
discussed
below.
effects
Rate
Constants as 8
a functlon
Function of
of Nutrfe
Nutrient Concentration -- Ttre
The flret
first polnt
point
Rate Constsqqe
ln
changea
ffect
of
to be considered with respect to nutrients is the effect of changes in
of
to
variety
Due
to
a
variety
of
Dle
between test
tect series.
aerlee.
the
nutrient corcentratton
concentration between
the nutrl€nt
nae
nutrl.ant concentrations
eoneentretLone was
on the
the nutrient
reasons, quantltatlve
quantitative information
Lnformatl,on on
reasons,
be
can be
the
sampLes
betreen the samples can
However, relative
dlfferences between
relatLve differences
llorever,
not
obtalnad.
not obtained.
estlmated.
estimated.
phenmenon caused
cauaed
upwel.llng phenomenon
tha upwelling
of this
thla work the
During
Durlng the course of
!illth respect
raepect
coneentretl.on. With
nutrtent concentration.
Ln nutrient
relatively large
fluctuatlons in
large fluctuations
relattvely
up
-Pr freshly
contaln up
may contain
Oregon coast
coast may
off the
the Oregon
water off
upnelled lrater
freshly upwelled
to PO4
to
PO4 - -P,
the
I'n the
An average
probably be
be in
pg-atorns/l. An
average concentration
concentratlon would probably
to 3.0
3.ti jig-atoms/i.
to
-1t. In
the concentraconcentratn aurfece
surface ttetetrsr
waters, the
pg-atoms/l of
PO4-r -P.
range of
of 1.5-2.0
1.5-2.0 jig-atoms/I
of PO4
renge
go to
zero.
to essentially
tlon may
aeeentlalty zero.
tion
may go
(hegon State
provtded
State University
Unlversity provided
et Oregon
The
Departrrent at
Oceanography Department
The Oceanography
upwelltrtrlch
per{od
for
durlng
the
experlmental
datee
information
on
the
dates
during
the
experimental
period
for
which
upwellon
the
tnforsratlon
Ln
Sertea
used
water
sea
The
data
indicated
that
that
the
the
sea
water
used
in
Series
The
lndlcated
Lng waa
obsenred.
ing
was observed.
for
that for
and that
was marginal,
narginal, and
Serlee 3 was
water for
for Series
the water
upcelled water,
2 wae
was upvelled
water, the
20oC
runa
for
the
This
shows
that
for
the
20°C
runs
that
flater.
sholtg
and 66 rae
aurfaee water. Ttle
Serles 4,
Series
4, 5 and
was surface
for
cutrrea for
rtre curves
poselble PO4
encountered' The
-P was
was encountered.
Po4 r -P
of the
the possible
a wlde
wide range of
have
llttle
spparently
rnagnltuda
of this
thls magnitude apparently have little
these tests
tests indicate
changes of
that changdg
lnd[cate that
these
rate.
the degradation
degradatlon rate.
on the
effect on
effect
,
{n concenconcenchange in
tha change
ls the
be considered
The
polnt which
whtch should
coneidered is
should be
Ttre other
other point
of aa
the
effect
To
properly
evaluate
the
effect
of
properly
evaluate
glven test
test run.
run. To
tration wlthln
within a
a given
tretlon
relattve
be
examlned
change
nutrient content,
content, this
change nust
must
examined relative to
to the
the
thle change
change in
Ln nutrlent
by
connputing
le
done
Normally
this
is
done
by
computing
preaent.
Nornally thta
of organic
organtc material
materlal present.
amount
amount of
lnformatlon
nutrient information
quantLtatlve nutrient
Since
Stnce no quantitative
nutrlent ratios.
B.O.D.
B.O.D. to
ratlos.
to nutrient
an
coalPutean
In
order
to
compute
order
to
In
were established.
retlos were
establtshed.
was obtained,
was
arbl.trary ratios
obtal.ned, arbitrary
contained
contelned
sasta
and waste
fresh water
weter and
the fresh
arbitrary
that the
was assumed
aeeumedthat
Lt was
arbltrary ratio,
railo, it
any test
tert
of any
concentratlon of
nutrlent concentration
the nutrient
Tlrerefore, the
materl.al. Therefore,
nutrlent material.
no nutrient
no
waa
aalLnlty was
teet salinity
the test
and the
the salinity
aallnlty and
in
given run was
was proportlonal
proportional to
to the
ln a gtven
concentre'
$gste concentrathe waste
B.O.D. term
telm the
For the
the B.O.D.
the ratio.
ratio.
ueed for
for one
one term
term in
tn the
used
wa8te coneonproport{onal to
the waste
to the
B.O.D. is
tion
was used
used since
B.O.D.
Le proportional
the initial
lnltlal
tton was
al.nce the
ratiog
B.O.D./nutrlentr ratios
B.O.D./eallnltyr or B.0.D./nutrient,
arbltrary B.O.D./salinity
The
Ttre arbitrary
centratlon.
centration.
for the
the
eallnlty for
were computed
dlvldlng the
tho waste concentretlon
concentration by
by the salinity
lr€re
co6puted by dividing
wlth the
the
8, along
al'ong wtth
The resulta
results are shown
ln Table 8,
ehown in
test conditions.
condl.tl.ons. Ttre
six test
cl.x
corresponding rate constants.
GomputatLona
proposed is
100t1. Computations
ls 100:1.
cmonly proposed
An optimum
ratlo commonly
B.O.D./P ratio
An
optlmum B.0.D./P
8ea weter
indicate that
water
lf sea
that if
tegt conditions
condltlons tndlcate
various test
baeta for
fsr the
the various
on this
thls basis
of
deflof
defidegree
htgh
a
lo
there
is
considered
the
only
nutrient
source
there
is
a
high
degree
source
nutrlent
only
the
ls conetdered
This leads
possibility that
that degradatlon
degradation rate
rate nlght
might be
be
to the
the pocstblll.ty
leade to
c1ency.
ciency. Ttrls
8
of
lable
ratlo.
An
rxanlnrtlon
An
examination
of
Table
8
of
!.o.D./saltntty
a function
of
the
the
B.O.D./salinity
ratio.
functlon
2OoC
the 20°C
for the
true for
ls true
thLg is
qualltattve
sen8e, this
shows
sense,
ln a qualitative
at least
leaet in
thet, at
ahowo that,
lndleates ea hlgher
The hlgher
higher B.O.D./oaltntty
B.0.D./salinity ratlo
ratio indicates
higher nutrl'ent
nutriegt
testg.
tests. Ttre
glorrer
tt
At 12
C,
12oq
raie".
the
to
deficiency
and
these
values
correspond
to
the
slower
rates.
valueg
defl.ciency and theae
-39-
pattern here shows
showe
not apparent.
The pattern
however, this
apparent. The
thla relationship
relattonrhlp is
ls not
to the
tha
glven lra8te
faeter rate
rete corresponds
corrssponde to
that
waste concentration,
concentratLon, the
the faster
that for
for a given
more
nore nutrient
nutrlent deficient
def{clent condition.
conditl.on.
TABLE 8
TABLE
Ratloe
Arbitrary
B0.D./Salinity
Arbltrary B.
o.D. /saltntty Ratios
B0D./Salinity
B.o.D.
/saltntty
Serlee
Series
Tests
Teats
2 1 33,
r& &
2,
4
4
5,,
5
6,
5,
3,
3,
4,,
4
1,
1,
2,
2,
5a
5a
6a
6a
3a
3a
4a
la
1a
2a
2a
0.210
0.210
0.173
0.173
0.126
0
.126
0.125
0
.125
0.114
0.114
0.094
0.094
0.120
0.120
0.200
0.200
0.280
0.280
0.462
0.462
0.400
0.400
0.667
o.667
5 &&6 6
6,
6,
5,
5,
4,
4,
3,
t,
2,
2,
1,,
1
6a
6a
5a
5a
4a
3a
3a
2a
2a
Ia
1a
0.092
0.092
0.076
0.076
0.043
0.043
0.039
0.039
0.036
0.036
0.034
0.034
0.200
0.200
0.120
0.120
0.462
a.462
0.280
0.280
0.667
0.667
0.400
0.400
k
nutrl.ent
apparent nutrient
preacnce of
of this
One
possible explanation
thla apparent
for the
the presence
One poeclble
explanatl.on for
the
at
metabol{c rate
rate at the
dependency
loner metabolic
le the
thc lower
and not
nog at
et 12°C
12oC is
at 20°C
zOoCand
dependency at
require
nag requlre a
greater bacterial
bacterLal activity
actlvlty ma
20oC the
the greater
lower
temperature. At 20°C
lorrer temperature.
For
12"C.
at 12
matertal than
than at
proportionally
C.
groater amount
proportlonally greater
of nutrient
nutrient material
stount of
def[nutrlent defils aa nutrient
20oCthere
be that
there is
this
that at
et 20°C
parttculer system,
lt may
nay be
thle particular
system, it
factor
oth€r factor
aad some
sme other
le adequate
adequate and
ciency wtrtle
while at
aupply is
12eC the
the nutrient
nutrlent supply
at 12°C
clency
rate.
controls
the degradation
degradatlon rate.
eontrols the
tempereture
the lower
Loner temperature
at the
It
of the
the rates
ratee at
be noted that
thet four
four of
It should
ahould be
Ln
changee in
poselble that
that slight
altght changes
It is
ls possible
another. It
are very close
cloee to
to one
one another.
of these
these values.
values.
the curve
reerrangedent of
sone rearrangement
of best fit
cau8e some
cunre of
f,lt could cause
be large
enough
rrculd be
large enough
changee would
The author
that the
the changes
feel, however,
howev€r, that
does not
The
author does
not feel,
B.O.D.y'nutrl.ent
and B.O.D./nutrient
between rate
rete and
to
brlng about a very close correlation
cotrelatlon between
to bring
ratio.
ratl.o.
above,
dlscussed above,
Considering
nutrlent effect
effect discussed
of the
the nutrient
the aspects
aspecte of
all the
Gonslderlng all
the
ln
changes
of
it
appears
that
within
the
range
of
values
encountered
changes
in
the
valueg
wlthln
appeara
that
It
rate.
on the
degradatlon rate.
the degradation
nutrient
effect
effect on
have little
ltitle
nutrient concentration
concentratlon have
dtfference between
Temperature
marked difference
between valuee
values of
of
lc a marked
there is
Coefflclents -- There
Temerature Coefficients
0
calculated
from
the
experimental
data
and
those
reported
In
the
literaffiEper{nenta1dataandthogereported1nthe11tera.
er€ in
tn the
the
Most
used for
for domeatlc
domestic eerage
sewage are
values conmionly
cormonly ueed
ture.
of the
the values
ture.
llost of
ln
magnl.tude
(194S)
thls
Gotaas
(1948)
found
values
of
this
magnitude
in
valuea
of
Cotaas
range
1.040
1,060.
rangc 1.0/+0 1,060.
(1963)
Rarpe
(1963)
Earpe
w8ter.
eea
ln
his
study
of
the
degradation
of
sewage
in
sea
water.
of
sewego
hla etudy of the degradatlon
The only
only
welteo. Ttre
rrlth kraft
kraft wastes.
hls study
reported
etudy with
1.06 for
for his
near 1.06
reported aa value near
(1941).
ltloore
of
waa
that
study
reporting
values
as
high
as
those
found
was
that
of
Moore
(1941).
those
found
8t;dy reportlng valuee ae hlgh es
temparature
ln the
the temperature
sewagcin
dmestl.c sewage
He
for domestic
for 00 of
of 1.145
1.145 for
He reported
valuc for
reported aa value
ln this
thls
used
At
the
temperatures
corresponding
to
these
used
in
those
to
0.5 - 5°C.
5oC. At the tenpereturea corr€apondlng
range 0.5
experiment
dropped to
to 1.065.
1.065.
the value dropped
experlment the
-40-40g.
of 9.
glven for
hlgher values of
theae higher
be given
for these
can be
No
explanatlon can
deflnlta explanation
No definite
tha rates
ratea
aneountered, the
the range
range commonly
comronly encountered,
wlthtn the
be within
In
then to
to be
for them
order for
In order
data
The
lhe data
ae fast.
fast.
twl.ce as
be approximately
approxlmatelyi twice
would be
at the
teqersture
et
the 12°C
12oC temperature
be
nay be
good fit.
It may
It
flt.
obtalntng aa good
Ln obtaining
that much
latltude in
does
not allow
much latitude
allop that
doec not
nutrtent
the apparent
apparent nutrient
of the
the effect
effect of
that
tenperature the
et the lower
loser temperature
thst at
expertTtris experirate. This
the.rate.
further reducing
reduclng the
thereby further
deficiency
nagnlfted, thereby
deflcl.ency is
[a magnified,
pertatn
0
of
of
9
pertain
valuee
these
that
prove
conclusLvely
doee
not
ment
certainly
does
not
prove
conclusively
that
these
values
ment certalnly
good
nae
there
and
however,
These
were
computed,
however,
and
there
was
good
lrere
computed,
values
waste.
Thoee
for kraft
kraft waste.
for
to
needed
teats
Further
tests
are
needed
to
teet
r$rroo
Surther
the
varloue
duplication
dupltcetlon from
from the various test runs.
polnt.
thle point.
thoroughly examine
thoroughly
examine this
treea'
dead trees,
llgnln in
ln dead
genarally known
that lignin
known that
Pearl-Benson
Tests -- It
It is
ls generally
Pear!-Beneo!_!qq+.
etc.,
very
fleaves,
figraded
a t a v eis
r y degraded
s 1 o w r a t eat
b y tah e
b a c tslow
e r l ' arate
i n t h eby the bacteria in the
should
degradatlon should
go11. There
that lignin
llgnln degradation
to suspect
susPect that
no reason
reason to
Le no
Ttrere is
soil.
of
decay
The
slow
decay
of
ltre
aquatLc environment.
envLronnent.
an aquatic
rate in
ln an
at aA faster
faster rate
occur at
ts
truet
thls
If
this
is
true,
notlon'
rf
thle notion.
to support
eupport this
ln water
water tends
tends to
wood submerged
wood
aubmergedin
primarl'ly
llgnln
measures primarily lignin
test measures
the Pearl-Benson
Peart-Benson test
aesumedthat
that the
and if
tf it
lt assumed
and
gradual
slow gradual
ehowaa slow
should show
versus time
ttme should
in
pulping wastes,
wastes, data
data for
for P.B.I.
PB.I. versus
ln pulptng
that
lndlcate
theee experiments
Ln these
experlments indicate that
obtai.ned in
Ttre data obtained
Ln P.B.I..
P.B.L.. The
deciease in
decrease
c88€r
th€ case.
such is
1g not
not the
such
daye, 40 -- 50
about two
two days,
after about
that after
shott that
20oC tests
The
for the
the 20°C
teats show
data for
Ttre data
15
12 -- 15
In
followlng 12
the following
In the
wae depleted.
depleted.
P.B.I. was
percent
lnltlal
of the
the initial
percent of
P.B.I.
wag
P.B.I.
of
thE
tnttlal
more
days,
however,
only
about
ten
percent
more
of
the
initial
P.B.I.
was
about
ten
only
howevet,
daye,
Percent
general charactercharacterthe general
data exhibits
portlon of
of the
exhlblts the
the data
latter portion
Ttre latter
coneumed. The
Tfie
The
above.
stated
argunent
of
the
baele
istics
anticipated
the
basis
of
the
argument
stated
above.
on
the
antlclpated
lstlcs
explanatton.
different
explanation.
a
dlff,erent
requtrea
decrease
presence
rapld
Lntttal rapid decrease requires a
presence of
of this
thls initial
meesures
test measures
Pearl-Benson test
the Pearl-Benson
be that
The
most logical
that the
to be
appears to
loglcal answer appears
iLe ro"t
preclpltated
la
that
llgnln
or
somethtng
in
the
waste
other
than
lignin
or
that
lignin
is
precipitated
sonethlng tn ttre lraste other than ltgnl.n
blodegradaBlon.
than biodegradation.
from
waste by
by other
other mechaalame
mechanisms than
fron the
the-waate
consumed0
these
that these
eholtn that
condeneates have shown
Tests conducted
conducted on evaporator
evaporator condensates
Teets
the
fact
despite
P.B.I.
liquids
can exhlbtt
exhibit aa relettvely
relatively h{gh
high apparent
apparent PB.I. despite the fact
llqutda can
thts
thet
thought
It
is
thought
that
this
present.
It ls
derlvatlvee present.
ttgntn derivatives
that
there are no lignin
that there
eondensatec.
the
condensates.
the
found
tn
phenoll.c compounds
compounds found in
apparent P.B.I.
P.BI. is
to phenolic
le due
due to
apparent
overnlght.
to stand
etand overnight.
allowed to
are allowed
the samples are
This
tf the
wl1l disappear
dlsappear if
P.B.I. will
Thls P.B.I.
""rpiu"
volatilization.
phenole through
through volatllization.
of the
the phenols
This loss
to
to loss
lose of
attrlbuted
loag is
ls attributed
Thle
duo
18 due
data is
P.B.I. data
ln the
the P.B.I.
drop observed
obsenred in
It
that
tnltlal
drop
thet the
the initial
ts likely
llkely
It is
possl'other
The
other
possiTtre
atmosphere.
to the
the atmosphere.
non-ltgnln
corrpounds to
of non-lignin
to
compounds
to the
the loss
losg of
whlch
are, some
bilities
are
some non-volatlle
non-volatile compound
compound preaent
present which
that there
there are,
bllltles
are that
or
or
blologlcally
degradable biologically
raadlly degradable
and is
ts readily
exhibits
P.B.I. and
en apparent
apparent P.B.I.
exhlbltg an
other processes
or other
preclpltatlon
Processes
that lignin
is
precipitation
or
adsorptlon,
lg removed
removed by adsorption,
that
llgnln
blodegradatlon.
than biodegradation.
than
be
nlght be
whlch might
any trends
trendg which
polnt out
out any
to point
Toxicity
Before attempting
attefipttng to
Toxlctt)f Test8
Teste -- Before
data
the data
to discuss
dLscues the
approprlate to
discernable in
data,
data, it
lt is
ie appropriate
the toxicity
toxlclty
G the
dtscerdble
large
teats show
eholt aa large
bioeeeay tests
The results
from the
the bioassay
obtalned from
resulte obtained
Ttre
ltgelf.
itself.
the data
variability
for
primarily in
data Pertalnl'ng
pertaining to
to Percent
percent
in the
some tests,
tests, primartly
for some
varlablllty
wLth
but even
even with
consLstent, but
The TLm
much more consistent,
data was much
IL,o data
D-Normal larvae.
D-Normal
larvee.
ratlonally
whlch cannot
cannot rationally
toxlclty
ln toxicity
Lncreases in
it
which
eu'dden increases
Beveral sudden
It there
there were several
I'n
lnetances in
several instances
there were several
During Serles
Series 2 and 3,
3, there
Durlng
be explained.
explained.
teet
the
ln
eparmlng
obtal.n
to
faLlure
which
lost
due
to
failure
to
obtain
spawning
in
the
test
to
were
lost
whlch samples
eamplee
ntls
This
gape in
data.
the data.
|n the
These
ln large
large gaps
resulted in
losseg resulted
tte"" losses
organlema.
organisms.
tool in
ln
tool
be
valuable
e
may
bloaeaay
author
feels
that
while
the
mussel
bioassay
may
be
a
valuable
mueeel
whlle
the
that
anihor feelg
of
method
of
method
a
as
value
lts
basls,
determining
toxicittes
on
a
one-time
basis,
its
value
as
a
one-tlme
deterurlnlng toxtcttlea
varlablllty.
thls variability.
due to
to this
following
degradation
may be limited
llmlted due
degradatlon may
followlng
-41-
ln the
the
varlatlon in
ltttle
very little
With
there
[e very
variation
there is
to salinity,
sallnity,
Wl.th respect
respect to
teete
conducted
the
tests
conducted
between
tn
toxlclty
degradetlon
of degradation in toxicity between
rate
and amount
arnountof
rate and
ppt appears
sPPears
25 ppt
at' 25
rate at
the rate
In some
some cases,
casesr the
ppt and
at 15
15 ppt.
at
and those
those at
at 25
25 ppt
Ppt' In
not
appeer
does
tt
that
small
ls
so
slightly
faster,
but
the
difference
is
so
small
that
it
does
not
appear
altghtly faoter, but tha dLfference
be significant.
rlgnlflcant.
to be
to
waste conconrerPect to
to waste
wtth respect
lB examined
exa,nLnedwith
When
of toxicity
toxlclty is
t{hen the
the removal
removal of
ls
A
valid
comparison
is
A
vall.d
cmparlson
noted.
are noted.
differences are
centration,
no significant
algntfl.cant differences
centratlon, no
kraft
kraf
C
te8ts uelng
possible only
only wl.th
with the
using seven
seven percent
percent and
and ten
ten Percetrt
percent
the tests
poseible
faahton.
alnller fashion.
ln aa similar
raported in
are reported
since
of these
theee tests
tests are
the results
results of
llnce the
degradatlon was
fagter rate
The
rate of
of degradation
was obtalned
obtained
tesfc indicated
lndlcated a faster
Ttra B.O.D. tests
toxtclty
that the
the toxicity
acsumedthat
tt is
is assumed
If it
waste concentrations.
concentr&tl.ong. If
the lower
lower waste
with
wlth the
of
rate of
the rate
that the
would suspect
suspect that
one would
is due to
various organic
organl.c compounds,
compoundo, one
to varl.oue
ls
concentraltaste concent'ralower waste
at the
the lower
lncrease at
degradation of
would also
also increase
sf toxicity
degradatlon
toxl.clty would
ltaste
of the
the three
three percent
This nay
may indeed
ln the
the case
ceee of
happen in
Percent waste
lndeed happen
ttons.
tions. Ttrla
be
be
cannot
levels
other
loadlng
wlth
concentration,
but
a
comparison
with
the
other
loading
levels
cannot
but
conparlson
concentratlon,
nede.
made.
influence
have aa large
large I'nfluence
to have
appeare to
The
of the
the environment
envl.rornent appears
Ttre temperature
tenperature of
teste
shon
20oC
the
tor
A
study
of
the
TL
for
the
20°C
tests
show
the
A
of
study
toxlclty.
of toxicity.
removal of
on
on the
the removal
\
days
days
ten
flret
the
over
toxlcfty
ln
that
there
is
a
significant
reduction
in
toxicity
over
the
first
ten
reduction
slgnlflcant
that there !s
aPProxlmetely
approximately
up
2.5
to
goee
2.0
On
an
average,
the
TLm
goes
from
2.0
2.5
up
to
from
8verage,
T16
On en
of
of the
the test.
test.
On the
the
On
toxl'clty.
ln toxicity.
percent reduction
reductl.on in
300 percent
to about
ebout aa 300
amounts to
7.O. This
llhl.e amounts
7.0.
in
ln
decreaee
e
8ma11
only
show
rune show only a small decrease
the 12°C
12oC runs
other
from the
data from
the data
other hand, the
the
be expected on
A slower
removal
on the
rete would be
renoval rate
A
perlod'
slower
over
test
the
TLm
over
the
test
period.
\
temPeraturest
colder
at
the
actlvlty at the colder temperatures,
btological activity
basis
ln biological
Uaita of
of the
decrease in
the decrease
of
evaluation of
does not
but
not pennlt
permit a
a quantltattve
quantitative evaluatLon
but the
nature of
of the data does
the nature
theee changes.
changes.
these
bl'oassay
the reeutta
It
must be remembered
remembered when
when considering
considering the
results of
of the bioassay
It rmrst
It
is
improper
lmproper
la
organLcm. It
one test
pertatns to
test organism.
onLy one
to only
tests
thet this
thls data pertains
tests that
organl'sme.
other organisms.
to other
theae results
reeults to
and extrapolate
extrapolate these
at
point to
to try
try and
at this
thls point
lndlcaLn P.B.I.
Results of
work indicate
that changea
changes in
P.B.I. are
are not
not indicalndtcate that
of this
thie work
Reeulte
There
does
waste. Ttrere does
the waste.
of the
charact€rl.8tlcs of
adverge characteristics
tive
of the other
more adverse
other more
tlve of
toxLctty.
or toxicity.
B.O.D. or
and B.O.D.
not
correlation betlteen
between P.B.I.
P.B1. and
appear to
to be any correlatlon
not appear
having
rtdel'y
widely
havlng
for
samples
be
The
same
P.3.1.
reading
can
be
encountered
for
samples
encountered
can
fire sarne P.B.I. readlng
galns
lnfontatlon gains
Ttrtg information
characterl.gtl.ce. This
different
toxl.clty characteristics.
and toxicity
B.O.I). and
dlfferent B.O.D.
considered.
consl'dered.
are
test
Pearl-Ben8on
added
importance
when
the
usee
uses
of
of
the
tha
Pearl-Benson
test
are
the
added lmportance when
pollution
of pollutlon
lndlcator of
ln the Northwest as
This
widely used
used in
as en
an indicator
le rldely
tegt is
Ttrta test
proceeded
haa
Pollution
litigation
has
proceeded
lltl.gatton
Pollutlon
lnduotry.
from the
pulp and
paper industry.
and paper
the pulp
howevert
remal'ne, however,
fect remains,
Ttre fact
pl,ecea of
of evidence,
evidence. The
prlmc pieces
using P.B.1.
data as
ig prime
ualng
P.B.I.- data
P.3.1
readings
readlngs
P.B.I
between
no relationship
relationghip between
that
ttttte or no
ls apparently
apparattlly little
there is
that there
pollutlon
and the
condition of
of the
the equattc
aquatic ennlronmnt
environment wlth
with resPect
respect to
to pollution
and
the condl.tlon
effectg.
effects.
--42-.
42'
ANDIpXTC
OF ORGANIC
ORGANTC
FOAM
AND
TOXIC
SEPAMTIoN OF
roAlt SEPARATION
EFTLUENTS
KRAFTMILL
MILL EFFLUENTS
MATERIALS IN
IN KRAFT
MATERIALS
foanlng
natural foaming
the natural
and the
nature and
Introduction
Becauseof
organlc nature
of the
Introductton -- Because
the organic
lnvestlgate
wag
to
declded
characteristics
of
kraft
mill
effluents,
it
was
decided
to
investigate
lt
of kraft ntlL effluents,
;frerarffiElca
The
The
treatnent.
of treatment.
es a nethod
the feasibility
of ualng
using foam
method of
separatlon as
of
foan separation
the
feaslbtllty
as
reductton
by B.O.D.
and C.O.D.
C.O.D. reduction as
treatment efficiency
B.O.D. and
was evaluated
evaluated by
affLclency was
organtsme.
narlne organismé.
to marine
toxlcl.ty to
well
well as
ae the
the decrease
decreace in
ln toxicity
pulp and
and
kraft pulp
fron aa kraft
obtalned from
Samples of
whole nlll
mill effluent
effluent obtained
Sampleo
of the nhole
sample.
the sample.
through the
by sparging
alr through
paper ntll
opargtng air
foamedin
column by
paper
mill were
were foamed
tn aa column
wac
catlontc surfactants
surfactantg was
and cationic
anlonlc, and
The
addlng nonionic,
nonlontc, anionic,
Ttre effect
of adding
effect of
of,
the effect
effect of
40'C to
as8es8 the
25t'C and
and 40°C
to assess
were foamed
at 25°C
Sanples werG
foaned at
evaluated, Samples
evaluated.
temperature.
be formed,
and
fonned, and
not always
alwaye be
would not
foam would
It
was observed
stable foam
observed that
that a
I stable
It was
be necessary
neceasary
may sometimes
sometluec be
agent may
ectlve agent
that
of a surface
aurface active
addttton of
that the addition
percent and
and C.O.D.
G'O'D.
to 35.2
35.2 percent
B.OD,
15.8 to
fron 15.8
B.O.D.reductions
r€ducttons from
for foam
foau stability.
stablllty.
for
of
surThe
addition
of
surcdditlon
Ttre
percent
were
obtalned.
20.2
reductions
from
79
to
20.2
percent
were
obtained.
7.9
to
fron
reductlons
reducB.O.D. and
C.O.D. reducand C.0.D.
tncreaee B.O.D.
dld not materlally
face active
materially increase
actlve agents
agents did
tion.
tlon.
organlen
(Uytllug,cdullc
ueed as
the test
test organism
ae the
wae used
The
mussel (Mytilus
edulia L.)
L.) was
bay uuesel
Ttre bay
of
to
1.8 to
danrage
TL's
toxicity
causing
507.
damage
of
1.8
50%
teets- TLils toxtcLty eauetng
for
toxlelty teats.
for the toxicity
TL's
waste.
TL6fc
untreated
the untreated waste.
on the
observed on
3.7 percent
percent concentratton
concentration were
were observed
3.7
reductlon
The toxicity
toxlclty reduction
after foaming.
foamlng. ?he
percent were
were obtained
obtalned after
up
up to
to 8.4
8.4 percent
before
foanfng)
waste
(raito of
TLsrof
of waste before foaming)
to TLm
foanlng to
after foaming
factor (ratio
of Tlo
TLm of
of waete
waste after
factor
up
Reduction
factors
up
factors
Reductlon
reductton.
was used
of toxicity
toxlclty reduction.
was
uaed as the
measure of
the measure
and
of surfactant
surfactent and
addl.tton of
the addition
to 2.3
2.3 rere
were obtained uhen
when foamed
without the
foamad lrlthout
to
Lower
reducLower reduceurfactant.
nonl.onlc surfactant.
LA, aa nonionic
when
wtth Krystallamide
Kryetallarnlde LA,
when foamed
foamedwith
gurfactante.
ugtng ionic
Lonlc surfactants.
tion
were observed
observed when
when using
factors lrere
tlon factors
toxictty
or toxicity
B.O.D.r C.O.D.
C.0.D. or
Increasing
affect B.O.D.,
dld not affect
temperature did
Increaelng the temperature
gener6ted at
at the
the
usually generated
was usually
However, a larger
volume of
of foam
foarn was
lerger volum
reduction.
reductl.on. However,
higher
htgher temperature.
tenpcreture.
(1) wtthout
without
phaaea: (1)
three phases:
ln three
was conducted
conducted in
The study
etudy was
Method of
of Study
Study -- The
aur(2) with
nonlonlc surof aa nonionic
additton of
the
addition of
(2)
wlth the
the addition
surfactant,
of a surfactant,
tffiitron
of
The
degree of
The degree
eurfactantg.
(3) wlth
of ionic
tonlc surfactants.
factant,
and (3)
with the
the addition
addltlon of
faetant,
B.O.D.r C.O.D.
C.O.D. and
ln B.O.D.,
treatment
was analyzed
reductlon in
the reduction
anatyzed by the
obtalned was
treatment obtained
toxlclty.
toxicity.
follows:
are as
es follows:
The
thelr purpose
conducted and their
Ttre tests
testc conducted
PurPose are
uee of
of aa suraurwlthout the
the use
foamed without
wag foamed
weote sample
eampte was
i. A whole waste
,.,1.
i'fecC
seParatlon
foan separation
the natural
natural. foam
face actl.ve
active additive
to evaluate
evaluate the
addltlve to
'
'
potentlal,
potential.
uged to
to
was used
IA, was
A
Krystallamide
Kryetallarnlde LA,
A nonionic
nonlonic surfactant,
rurfactant,
a
63-67
Krystallamide
LA
is
a
63-67
IA
le
Krystallarnlde
increase
the
foam
stability.
lncrelse the foam etablllty.
The
effect
Tfte effect
d{ethanolaml.de.
acid diethanolamide.
percent solution
pGrcent
of lauric
laurlc acid
aotutlon of
surfectant.
ualng
thls
of
gas
flow
rate
was
also
evaluated
using
this
surfactant.
ttso
evaluated
ftow rate we8
of
2.
2.
-43-43\tas used
uced to
to evaluate
evaluate
A
A cationic
AmronJrxLO,
IO, was
catlonlc surfactant,
surfactant, Ammonyx
or electroelectrothe
of
using a surfactant
to complex
cornplex or
the feasibility
feeslbtltty
of uelng
eurfactant to
nonand nonactive and
statically attract
attract the anionic
anton{c weakly surface active
rtattcslly
eurfactant
waste. The
The cationic
surface active
actlve materials
materlale in
the waste.
catlonic surfactant
rurface
ln the
percent
Ammonyx LO
le a 30
30 percent
Amonyx
LO is
war
was evaluated at
at two
two concentrations.
concentratlons'
oxl.de.
solution
of
lauryl
dimethyl
amine
oxide.
solutlon of lauryl dtnethyl anine
3.
,.
was used
uaed to
to
An
An anionic
eulfate, was
anlonlc surfactant,
aurfactant, sodium
eodlum lauryl
lauryl sulfate,
complex
to complex
evaluate
of
uslng aa surfactant
aurfactent to
the feasibility
feaslblltty
of using
avaluate the
eurface
or electrostatically
attract
csttontc weakly
weakly surface
ettract the
the cationic
electrostatlcslly
The
the waste.
wa6te. The
and non-surface active
matertela in
tn the
acttve and
acttve materials
* active
anionic
at two
two concentrations.
concentrStione.
anl.onfc surfactantwas
aurfactant wapevaluated
evaluated at
4.
4.
tn tandem
tendcn
The
lrere foamed
fosmedin
Ttre anionic
anlonic and
and cationic
catlonlc surfactants
aurfactants were
by the
the
bel.ng removed
to
materials were
were being
removedby
to determine if
lf different
dtfferent materiale
ternparasurfactants. Ttris
an elevated
elevated temperaThis test
aurfactants.
test was
was conducted
conductedat
at an
appralae its
ture
lte effect.
cffect.
ture to appraise
5.
5.
foanredin
ln
rrere each
The
each foamed
anlonlc and
and cationic
eurfactants were
Ttre anionic
cattonLc surfactants
eurfacttnt
The nonlontc
nonionic surfactant
tandem
with the
nonlonlc surfactant.
The
the nonionic
surfactant.
tandemwlth
the bulk
glve foam
was
remove the
bulk
used to
order to
to remove
was used
to give
foem stability
etabtltty in
ln order
ba
to be
whleh were
of
were thought
thought to
of the
the remaining
remalnlng ionic
lonlc surfactants
eurfactante which
treated
significantly contrlbutlng
contributing to
of the
the treated
the toxicity
toxlclty of
to the
elgnlflcantly
al.ao evaluated.
evaluated.
was also
waste.
The effect
effect of
of elevated
temperature was
wa8te. Ttre
elevated temperature
6.
6.
ln aa
sample in
Batch
were conducted
uelng aa one
one liter
llter sample
Batch foaming
foanring tests
teets were
conducted using
the
from the
plctured in
drawn from
23. Compressed
alr was
was drawn
foaming
ln Figure
Flgure 23.
Compreseedair
foarntng column
column pictured
pst by
by aa
precsure was
to 15
15 psi
laboratory
was reduced
reduced to
and the
laboratory supply lines
llnee And
the pressure
manually
rlas manually
The air
was filtered
preoaure regulator.
the flow
flow was
flltered and
pressure
Ttre
alr was
and the
regulator.
by ae
The
air
flow
rate
was
measured
by
waa
measured
alr
flow
rate
controlled
through
a
needle
valve.
needle
Ttre
velve.
controlled through
through
The
air
entered
the
column
through
the
col.umn
air
Roger Gtlnont
Cilmont instrument
flowrneter. Ttre
entered
Roger
instrument flowmeter.
movable
glaes filtering
in aa movable
tube fitted
fltted in
a medtum
medium poroalty,
porosity, fritted
frttted glass
fllterlng tube
plug
bottom of
of the
the column.
colurnn' A
rubber stopper whlch
which was
the
was used
ueed to
to
the bottom
posltloned in
atopper.
mercurial
ln the
rubber stopper.
ttas positioned
the rubber
mercurlal thermometer
thernroneter was
of 1.5
1.5
The
flve foot
foot length
was constructed
from aa five
length of
cotumn was
constructed from
foamtng column
Ttre foaming
column
The foam
glass pipe.
ptpe. Ttre
top of
of the
the column
from the
the top
foam exited
exlted from
inch dlameter
diameter glass
lnch
tape
A varlac
variac controlled
heatlng tape
control.led heating
degree elbow.
through a
90 degree
elbow. A
a removable
removable 90
deslred liquid
the desired
ltqutd tempereture
was
maintain the
temperature
around the
to matntatn
etapped around
the column
column to
wa8 wrapped
movable
by the
The
was varied
varled by
the movable
hetght of
of the
the liquid
liqutd was
during
durlng the
The height
the tests.
tests.
the restdence
resldence
order to
rubber stopper
to allow
allow the
bottom of
of the
cotumn in
ln order
ln the
the bottom
the column
stopper in
After
After
rates.
flow rates.
at varying
varylng flow
time
of the
approxl.mately equal at
foam to
to be approximately
the foam
tl,ne of
foam
broken in
tn aa centrifugal
c€ntrlfugel foam
leaving the top
of the coluiiin,
column, the foam
was broken
foam was
leaving
top'of
beaker.
breaker and
ln aa beaker.
and collected
collected in
premeasuredone
one liter
llter
The
of bringing
brlnglng aa premeasured
operetlon consisted
consiated of
foarntng operation
the foaming
1he
bath. The
water bath.
ln aa water
sample
waste to
the test
test temperature
temPerature in
to the
eample of
of the
the ltaste
column
was charged from the
with the
sample and the
the proper
proper alr
air flow
flow
the top
top wlth
the eanrple
column wae
The sample
was foamed
at a
foamed at
was
Ttre
sanple was
by means
of aa needle
needle valve.
valve.
was adjusted
meanaof
adJuated by
(* 2°C)
2oC)
(t 10
percent) and
constant
temperature (±
and aa constant
constent temperature
rate (±
fO percent)
flow rate
constant flow
of the
the
top of
until
sould exit
frour the
the top
and no
no more
more foam
foam would
extt from
untl1 the
the foam
foam broke and
momentarlly.
ts drain
draln momentarily.
The remalntng
remaining foam
foam ln
in the
the column
column was'allowed
wasallowed to
column.
column. Ttre
tube
tygon tube
through aa tygon
Then
was drained
drained from
fron the
column through
bulk liquid
the column
llquLd was
Ttrcn the
the bulk
foam
bottom of
of the
the column.
column. The
The foam
fitted in
et the
the bottom
fltted
ln a rubber stopper at
t{
tcg
il! fit$
FilE-*,#t [$E;'g;E
air supply
pressure regulator
control valve
filter
surge chamber
needle valve
flow meter
by-pass valve
gas sparger
thermometer
3
o|{
9.
10.
11.
12.
13.
14.
6.
7.
8.
4
5.
3.
2.
1.
1
2
T,g#* tst€ {i
HLgr H955[$$E$$
5
6
7
ta
5
+,
d
tt
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g
&
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g
c)
E
t.
c)
A
xc)
o
r+l
U
+)
d
o
E
o
(a
fi
fl
N
q)
a
Figure 23. Schematic of experimental apparatus.
foaming column
motor
foam breaker
foamate collector
4
11
'I
14
l3
12
-44-
H
t4
bt)
-45-
draLned
was then
then drained
and was
col.lapee and
to collapse
allowed to
remaining
was allowed
the column
column was
reogLnLng in
ln the
approxlmatee
method approximates
Ttrts method
foamate. This
wlth the
the foamate.
comblnad with
from the
and combined
the column
column and
been
had been
nodel had
flow model
contlnuous flow
found if
lf aa continuous
the condltlons
conditions that
that would be found
the
uged.
used.
and
foamlng, and
of foaming,
24 hours
wlth 24
hours of
conducted with
B.O.D. and
were conducted
tests wcre
and C.OSD.
B.o.D.
G.o.D. tests
were
conducted
Toxicity
tests
were
conducted
tests
Toxlctty
foanlng.
after
pH was
wao measured
measuredinuuediately
lmedlately after foaming.
pH
Nerpoatt
at Newport,
located at
Lab.oratory located
Sclence Laboratory
Marlne Science
Unlverelty Marine
at the
Oregon State University
.t
tt" Oregon
scheduling,
and
of
aanples
in
transportatlon of samples and
ln transportation
dffftcultles
Ttre difficulties
Oregon. The
Oregon.
A11
All samples
were
aanples were
teats.
the toxicity
toxLeLty tests.
performtng the
delaya in
ln performing
resulted
somc delays
Ln some
re"nlted in
conducted.
conducted.
were
teetg
the
until the tests were
bottlee until
stored at
ln stoppered
atoppercd glass
st 4°C
4oC in
ilaes bottles
waete
untreated waste
Ln untreated
surfactant in
nontonlc surfactant
Initial
uslng the
the nontonic
tests using
Inittal tests
settled
ltaste
the
Fibers present
waste settled
ln
Fibers
dtfitcultl'ea.
ceveral difficulties.
encountered
Preoent in
encountered several
were
column
walls,
and
some
were
eome
and
the column walla,
to the
adhered to
bottqm of
the column, adhered
to
of the
the bottom
to the
tests
the C.O.D.
C.O.D' tests
from the
obtained from
Resulta obtained
foam. Results
over in
tn the
the foam.
carried
cerrled over
fLbers. Several
of the
the fibers.
dletrtbutlon of
uneven distribution
to the
dua to
the uneven
were
were erratic
Grretlc due
problem.
flber problem.
the fiber
ellmlnate the
to eliminate
order to
tn order
pretreatment nethods
methods were
were tried
trted in
pretreetment
glacc
through glass
flltraCLon through
centrifugLng, filtration
ho,nrogenlzatLon,centrifuging,
Among these
were, homogenization,
iroog
these flere,
results.
conaletent results.
Sedimentation gave
gave the
most consistent
the rnost
wooll and
sedlmentatton. Sedimentatlon
wool,
end sedimentation.
hoirrct
12 hours,
approxlmatety 12
for approximately
were settled
settled for
oamplea were
On ait'aubsequent
all subsequent work,
work, samples
On
prlor
to
glass wool prior to
through glass
f,iltered through
and filtered
otf and
the supernatant
was drawn
drawn off
supernat;nt was
foaming.
after
separatLon, after
foam separation,
of foam
eff{ctency of
treatment efficiency
To evaluate
evaluate the treatment
To
conducted
conducted
were
testg
toxlclty
and
B.O.D.,
G.O.D.,
foaming
in
the
column,
B.0.D.,
C.0.D.,
and
toxicity
tests
were
Column,
foamlng ln
foarnate.
and
bulk
llquid,
surfactant,
bulk
liquid,
and
foainate.
wtth
eurfactant'
waste
whole waste with
$agte, whole
on
whole waste,
the whole
on the
the
practices
set
B.O.D.
with
B . o . D . aand
n d GC.O.D.
. o . D . wwere
e r e mmeasured
e a s u r e d in
l n aaccordance
ccordancew
lththepractl.cegset
and Wastewater
Wr-t"J-?nd.t'lastegatgr
of Water
tr**tlgtlon. of
forth
Methods for
for the
th" Examination
ln Standard
Standard U"thoda
forth in
Modification
of
of the
the
Modlficatlon
iberg
(1).
In
(1).
fn the B.O.fl. determination, the Aisterberg
tter€
Samples
were
Samples
oxygen.
dlssolved oxygen.
Winkler Method
used to
to measure
measuredissolved
wae used
Method was
lflnkler
eamplea
the samples
test, the
C.O.D. test,
the C.O.D.
In the
(+ 2°C)
days, In
flve days.
for five
2oC) for
20oC (±
at 20°C
incubated at
no
and
silver
sulfate
as
a
catalyst
and
no
catalyst
as
a
ueing sllver sulfate
were
tio hours using
for two
were refluxed
refluxed for
was
Hydrogen
ion
concentration
was
concentratlon
rtere applied.
applled._- Hydrogen lon
chloride corrections
correctlong were
chlorlde
pll meter.
meter.
Northrup pH
measured
and Northrup
by aa Leads
Leads and
measured by
(MYellus edulia
L.)
gdults L.)
mueeel (Mytilus
bay mussel
the bay
using the
Toxicity tests
were conducted
condueted using
tests were
Toxlctty
Ttre
The
proJect.
the project.
wtth the
aseoclated with
blologtets associated
by biologists
organlem by
test organism
as the test
prevlously.
previously.
deeerlbed
been
have
techniques
for
this
analysis
have
been
described
analyaio
for
thle
technlquee
foamand foamand foamate, and
bulk liquid
ltquid and
of bulk
votuncr of
Results
condLttons, volumes
Teat conditions,
Reeultg -- Test
and
C.O.D.
pll,
Results
of
pH,
B.O.D.,
and
C.O.D.
B.O.D.,
of
Reaulta
9.
ln
Tabte
tabul.ated
ing
time
are
tabulated
in
Table
9.
It[-IIne
Figures
Flgurea 24
24
reepectl'vely.
12 respectively.
and 12
1,1, and
10, 11,
analysis
ln Tables
Tablec 10,
tabulated in
ar€ tabulated
analyslc are
dtgcueaton
For
a
complete
discussion
corplete
teots.
of
Coxlclty
and
25
show
typical
results
of
toxicity
tests.
ana iS show typtcal reeultc
Science
of Science
l{aster of
the Master
to the
dlrected to
le directed
reader is
of
the reader
obtalned the
the results
resulte obtained
of the
ttFoanrSeparatlon of
Toxlc
and
Organic
and
Toxic
Organf'c
of
entltled
thesis
J. L.
Blazler entitled "Foam Separation
L. Blazier
thacls by J.
1965.
1965.
UnlversLty'
Stite
w."t"stt
Oregon
Materials
in
Kraft
Mill
Wastes"
Oregon
State
University,
Marertale fu frailiiii
varl'ed
effluenta varied
n111 effluents
the kraft
As expected,
of the
kraft mill
characterLstlcs of
the characteristics
Aa
expeeted, the
to
9'0
ptl
frm
The
pH
varied
from
9.0
to
varLed
Ttre
testeo
of
the
considerably
course of the tests.
the course
during the
conglderebly during
to
varied
from
577
to
577
fro'n
varled
C.O.D.
and
69/l
342
B.O.D.
varied
from
210
to
342
mg/i
and
C.O.D.
to
210
10.5. B.O.D. varled fronr
concentration.
percent
concentratl'on.
3.7
to
gOl
The
range
of
toxicity
was
from
1.8
1.8
to
3.7
percent
wae
from
967 ^glt.
mg/i. Ttre range of toxfcl.ty
teat
dlfferent test
an accurate comParlson
For this
comparison betlteen
between the different
rea8on, an
this reason,
be
mede.
cannot be made.
conditions
surfactante cannot
and surfactants
condltlons and
I'E
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Test Conditions, Volumes and Foaming Time
0)
E
253
222
500
140
175
200
240
722
385
195
322
165
258
E
d
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730
775
495
852
823
796
758
770
612
804
670
827
740
Volume, ml
Bulk
liquid Foamate
o
+r
d
F
-47-47-
10
T A B L E 10
TABLE
AnalYsis
p H Analysis
o f pH
Results
R e s u l t s of
Whole
T
est
Test
1I
2z
33
4
55
6
7a
7a
7b
8a
8a
8b
9a
9a
9b
10
IQ
Whole
waste
waste
1 0 .33
10.
r 0 .3
10.
1 0 .5
10.5
1
0 .5
10.5
t10.
0 , 00
r 0 .0
10.0
1 0 .4
10.4
10.2
IO.2
9.. 0
9
8.4
8.4
9
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9.0
8.4
8.4
9.0
9.0
waste
waste
w
/surf .
w/surf.
I10.
0.3
1
0 .33
10.
1 0 .4
10.4
10.4
10.4
1 0 .0
10.
10.0
10.0
r0.4
10.4
t o .z
10.2
9.
9 .0
8.6
8.6
9.0
9.0
8.6
8.6
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10.
L 9 ,2Z
10.
10,,2
l0.,2
10.5
10.5
9.
9.7
9.8
9.8
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10.2
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10.1
8.
8 . 44
8.0
8.0
8,4
8.4
8.2
8.2
8.4
8.4
Foamate
Foarnate
9.
9 . 66
9 .9
9.
r0.0
10.0
9.5
9.5
8 .8
8.
9.2
9.2
9.8
9.8
9.5
9.5
8 .7
8.
8.2
8.2
8.4
8.4
8.2
8.2
8.6
8.6
Enrichment
ratio
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1.67
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1. 68
1.64
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1. 62
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58
3
54
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296
296
295
280
313
297
392
303
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TABLE 11
Results of BOD Analysis
o
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64
A
92 (1)
Reduction
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58 (1)
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49
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N
Test
TABLE 12
Results of COD Analysis
o)
ta
o
142
59
Reduction
Ag
-t
74
53
151
128
103
101
r'r C
0r€
F{
Ft
vv
EO
6
(.)' Su
\orn
Frn
d
Fl
l-O'
\OO
7.2
20.8 (1)
17.0
0.4
17.3 (1)
16 4
g
reduction
Percent
tr
f'l
F{FlF{N04N'-r.{
2. 31
1. 83
k
2.40
3.00
d
H
1. 71
u
.<ftil-lOO'-{(Y)O
OO\f*$Oflco!{r
1.94
o
.lJ
1. 84
g
,.9
1. 76
(u
Fl
q)
h
F,|
rd
k
o
o
-50-
100
100
Temperature
250 CC
Temperature -- 25o
l0 cm./min.
crn./rnin.
Fiowrate
Flow rate -- 10
whole waste
O - whole
o
90
50 longh
mg/i
with 50
waete with
whole waste
c -- whole
L'A
Krystaiiamide
Krystallamide LA
iiqQid
bulk
liquid
O - bulk
foamate
O - foarnate
80
70\\
+-r
d
f
A
6 ( )60
u
o
t{
a)
a
TLxn--
TL'm
t
t
I-
.A
F{
\
o
II
ul
q4O
c
40-
I
I
I'\
I
I
I
II
I
I
\
I
I
I
I
I
I
E
d
E
3
33O0
5
20-
?
I
I
I
I
0
I
I
0
11 2 3 4
2
3
4
concentratton
concentration -- percent
Percent
1'
e s t 1.
e s u l t e -- ttest
Figure
Toxicity
o x i c i t y r results
26. T
F
i g u r e 24.
5
6
7
-51-
100
100
40o C
C
Temperature
Temperature - 40°
l0 cm./min.
Flow
rate - 10
cm. /rnin.
Flow rate
whole waste
o -* whole
O
mg/i
30 t^gh
with 30
whole waste with
O - whole
sulfate
sodium
lauryl sulfate
sodium lauryl
liquid
bulk liquid
O - bulk
foamáte
O foamate
70
4)
U
4)
l1
t
TLm
I
o
(u
o
o
t
_l
I
I
I
-,1_
t
I
I
I
t
E
I
I
I
d
E
,.
I
o
I
c
t
I
20
I
t
I
t
1
0
I
0
1
a
3
I
4
I
5
concentration
concentration -- percent
Percent
7a'
t e s t 7a.
Figure
Toxicity
e s u l t s -- test
o x i c i t y rresults
F i g u r e 25.
t5. T
6
7
-52-52-.
proof foam
foam provolune of
generally increased
the volume
Increasing
lncreaaed the
Bempereture generally
Increagtng temperature
C.O.D.1
B.O.D.1
ln.the
dlfference
waa
no
stgntftcant
There was no significant difference in the B.O.D., C.O.D.,
duced. There
duced.
reducttons.
and toxicity
toxlc{ty reductions.
and
euruslng the
nonl.ontc surthe nonionic
gae flow
lrhen using
rete when
flow rate
the gas
Gas Flow Rate -- Increasing
Increagtng the
$rs
foamate
of
A
smaller
volume
of
foamate
snaller
foam.
of the
the foam.
etabtllty
decr€ased the
the stability
factant decreased
of
Factsnt
slgntflcant
there wa8
flow rate,
rate, but
was
but there
was no significant
lncreaged flow
at the
the increased
was collected
coLlected at
greater
A greater
A
reductLons.
and toxicity
toxlclty reductions.
B,O.D., C.0.D.,
C.O.D., and
ln the
the B.O.D.,
difference
dlfferonce in
rate.
flow rate.
hlgher flow
at the
the higher
waa observed
observed at
ratio was
enrichment ratio
enrlchment
flow rate
was produced
produced at
at a flow
rate of
of 10 cm./mln.
cm./min. when
when the
the
An unstable
unstable foam
foan wae
gurfactant
ratc
flow rate
the flow
increasing the
was foamed.
foanred. By increasing
wtthout aa surfactant was
whole waste without
produced.
wag produced.
foam was
moderately stable
etable foam
to 20
20 cm./min.,
cm/mm., a amoderately
to
percent.
llore significant
eLgnlflcent
More
35.2 percent.
to 35.2
15.8 to
B.O.D. reduction
ranged from
from 15.8
B.O.D.
reduetlon ranged
wlth the
the
Tests
testo with
quantlty reduction.
reductfon.
the quantity
le the
the percent
reductlon is
than
percent reduction
than the
6O
at 60
ng/l at
55 mg/i
of 55
anionic
B.O.D. reductions
reducttons of
lndlcated B.O.D.
anlonlc surfactant
surfactant indicated
eurfactant
et 30
30 mg/i
rng/l surfactant
^glt at
63, 54,
and 54
54 mg/i
surfactant concentratlon;
concentration, and 63,
54, and
eurfactant
wlth
materiale
comblned
anlonl.c
surfactant
Apparently
the
anionic
surfactant
combined
with
materials
the
Apparently
concentration.
concentration.
not
at
all.
quantltles
or
only
srnall
ln small quantities or not at all.
in the
waste only in
the waste
ln
of 93 mg/t
B.O.Ir. reductions
reducttons of
With
mg/i 8B
at 200
200
l{|th the
Burfactant, B.O.D.
catlonlc surfactant,
the cationic
surfactant
rng/l
at
54
rng/l
mg/i
surfactant
concentration,
and
69
and
64
mg/i
at
100
mg/i
surfactant
concentratlon;
rng/l aurfactant
by McCormick,
McCorml'ckt
work by
prlor work
baete of
of prior
On
On the
the basis
obtalned.
concentration
were obtained.
concentratlon
frorn the
the
of
llgntn
removal of lignin from
atd in
the removal
ln the
this
was expected
to aid
expected to
thle surfactant
eurfactant lras
blological'
by
degradable by biological
be readily
readlly degradable
to be
consldered to
ls not
not considered
Llgnln is
eample. Lignin
sample.
to the
action and should
not contrlbute
contribute elgnlflcantly
significantly to
the oxygen
oxygen dernand
demand ln
in
should not
action
of
some combination
combinatlon of
It appear8
appears that
that there
was some
there wac
B.O.D. test.
It
the
teot.
the five
flve day
day B.O.D,
greater
gtve
the greater
to give the
wacte to
the waste
in the
the
with organic
materlal in
with
organl.c material
surfactant
the surfactant
eome
Without
I{tthout some
concentration.
hlgher surfactant
aurfactant concentration.
B.0 D. reduction
at the
the higher
B.O.D.
reductlon at
high concenconcenueeof
of high
the use
foamate, the
of foamate,
external reflux
volume of
the volume
to reduce
reduce the
reflux to
external
ln
greater reduction
reductlon in
obtaln greater
to obtain
trations
of
surf,actant to
of the
the cationic
catLonlc surfactant
tratlons
produced.
foamate produced.
of foamate
amount of
large amount
practtcal due
to the
the large
B.0.D would
due to
be practical
would not
not be
B.O.D.
surfactant
the anionic
anionic surfactant
wlth the
foamed with
The
foamed
wae first
lraste was
flret
whole waste
Ttre whole
An
An
surfactant.
wlth the
the cationic
catlonlc surfactant.
foamed with
and thebulk
was then
then foamed
the bulk liquid
ltquid was
that
This
indicates
that
lndtcatee
thte
obtalned.
waa
ng/1
of
additional
B.0.D.
removal
of
38
mg/i
was
obtained,
B.O.D.
38
removal
addlttonal
dl'fferent
with
different
probabLy
conblntng
are
surfactants
the
cationic
anionic
surfactants
are
probably
combining
with
and
anl.onl.c
the catlonlc
ltaete.
in the
the waste.
materials in
materlals
gurfactant,
of 67 and
reductl.ons of
B.O.D. reductions
nonl.onic surfactant,
In
with the
B.O.D.
teete with
the nonionic
In tests
reducthe
58
ng/f
This
is
slightly
higher
than
the
58
mg/i
reduchlgher
than
sltghtly
ts
Ttrle
obtalned.
I'tSlL were obtained.
74 mg/i
latter
However,
the
latter
the
a
use
of
surfactant.
the
tion
obtained wlthout
without the
of a surfactant.
tlon obtalned
ln
di.fference in
the difference
for the
account for
could account
waste
which could
concentrated wtrlch
neste was less
lesa concentrated
renoval.
removal.
lonlc suraurthe ionic
sample uel.ng
Tests were
were conducted
conducted on the
same lraate
waste sample
using the
the aane
Tests
dlfference
ltae
appreclable
There
was
no
appreciable
difference
Ttrere
wlthout aa surfactant.
surfactant.
factants
and without
factants and
methods.
three methods.
the three
in B.O.D.
B.O.D. reductlon
reduction between the
ln
B.O.D.
the B.0
As
D.
AB in
ln the
percent.
20.2 percent.
to 20.2
7.9 to
C.O.D. reductions
ranged from
from 7.9
reductlons ranged
by
removed
amount
removed
by
amount
the
between
dlfference between the
test, there
was no significant
difference
algnlflcant
there waa
tegt,
cattonl'c
The
The cationic
surfactant'
of the
anLonl'c surfactant.
the anionic
the two
concentrations of
two concentrattong
the
--5353th€
at the
ntren tested
tested at
of CC.O.D.
surfactant
0.D. when
Burfactent removed
rononed a larger
larger percentage
Percentage of
rurfactlnt
be expected
lf the
the surfactant
would be
higher
as would
expectcd if
hlgher surfactant
eurfactant concentration
concentratlon as
coublned
the lignin.
ltgnln.
combined wlth
with the
rlthout
we8 removed
removedthan
thcn without
Using
0.D. was
Uslng the
the nonionic
aonton{c surfactant,
aurfactant, less
leec CG.O.X}.
8.O.D.
waa
obtalned
la
ths
The
opposite
result
was
obtained
in
the
B.O.D.
of aa surfactant.
the
curfactant.
Ttrc oppoatte rcrult
the use of
whcn
C.O.D. reduction
reductl.on when
ras noted
Ln C.0.D.
No appreciable
apprectablc difference
dlfferenco was
noted in
analyel.c. No
analysis.
end
lsnfc surfactants
aurfactantr and
ualng the
tha ionic
tests rcre
were conducted on the
tests
cane waste using
thc same
wlthout aa aurfactant.
without
surflctant.
(ratlo of
to tLr
bulk liquid
of bulk
ltqutd tO
of TLm
Tt of
The toxicity
Ttre
toxiclty reduction
reductlon factor
f,aetor (ratio
Wtth the
the cationic
catLonlc
from 1.1
2.3. With
of waste before foaming)
foaulng) varied
varled from
1.1 to
to 2.3.
of
consentraof 1.1
ng/t surfactaut
surf,actaot concentraat 200
200mg/I
surfactant,
turfectant' reduction
reductlon factors
f,actorg of
l.l at
obscrned.
rere observed.
concentrltlon were
tion; and
and 1.7
and 1.5 at
mg/i surfactant
tlon3
1.7 and
rt 100
100 ng/l
aurfactant concentration
60 ng/l
of 1.6 et
With
at 60
mg/i s,trsurWtth the
factorr of
the anionic
enl.oalc surfactant,
reductton factors
eurfaetent, reduction
conrt 30
ng/l surfactant
curfactent con30 mg/i
factant concentratton3
concentration; and
factant
and 1.9,
1.9, 1.7,
1.7, and
and 1.5
1.5 at
wcre observed,
centration
centratton were
observed.
gurfactant, reduction
lor
2.3 at
at the
the low
factsra of
of, 2.3
Using the nontonlc
nonionic surfactant,
reductton factors
Ual,ng
l{hcn
When
foamed
f,oamd
obtorved.
2.0
htgh
flor
rate
wer€
flow
rate
and
2.0
at
the
high
flow
rate
were
observed.
flow rate and
at
appeare that
that
2.3. It
It appears
f,actor was
wee2.3.
without
reduction factor
wlthout aa surfactant,
aurfactant, the
th€,rcductlon
wlthout
a
botneen
surfactent
foulng
there is
difference
ls no significant
dlfferance between foaming without a eurfactant
there
elgnlflcant
with a nontontc
noutonic surfactant.
and stth
eurfae8ant.
nonl.onl,caurfac
obsenrcd that
the nonionic
rurfactant
It
was observed
taut dtd
did not
not contrlbute
contribute
It ras
that the
raate in
ths concentrations
concentratlons
ln the
of the
the whole
wtrole waste
significantly
to
toxlclty of
elgnlftcantly
to the
the toxicity
the
to the
had aa significant
contrlbutloa to
contribution
anlontc surfactant
elgnlflctnt
used. The
Itre anionic
eurfactant had
used.
not concluconclumre not
Toxicity tests
with the
surfactant were
the cationic
catlonie surfactant
toxicity.
toxlcity.
Toxlclty
teate rrtth
glve in
foancd
ssra foamed
In certaln
certain tests
surf,eetants were
sive
matter.
terts the ionic
lon{c aurfactants
ln this
thla matter.
In
lonlc
bulk of
of residual
recldual ionic
the bulk
in
with the nonionic
r€oove the
noalonLc surfactant
eurfactant to
to remove
Ln tandem
tanden wlth
nhet
obeeped over
wer what
waa observed
No
decreare in
ln toxicity
toxlclty was
No additional
addltl.onal decrease
surfactanta.
iurfactanti.
The
anlonlc curfactantrl
Tlre anionic
was
rlth the
aurf,ectant.
rar obtained
obtalned with
the cationic
catlonlc surfactant.
et the
thc
lcvel as
the same
arne level
bulk liquid
to approximately
epproxlnately the
bulk
toxlctty was
wec reduced
reduced to
llqul.d toxicity
gurfactmto
wl.thout ae surfactant.
bulk liquid
bulk
of the
foanl.ng test
test without
the foaming
llqutd of
-54-54-
OF EVAPORATOR
EVAPORATOR
CONqETSATES
TREAThENT
CONDENSATES
TREAfiENT OF
BY
BY ACTIVATED
ACTIVATtsDCARBON
CARBON
- This
of
phaee of
the feasibility
feaalbtllty
of the study
etudy examlned
General examined the
of enploylng
employing
General,
Ttrle phase
nedl.a
adeorptlve media
granular activated
as an
an adsorptive
process utilizing
carbon as
actlvated carbon
a unit
unft process
utlllztng granular
pollutanta
kraft
evaPorator
from
and toxic
toxlc pollutants from kraft evaporator
for the removal
removal of
of organic
organtc and
for
Gompany
Carbon Company
Plttaburgh Carbon
carbone, Pittsburgh
Two different
actlvated carbons,
dlfferent activated
condensates. Two
condensates.
B
A
and
resPecttvely'
aB type
type A and B respectively,
hereinafter as
destgnated hereinafter
type SGt
SGL and
and type CAL
CAL designated
thetr
terut of
of their
ln terms
These carbons
carbons are evaluated in
were
utlllzed in
etudy. lheae
were utilized
ln this
thle study.
(BOD)t
Demand
OxygenDemand (BOD),
Blochemtcal Oxygen
ability
naterlals exerting
exerttng Biochemical
to remove
organlc materials
abtltty to
reuove organic
(TOC),
(COD), total
Chemical
organic carbon (TOC), and
and Pearl-Benron
Pearl-Benson
total organtc
O<ygenDemand
Demand(COD),
Chenlcal Oxygen
(PBI).
Index (PEt).
Index
two cerbona
for each
Adsorption isotherms
were established
each of
of the two
carbons
Adsorptlon
lsotherms were
establlehed for
theee
of these
parameters stated
Reeults of
above. Results
stated above.
ustng the
waste strength
using
the waste
strength parameters
capaclty
adeorptlve capacity
ul.tlmate adsorptive
the ultimate
used to
to estimate
isotherm tests
lsotherur
tests are used
estlmete the
be attained
condltlone.
at equilibrium
which should
whlch
should be
attalned at
equlllbriun conditions.
In
attempt to
satisfy an accepted relatlonshlp
relationship explalnlng
explaining adeorptlon
adsorption
to satiafy
In an attempt
models.
mathernaticel models.
to several
phenomena,
phenomena,the
waa applied
applled to
several mathematical
data was
the isotherm
tsothem data
the
to lend
The
was found to
best and
and to
lend the
flt the data best
to fit
Freundltch relationship
relatlonehlp wae
Ttre Freundlich
the
fron
developed
plauslble
tsotherns
the
adsorptlon
most
plausible
explanation
of
the
adsorption
isotherms
developed
from
the
of
most
explanatlon
data.
experlmental data.
experimental
to
eubJected to
Ehe waste
studleg, the
After
waste was
was subjected
lsotherm studies,
After completion
completlon of
of batch isotherm
COD
COD
pl.exiglasa
upflow
columns.
contact
with
granular
activated
carbon
in
plexiglass
upf
low
columns.
contact wlth granular acttvated carbon ln
ln
poettlon of
adsorptton wave
the adsorption
of the
measurements
wave in
uaed to
the position
wrre used
to ascertain
aecertaLn the
meaaurementswere
wlth
efflcLency
ln adsorptive
adeorptive efficiency with
change in
the
column and
the change
to determine
determlne the
and to
the carbon column
PBI and
and
carbon, PBI
organlc carbon,
In
measurements, BOD,
BOD,total
total organic
add{tlon to
to COD
CODmeasurementg,
time.
tl.me.
In addition
lndtcatlon
an
toxicity
analyses were
were performed on selected
selected aamplee
samples to
to obtain
obtain an indication
toxlclty analysea
by these
nethods.
these methods.
measuredby
of
removal of
of substances
subatances measured
of the
the removal
of evaporator
evaPorator
procees for
treatment of
for the
the treatment
A
major objective
A maJor
of a process
obJectlve of
To evaluate
evaluate
waote. To
from the
the waste.
condensates
organl.ce from
of toxic
wa8 the
removat of
toxl.c organics
condensates was
the removal
bloaasay
by activated
carbon' aa bioassay
provlded by
actlvated carbon,
the
toxlcity reduction
the degree
degree of
of toxicity
reductlon provided
technique
using the
mussel, Mytllue
Mytilus edulle
edulis wae
was employed
employed aa
as descrlbed
described
the bay muaeel,
technlque usl.ng
in prevlous
previous sections
of this
thls report.
report.
sectl.one of
ln
- Evaporator or
foul condensete8
or foul
Characteristics of
Condensates condensates
of Evaporator
Evaporator,Condeneates
Ch4racteflstlcg
dlscharged
total weste
comprise approximately 15-20 per cent of the
waste volume
volume discharged
the total
of
the whole
content
However,
in
terms
of
the
organic
content
of
the
whole
organtc
of
the
llowever,
ln
terms
to
kraft
mill
sewer.
to kraft mll! eewer.
per
of
cent
40'75
from
mill
effluent,
evaporator
condensates
may
contribute
from
40-75
per
cent
of
may
contrlbute
condeneatee
ntll effluent, evaporator
preeents
a
typlcal
Table
13
presents
a
typical
13
BOD.
Table
as
the total
organic
load
expressed
as
BOD.
total organlc load expressed
analysis of
of the
evaporator condensate
condensate waete
waste samplee
samples used during
during the
the course
course
the evaporator
analysle
of this
this research.
reaearch.
of
to the wtrole
The contrfbutlon
contribution of
of evaporator
evaporator condenaatee
condensates to
whole mlll
mill efftuent
effluent
lhe
perronnel
In
mills
where
personnel
nhere
In
nLlla
quite
n111s.
for
eof,re
toxicity appears
appears to
large for some mills.
to be quite large
toxlclty
of
the
discharge
of
by
d{echarge
problems
brought
about
cognizant of
of pollutlonal
pollutional problems brought about by
are cognlzant
prectlclng
probleme
by
theae
to reduce these problems by practicing
strong
wastes, an effort
effort hag
has been
been Dade
made to
strong wsstea,
condenslteg
utlllze the
the condensates
Several rnllle
mills utilize
process waste
lraste waters.
reters.
various process
reuse of
of varlous
--5555-
13
TABLE13
TABLE
Condenaates
Evaporator Condensates
of Evaporator
Characteristics of
Charactarlstlce
BOI'
BOD
460-510
mg/i
460-510 mg/1
coD
COD
790-910
mg/i
790-9t.0ne/l
PBI
untts
PBI units
11,000-20,000
11r000-20,000 FBI
organtc carbon
Total
Total organic
s/l
tS5-187n
185-187
mg/i
to llyttlug
edulle
Mytilus edulis
T111to
( A v e . -. 1.27.)
1..2%)
0.7-2.67.
0 . 7 - 2 , 6 % (Ave.
eollds
Suspendedsolids
Suspended
mgll
3 0 - 7 0 mg/i
30-70
pH
pH
7
.2.7.8
7.2-7.8
at source
source
Tenperature
Temperature at
c
7
5-900C
75-90°
grease
hexane extractable
extractable grease
Total
Total hexane
(A,rg.)
107 rng/l
107
mg/i (Aug.)
waehers
from the
evaporators at
at flrst
first stage
stage pulp
pulp waah
wash water
water ln
in the
the drum
drum washers
fro,n
the evaporators
hot
as hot
mlllg
other
in
stlll
uged
Condensates
are
used
in
still
other
mills
as
prlor
Gondeneates
to final
washlng,
flnal washing.
prior to
conglderable
However,
in
a
considerable
ln
llowever,
putrposes.
and
other
waterfor
chemical
makeup
and
other
purposes.
water for chemlcal naieup
disThese disto the
the sewer.
8€rr€!. Ttrese
dlrectly to
plants they
dlscharged directly
number of
are discharged
they are
number
of plants
unlque
and
nsLure
glmllar n111
varlable
similar
mill practices
are
responsible
for
the
variable
nature
and
unique
the
for
practlces are reeponslble
Ttre Flow
Flov
plant. The
from any
dlscharglng from
character
any glven
given plant,
streem discharging
of the waste stream
character of
condensate
condensate
of
polnt
of
orlgtn
the point of origin of
Diagram
preeented in
showethe
25 shows
ln Figure
Flgure 26
Dtagran presented
rwastes.
agteg.
Tollerence
Investigations
conducted by
by t{arren
Warren establlghed
established 24-hour
24-hour l'ledlan
Median Tollerauce
conducted
Investlgatlons
from
3.5
to
17 per
per
to
3.5
from
ranged
nhlch
condengaee which ranged
gupptes to
to evaporator
Limits
for
evaporetor condensate
for guppies
Ltnlts
the
contribute
the
contrlbute
be
to
eald
can be said to
In
condeneates can
general, evaporator
evaporator condensates
In general,
cent.
cent.
effluent'
whole mill
m111 effluent.
of the
the whole
most toxic
fractLon of
moet
toxlc fraction
dlgestlol process
the digestion
durlng the
wtrtch occur
occur during
The
Process
reactlons which
hydrolysis reactions
Ihe hydrolysis
and
hemlcelluloseg
realns, hemicelluloses
molecule, resins,
llgnln molecule,
conrplex lignin
cleave
complex
cleave the
the relatively
relatlvely
maJorlty
The
majority
Ttre
by-producte.
varied by-products.
many varied
gtvee rise
to many
rlse to
other components
components and gives
other
removed
diesolved and removed
thus dissolved
are thus
and are
are alkali
solubte and
of
alkall soluble
cornpounds are
these compounds
of these
the
out
ln the
process carrled
During
process
carried out in
concentratlon
the concentration
During the
cooklng liquor.
llquor,
by the
the cooking
conoff
and
later
conlater
off
digtllled
evaporators, volail.le
volatile organic
organic materlala
materials are
are distilled
evaporatora,
condeneates.
evaPorator condensates.
the evaporator
present in
ln the
fractl.on present
densed to
organtc fraction
the organic
to form
fornr the
denaed
che evaporating
avaporatlng process,
Processt
unlform
Due to
uniform temperaturea
temperatures ueed
used tn
in the
falrly
to the
the fairly
lhre
within
contained rlthtn
ehould be contained
eondensate should
ttre condensate
present in
tn the
the organlc
organic conetituents
constituents present
the
extreme
the extreme
not posess the
thus, not
and thus,
range and
welght range
narrow molecular
a fairly
narrow
molecular weight
falrly
fron kraft
kraft
streanrs from
tn other
other rraate
found in
complexity
with compounds
waste streams
compounde found
Lnherent wtth
conrplexity inherent
the
include
the
lnctude
condensatea
from
leolated
courpounds
A
few
of
the
compounds
isolated
from
condensates
of
the
few
ntlle.
mills.
ketonea
ghort chain
and ketones
aleohole and
chain alcohols
guieol, various
varlous short
turpenes, reeLn
resin aclde,
acids, guicol,
turpenes,
yet
unldenttffed.
as
besides
nondistillable
oils
as
yet
unidentified.
ol1e
besldes nondistlllabte
-56-
E
g
to kth
q,
.E-ts
Liquor
o
to Digester
FI
Figure 26. KraftPulping Process Plow Diagram
q
n|
Fo
|n
q
6
o
Kraft Paper Making Process
e
a
6
c,
o
A
g
h
A
b0
c
tU
o
o
lU
€
ii
Bue Lime
0,
0)
e
t
5g
.oJ(
n('
fr.
Hd
6g
&
d
o
&
0"
d
U
v
iH
r
e
ql
tU
E
r
n
.h
nl
k
Lime
d
g
a)
o
o
H
A
bo
E
d
h
I
ol
I
M
|d
rd
t\l
g
b0
:i
Wood fiber
g
pQ'
g
(,
#
rI1
E
o
o
(,
Weak Black Liquor
3
F
o
(t
Fl
.|(
o
d
Wood Chips
B.
ca
g
u
!
o
o
3
Eg
EF
{(,
3
A
P
=l
-57-57-
whtch
col.or which
mllky-yeLlow color
ts ap milky-yellow
condensste sample
sampte is
A typical
typlcal evaporator
evaporator condensate
floatlngt
of floating,
Aonsiderable
Conslderable amount
smountof
glves the
opalescent appearance.
appearance. A
the liquid
llqutd an opalescent
gives
by the
reduced
the reduced
odor is
lnparted by
present and
te imparted
foul odor
oily
usually present
and aa foul
resldue is
ts usually
olly residue
the sulfur
sulfur
and the
eulfur
sulfur conpounds,
compounds, euch
such ae
as methyl
methyl and ethyl
ethyl mercaptans,
mercaptans, and
Other
Other
odor,
glvee the
lnfamoue odor.
lts infamous
the waste its
This
Ttrls gives
of the
the alcohols.
alcohole.
analogues of
analogues
to
contrlbute to
no doubt
doubt contribute
wood no
from the
the wood
extracted from
volatile organic
volatll.e
organic compounds
compounde extracted
wel1.
of the
aa well.
the waste as
the obnoxLous
the
obnoxious odor of
sfrong
of aa strong
that of
double that
le approximately
approxfurately double
the lraste
The BOD
BOD and COD
COD of
of the
waste is
Ttre
condengate
percentage
of
the
maJor
unllke
domestlc
but,
selrage,
domestic sewage;
but,
unlike
sewage,
a
major
percentage
of
the
condensate
selrage;
prevLoucly discussed,
dLscueaedt
As
As previously
materl.als.
by dissolved
dLssolved organic
organLc materials.
BOD is
BOD
ls contributed
contributed
organieme,
aquatlc
and
flehes
numeroue
toxlc to
to numerous fishes and aquatic organisms,
found to
this
waste has been found
to be toxic
thls lraete
problem.
polLutlon
aquatlc pollution problem.
serl.oua aquatic
and ag
such, represents
represents a serious
as such,
responatble
material.s responsible
that materials
by Marvel
revealed that
ltarvel revealed
An
conducted
An investigation
conducted by
lnvestlgatlon
wlEh
by
extractlon
could be removed
removed by extraction with
for
in
condansates could
for toxicity
toxlclty
ln evaporator
evaporator condensates
to
ldentify
attempt
to attempt to identify
lnitlated
wae initiated
Thus
was
to
dterhyl
ether.
llhus an investigation
lnveotlgatlon
diethyl ether.
from
obtal.ned from
presenE in
extracts obtained
the ether
ether extracts
ln the
the toxic
toxl.c fractions
fractlons
some of
of the
present
some
of condensates.
condensates.
composlted samples
samples of
composited
fron
methode from
by various
varLoue methods
lsolated by
compounds were isolated
In
Marvel's work many
many compounds
In Marveltg
and
aromatlc and
altphatic,
mostly aliphatic,
lrere mostly
These
aromatic
lhese compounds
compounds were
the ether
extracts.
the
ether extracts.
gul.acol and
and aa
conslderable guiacol
eome hydrocarbons,
hydrocarbons, considerable
unsaturated alcohols
with some
unsaturated
alcohols rrlth
pentanol-1.
Howevert
However,
qulte toxic,
4-(p-tolyl)
toxlc, 4-(p-tolyl)
found to
compound whlch
which was found
pentanol-l.
to be quite
compound
of aa viscous
vLscous brown
lras comprised
comprised of
per cent
extract was
cent of
of the
the ether
over
over 75 per
ether extract
acld
A silicic
slllcic
A
acid
dietil.latlon.
at distillation.
attempts at
all attempts
reslsted all
resldue
residue whtch
which resisted
of complexity
complexlty
degree of
falr degree
tndlcatlng aa fair
chromatoplate gave rise
spots indicating
to eight
elght spots
rise to
chromatopl.ate
resldue composition
composLtLon.
of
of the
the residue
for
account for
could account
pentanol-1 could
4-(p-tolyl)
The
material identified
as
pentanol-1
as 4-(p-tolyl)
The material
ldentlfied
It
It
condensate.
of
the
toxtclty
per
total
of
the
only
about
seven
per
cent
of
the
total
toxicity
of
the
condensate.
cent
only about
toxl'city.
higher toxicity.
even higher
of even
resldue contained
contained materlals
was
materials of
that the
the residue
was apparent
apparent that
components
This
toxicity
components
ldentlfy
toxiclty
attempt to
to identify
This attempt
waste
chemistry
the
the waste
of the
complexity of
the complexity
lllustrates
chemistry illustrates
problems
precent and
and the
the problems
and quantity
quantlty of
of organics
organtce present
component.
slngle component.
to a single
toxicity to
toxlcity
terms
ln terms
in
terms
ln
in terms
lnvol.ved
involved
of
of
of
of
ln
in
thelr
their
variety
the variety
the
attributing
attrlbutlng
- Ttre
carbon
of_granutar
appllcatlon
Activated Carbon Treatment
The application
of granular -actlvated
activated carbon
Acttvated
Treatment and
thus
information
thus
infornatlon
new
relatlvely
ls relatively
11 wastes
to the treatment of pulpmill
wastes is
new
to treat
treat
granular carbon
carbon to
used granular
Bloodgood and Sami
El-Naggar used
Sami El-Naggar
1s incomplete.
Lncomplete.
is
a
from
originating
from
a
two wastes
wastee orlginating
of the
the two
an acld,
acid, caustl.c,
caustic, and a mixture
mixture of
air
of color,
color,
In
their
work,
work, removal
removal of
thelr
pul.ptng process.
In
semi-chemical wood
wood pulping
seml-chemlcal
Proceda.
selecting
for selecting
prlnclpal
reason for
was the
the principal
imparted
complexes, was
reason
the lignin
lfgnfn-"orp1"*e",
lnparted by the
from
developed from
sotherms rere
were developed
adaorptLon Lsotherns
FreundlLch adsorption
Freundlich
carbon.
activated carbon.
acilvaced
samples
waste
eamplea
the three
three waste
adsorption equilibria
data
by treating
treatlng the
data obtained
obtalned by
adsorptlon
equlllbrla
lsotherms
these isotherius
The results
of these
The
reeulte of
carbons.
actlvated carbons.
dlfferent
with three
activated
three different
each rith
select
various carbons
carbons and select
of the
the varlous
predlct equilibrium
capaclty of
equlllbrlum
to predict
were used to
capacity
treatment.
to column treatment.
appllcatlon
the
best carbon
carbon for
to
for application
the best
treatment
the treatment
concentrated
portlon of
lnvestlgatlon
concentrated on
on the
great portion
of their
thelr investigation
A great
COD
plt
wtth
1.7 'with aa COD
of 1.7
poaaeseed aa pH of
materlat possessed
Ttrle material
waete samples.
acid waste
eamptee. This
of
of the
the acid
was
color was
as color
material rneesured
measured as
Llgnln materlal
mgl]-, Lignin
BODof
of 225
225 mg/l.
of
mg/i and
ana SOD
of 1410
1410 mg/l
--5858-
short
Wtthln aa short
carbon. Within
wtth the
the carbon.
contact with
adsorbed
contact
upon initial
lnltlal
adsorbed completely upon
was
removal
was
removal
color
tn
decltne
a
time
after
initiating
column
operations,
a
decline
in
color
operatlona,
lnitlating'colurnn
tlme after
8oon
ras soon
reduction was
of color
color reduction
However, a fairly
Level of
falrly constant level
notlced.
noticed. However,
be
could
be
curve
breakthrough
percepctbte
e
untLl
achieved
and
it
remained
until
a
perceptible
breakthrough
curve
ach1eved and tt remaLned
defined.
defined.
te8tst
the column
column tests,
of the
any of
ln any
The
no BOD
BODremoval
removat in
obtalned no
lnvesftgatora obtained
The investigators
COD
COD
in
color.
wlth
reductlon
qulte
closely with reduction in color.
but
correlated quite closely
but COD
removal correlated
CODremoval
foot level
level
10.5 foot
the 10.5
at the
obtalned at
per cent
w€re obtained
cent were
removals
80 per
of 80
order of
on the
the order
removals on
waete.
acld waste.
of the
the acid
passegeof
after
of 50
llters of
50 liters
after passage
tests
adsorptlon tests
the adsorption
wlth the
Successful
reactivation studies
conbtned with
studleg combined
$uccessful reactivatlon
be
should
be
should
method
treatment method
the treatment
that the
conclude that
led
to conclude
lnvestlgators to
led the investigators
performance and
8nd
the performance
evaluate the
to evaluate
pllot plant
plant application
appllcatlon to
studied
tn a pilot
studled in
of the
the process.
economic
aepects of
economlc aspects
Proeesa.
- Morrts
the
descrlbe the
and l{eber
Method
Isotherm Analysts Morris and
Weber describe
Adsor@
of Adsorption
Method of
a
deflning a
as defining
carbon as
actlvated carbon
adsorption of solute from solution ontoo activated
phasea
equilibrium.
at
equllfbrlum.
and
llquld
eolld
distribution
of
solute
between
the
solid
and
liquid
phases
at
between
the
of solute
dtstributlon
of
or concentration
concentratlon of
nature or
of the
the nature
functl.on of
be aa function
This
may be
ratLo may
distrtbutlon ratio
Thle distribution
envttormnntt
environment,
the
syetematlc
solutee,
the solute,
presence
of
secondary
solutes,
the
systematic
aecondary
solute, Presence of
the
ls to
to express
expresa the
dlstrlbution is
thls distribution
The accepted
of representing
representlng this
form of
accepted form
etc. Ttre
etc.
the
the
temPerature'
a
constant
of CC at
at a constant temperature,
quantity
function of
ae aa function
quanClty of
X(;/m) as
of X(x/m)
eoltd
of solid
welght of
per unit
unlt weight
adsorbed per
of solute
solute adsorbed
quantity
the amount
amountof
quanttty X
belng the
X being
ltquld
the
in
the
liquid
of
solute
U"tog the
the concentration
concentratlon of solute present
adsorbent, and
d being
Present -ln
and C
aasorUent,
rradsorpclon
thls
frosl
obtalned
le
An
"adsorption
isotherm"
is
obtained
from
this
iaothermn
An
phase
at equilibrium.
iqutltbrlum,
phase at
distribution.
distrlbutlon.
eeveral
maytake
take several
and CG may
Isothermal
between XX and
relatlonshlps between
adsorptlon relationships
Isothermat adsorption
solid
solld
of
the
Single
layer
deposition
on
the
surface
of
the
forms. Sfnile layer deposltion on the eurface
different
dlfferent forms.
poseeas{ng many
many
systems possessing
Complexsystems
comnon. Complex
adsorbent
be the
thC most
most conmon.
to be
appears to
adsorbent appears
thus
a
somewhat
smewhat
layers,
mult.lmolecular layers,
different
Ln multimolecular
adsorb in
mey adsorb
adsorbates may
dtfferent adsorbates
adsorptlon.
the adsorption.
of the
descrlptlon of
adequate description
used for
for adequate
be used
more
muet be
model must
more involved
invotved model
wtrereae
adeorptLon, whereas
single-layer adsorption,
for single-layer
only for
The
model is
valid only
la valtd
Langnrrlr nodel.
Ttre Langmuir
rePresented
adsorption
represented
muttllayer adsorption
to multilayer
tppiiee to
the
Brunauer-Emmett-Teller model
model applies
the Brunauer-Enmett-Teller
energles
surface energies
unlform surface
Both
models
assume
agsumeuniform
Soth
nodele
leothermg.
by several
different
isotherms.
dtfferent
several
Derivations
of
these
these
of
D,erLvations
respect.
thls
ln
for
adsorption
and
are
thus
limited
in
this
respect.
thue
llmited
and
flr adsorptlon
be
wlll
attempt
will
be
attemPt
no
and
literature
isotherms
are
handled
adequately
in
the
literature
and
no
ln
the
adequately
handled
ieotherme are
thesle.
thle thesis.
Ln this
made to
them further
further in
verify them
made
to verify
(1) naximum
maximum
principal assumptions:
aesumptlons: (1)
three principal
The
Langmuir equation requires
requlres three
ltre Langnulr
of
saturated
layer
of
Layer
a
Baturated
surfaces
adsorption
occurs
when
the
adsorbent
surfaces
possess
a
Possess
adsorpttor, occ,rrs when the
(3)
there
and
(3)
there
and
constant;
ls
of
adsorptlon
solute
molecules;i (2)
the energy
energy of adsorption is constant;
aolutl molecules
Q) the
plane of
of the
the
the plane
in the
molecules in
adeorbate molecules
of adsorbate
actlvtty of
is no transmigratory
transmigratory activity
1g
(1)
of
(1)
the
layers
of
layere
assumes:
The Brunauer-Enunett-Teller
model assumes:
Brunauer-Enmett-Teller model
surface. Ttre
surface.
by
descrtbed by
condltlone described
to conditions
subJect to
are subject
adsorbate
the surface
surface are
at the
whlch form
form at
adsorbate which
formatton
initiate
formation
may
lnltlate
layers
(2)
the Langmulr
Langmuir equatlon;
equation; (2) the additlonal
additional layers may
the
condLtlon
(3) the
equlllbriurn condition
the equilibrium
and (3)
layer; and
flrst layer;
prior
the first
of the
prtor to
compl.etlon of
to completion
numbers
by
the
additional
numbers
addltlonal
the
provlded
of surfaces
eurfacea provided
will
typea of
several types
w111 involve
lnvolve several
state
its
steady
state
Lts
at
of
of moleculeamolecules on each
each surface
surface elte
site exlstlng
existing at
of layers
layers of
condition.
condltlon.
-59-59-
fornr deecrtbed
The Brunauer-Eumtett-Teller
equation takes
takes the
the elnpllfled
simplified form
described
Brunauer-Esurett-Teller equatton
Itre
by Morris
l{eber.
Horrls and
and Weber.
by
AC
-x- A
- c
(ce-c)(1+(A-1)a
x'o (Cs-C)(l+(A-l)
Xm
(1)
(1)
where
'where
the solute
solute
of the
concentration of
Ce r saturation
aaturatlon concentratlon
Cs
at
ln solution
solutlon at
aolute in
of solute
Cc
measured concentration
concentratlon of
Gc -r rneaeured
equlllbrlun
equilibrium
compLete
to form
form complete
adsorbed to
of motes
moles adsorbed
X, - the
th" number
number of
Xm
surface
on carbon
carbon surface
monolayer
monolayer on
r the
solute adsorbed
of solute
of molee
number of
X(or x/m) moles of
adsorbed Per
per gram
gram
the number
at concentration
concentratlon CC
or carbon
or
carbon at
I a constant representative
solute-surface
of solute-surface
representatlve of
A
A lnteraetlon
energy interaction
forn allowlng
linear form
convenlent linear
to a
e more
be rearranged
Equation
more convenient
allowing
nay be
rearranged to
Equatlon 11 may
data.
to
experlmental
its appllcatlon
application to experimental data.
lte
c
C
(cs-c)x
(C8-C)X
-_L + A-1 /S-\
N (m \ lsc/C5)I
AxD
AX
AXm
((2)
2'
rl11 assume
aaaume
equatlon will
the Brunauer-Emmett-Teller
Brunauer-Ehmrett-Teller equation
Data
which agree
with the
agree wlth
Data whlch
plotted against
agalnet
Ls plotted
ln Equation
EquatLon 22 is
term in
the left-hand
left-hand term
tf the
relattonshlp if
a linear
ltnear relationship
slope of
of thls
this ltne
line w111
will be
be (A-1)/\
(Al)/AXm wtth
with an
an lntercept
intercept of
of l/AXn.
l/AXm
ClCe. The
Ttre olope
C/C8
ta:
equatlon is
leothern equation
The
Ttre Langmuir
Langnulr isotherm
X bc
\uc
x r nTsat
X
(14-bc)
(3)
all
and all
adeorptlon and
of adsorption
energy of
to the
the energy
related to
in whlch
which b denotes
constant related
denotee a constant
tn
convenienC
Ttro convenient
and 2.
2. Two
Equatlon 11 and
ln Equation
thoee in
other
aameas
as those
are the
the same
synbole are
other symbols
are!
equatlon are:
linear
Langmuir equation
of the
the Languulr
forns of
ll.near forms
C.l.r.,C
x
X
bxm
x'n
bXm
Xm
!.1
x X m;
x
* !/r\
bxn
(4)
(4)
and
bXAC,)
\c//
data
of data
uaed for
for linearization
llnearlzatlon
be used
Either
of
may be
Ewo equations
eguetiong may
of these
these two
Elther of
eguation.
Langunrlr
the
of
which
conforms
to
requirements
of
the
Langmuir
equation.
which conforme to requlrements
(5)
(5)
--6060-
years,
been used
used widely
wldely for
for many
Freundlich equation
The
The empirical
has been
manyyears
emplrlcal Freundl.lch
equatlon has
The
Ttre relative
relative ease
and analysis
haa contributed
contrlbuted to
to its
ease of
of application
appltcatl"on and
an*lyale has
lte
popularl.ty in
purfflcatlon
whecher or
degree of
popularity
eetl.matl.ng whether
declred degree
of purification
ln estimating
or not
not the
the desired
psrElculsr activated
be attained
wlth aa particular
ffire equation is
ts as
can
can be
attalned with
set*.vated carbon
carbon. The
follows
followa:
X(x/m) ' kc'
x(x/n)
k"l/'
(6)
(6)
where:
where
X
weight of
X r the welght
of solute
solute adsorbed
rdeorbed
weight of
m r the wetght
of carbon
carbon
in
par unit
wetght of
unLt weight
of
X(s/ni) - the quantity of
X(s/m)
adeorbed per
of solute
solute adsorbed
carbon
llioll"ntlty
sol"utl.on
equilibrium concentration
concentratl.on of
of solute
eolute in
Ln solution
C
C r the equlllbrl.un
k - a conetant
constant
1/n
lln - a constant
A
linear relationship
A llnear
beobtained
fron the
the Freundlich
Freundl.lch equation
equatlon
relatlonshtp can
obtatned from
canbe
by taking
by
taklng the logarithm
logarlthm of
of both
both sides
sldes:
logX-logk+l/nlogC
logXrlogk*l/n1ogC
This
of a straight
of slope
slope
Ttrla expression
expreaeton is
the form of
llne of
ls in
ln the
of the
the equation
straight line
equatl.on of
:
paper
plot
A
plot
of
X
versus
C
on
log-log
paper
will
lo9-Lo9
wlll
and intercept
lntercept of
of kk at
at CC - 1.
of X versua C on
1/n
1. A
Un and
yteld
that
follow
the
Freundlich
equation.
yield a linear
Linear relationship
relatlonshi.p for
for data that follow the Freundllch equation.
If the
equatton
If
data satlgflea
satisfies the
the llnear
linear nature
nature of
of the
the Freundllch
Freundlichequatton
the data
graphlcal procedure
proeedure will
provlde an
ultlnate capacity
capaclty
w111 provide
of the
the ultimate
a graphical
an estimation
estlmstlon of
A
vertical
whleh could
A vertlcel
of
of the
be expected
the carbon
carbon which
eould be
ln column
column application.
applfcatlon.
expected in
gcale corresponding
the
line
point on
correspondlng to
to the
llne is
ts drawn
drewn from
fron a point
horl.zontal scale
on the
the horizontal
(Co). From
polnt of
on the
the isotherm
lestherrut
lnfluent concentration
influent
concentrarton (C0)
From the
the point
of intersection
lntersection on
po{nt
p1ot, aa horizontal
axis at
at wtrtch
plot,
which point
verttcal apis
horlzontal line
llne is
16 extended
exteudad to
to the
the vertical
of impurity
This val.ue
value X
X represents
the amount
amcunt of
tnpuri.ty
a
e value of
of XX is
obtafned. lhlg
represents the
le obtained.
adsorbed
weight of
when the carbon is
equilibrium rlth
with
unit velght
ls in
ln equ{llbrlum
adcorbed per unit
of carbon when
the
the influent
tnfluent concentration.
concentrs,tl-on.
An
of volwrc
volume of
of
An equation
equatlon expressing
adsorptlve capacity
capactty in
ln terms
terme of
expreosl.ng the
the adsorptive
fotrlowa:
as follows
solution
is
eolutton treated
treated when
when adsorption
of solute
le as
adesrptlon of
sol.ute is
la complete
co'mpl"ete
u". X(V)
l"Bfu]
Vc
((7)
7)
per cent,
folnowlng
Whenthe
the following
When
then 100
cent, the
the adsorption
adsorptlon of
of solute
I0$ per
aolute is
te less
lese than
be used
relationship
relatlonship may
may be
ueed.
X
*oo9
('/)
VcCO
vc
Co-Cl
co-ct
(8)
(8)
-6L-61-
rrhare:
where:
per unit
unlt
treated per
volume of
of, solution
V c r- the
the theoretical
aol,utl.on treated
Vc
theoretleal volume
weight of
of carbon
carbon
weight
per gram
gram of
of the
the influent
Lnfluent
carbon of
of carbon
xco -' the
the capacity
cepaclty per
concentretlona
concentrations
tegt
taotherm test
used in
ln the
the isotherm
of solution
sotutlon used
V
l l r - the
the volume
volume of
c o .-t hthe
e 1 n initial
1 t l a 1 s o 1solute
u t € c o nconcentration
c e n t r a t t o n 1 nin
s o 1solution
utlon
C0
C 1 --t hthe
e d edesired
s 1 r e d 1 elevel
v e 1 o fof
s o solute
1uterem
a l n t n g l n in
a o 1solution
u t l o n a t at
C1
remaining
equtltbrlum
equilibrium
thege equations
equettonf
wlth these
obtalned with
carbon obtained
Adsorption
actlvated carbon
Adaorptlon capacities
capacltles of
of activated
neceasarLly
are
not
reasons
and for
for several
maxlnum values
values and
Beveral, reasons are not necessarily
represent
represent the
the maximum
obtaln isotherm
fuothern
used to
to obtain
ts used
Pulverized
carbon is
PulverLzed ,carbon
column application.
appllcatlon.
attalned in
tn column
attained
.
decreaset
of adsorption
adaorptlon decreases
rate of
data and
that the
the rate
ehould be emphaslzed
and lt
it should
emphasized that
rlth
of
adaorptlon
rate of adsorption with
partlcle size.
In some
some instances,
wlth increasing
Lnstancee, the rate
lncreaelng particle
aLze. In
with
sttrlned
never attained
granular carbon
is never
equlll.brlurn is
bq so
that complete
nay be
eo slow
conplefe equilibrium
granular
carbon may
elon that
ultiuete
the ultimate
Consequentty, the
provtded in
perlod provided
eotumn. Consequently,
tn the
the column.
durlng the
during
the contact
contact period
carbon capacity
never realized.
capaclty is
ls never
reallzed.
carbon
- Data for
for determlnatlon
Experimental PTocedure
Procedure determination of
of leotherms
isotherms were
were obtalned
obtained
Experlnrental
flied volunee
by treating
volumes of
of evaporator
evaporator condensates
condensates wlth
with knswn
known nelghts
weights of
of
treattng fixed
adaorptlve
the adsorptive
uaed to
pulverlzed carbon.
to compare
comparethe
were used
Ttre isotherm
tsotherm values were
carbon. The
pulverized
propertleg and
and BB.
properties
capacl.tiee of
of carbons
carbone AA and
and capacities
Representative
of both
both carbon A and B were
were pulverLzed
pulverized tn
in a
a
Repreeentatl.ve samples
sanrples of
U.S.
a
by
through
parttcle
waehlng
graded
ball mtll
mill and
graded
to
uniform
particle
size
by
washing
through
a
U.S.
ball
unlform
elze
to
and
adeorptlon,
carbon adsorption,
of carbon
The iate
rate deternlnlng
determining step of
Standard
number325.
325. the
Standard sieve
sleve number
pulverby
partlcles,
was
ellmlnated
intra-particle
migration
of
adsorbate
particles,
was
eliminated
by
pulveradsorbate
lntra-partlcle
mlgratlon of
powdered
carbon
of
flnely
Surface
adsorption
on
finely
powdered
carbon
of
adeorptlon
on
carbon. Surface
lzatlon oof, the carbon.
ization
llmLtlng
onLy
rate
the
waa therefore
adsorbates
bulk solution
therefore the only rate limiting
the bulk
adsorbates from
from the
sotutlon was
varlable.
variable
for
was selected
selected for
A
of evaporator
condenssteawas
evaporator condensates
A representative
representative sample
eample of
provLde
concentratLons
would provide concentrations
whlch would
lfelghts of
carbon which
tests. Weights
of carbon
lsotherm tests.
the isotherm
placed in
1000
were placed
ln 1000
carbon were
of activated
actlvated carbon
ranging from
mg/i of
6000 mg/l
ranglng
fronr 100
100 to
to 6000
naate
of the
the waste
500 mlllillters
To
each flask,
milliliters of
flaek, 500
To each
flaeks.
urllltLlter Erlenineyer
Erlennreyer flasks.
milliliter
glaee wool.
Ttre glaee
wool. Theglass
contalning glass
funnel containing
sAmple wae
was introduced
through aa funnel
lntroduced through
s.ampte
grlt or
or scale
ecale
partlclea such
such as
as grit
provided to
foretgn particles
wool was
wae provided
to remove
removelarge
large foreign
present in
were present
Ln the
whlch
the samples.
aamples.
which were
of
basts that
values of
that, values
che basis
was selected
on the
eelected on
A temperature
of 500
5Oo C
C was
temperature of
be conservative
would be
conservatlve
thls temperature
temperature would
adsorption
at this
obtalned at
adeorptl.on capacity
capacity obtained
uhlch
at the
the source,
source, which
raw waste
and
of the
the raw
ttaBte at
of the
the temperature
and because
becauee of
temperature of
appllcatlon.
waste treatment
treetment application.
be considered
would
ln aa waste
would have
have to
congldered in
to be
placed in
conetant
in aa constant
and placed
Btoppere and
The
then sealed
wtth rubber
rubber stoppers
were.then
sealed with
flaeka were
Ttre flasks
weter
a 500C
50oC water
flaeke in
ln a
agitation
of the
the flasks
whlch allowed
allowed iunnersion
ftmerelon of
mechanlcmwhich
agltatlon mechanism
to an
an identical
ldentLcal
was subjected
eubJected to
waate only,
only, was
of waste
bath.
sample consisting
conelatlng of
A blank sample
bath. A
procedure.
procedure.
--6262-
be
to be
waa assumed
perlod of
hours was
assumed to
A contact
of two
tlro and
and one-half
one-half hours
contact period
betlteen
the
condltions between the
of equilibrium
long
allow eetabllshnent
establishment of
conditions
to aLlow
equlllbrlum
long to
the solute
ln solution.
solution.
solute and the
eolute
eolute remaining
remaln{ng in
sufflclently
sufficiently
adeorbed
adsorbed
bath and
end
the bath
from the
perlod, the
removed from
At the
flaeks were
were removed
end of
of this
thle period,
the flasks
At
the end
Filtration
Flltratton
by filtration.
powdered carbon by
fll.tration.
froira the
the powdered
the
were separated
separated from
the samples $ere
Buchner funnel
funnel
uas inserted
whlch was
Lneerted aa Buchner
wae
vlth aa vacuum
vacuum flask
fLask in
tn which
was conducted
conducted with
powdered
and the
the powdered
The
paper and
paper.
fllter
No. 40 filter
Ttre filter
containing
Whatman No.
fl.lter paper.
contalning t{hatman
were discarded.
dlacarded.
carbon were
organic carbon
carbon
BOD, COD,
PBI, total
totaL organic
for BOD,
COD, PBI,
were then
then analyzed
anal.yzed for
The samples
eanpl.es nere
the
fron the
quantlty of
was computed
computed from
The quantity
material adsorbed was
toxlclty.
of materlal
and toxicity.
blank
the blank
ln the
measured in
difference between the
of
adsorbaEe measured
concentratlons
of adsorbate
dlfference
the concentrations
treared samples.
samples.
{n the
the treated
concentratlons
remeining in
remaining
and the
the residual
reeldual concentrations
the adsorptive
edeorptlve:
valueg comparing
eomparlng the
prel.tminary batch
tests in
which values
After preliminary
After
batch tests
ln which
the
equlllbrluu
of
B
an
eattmate
propertles
obtalned, an estimate of the equilibrium
properties of
carbone A and
and B were obtained,
of carbons
carbon
was made.
mede. A carbon
appltcatlon was
carbon expected
tn column
column application
capacity
capactty of
of carbon
expected in
basle of
of
the
pl.aced
on
operation on the basis
adsorption column
was constructed
in operation
and placed in
conotructed and
adsorptlon
coLumn $as
tests.
theee
these preliminary
preliminary tests.
tubLng,
diameter lucite
luclte tubing,
2-1/2 inch
tnctr diameter
The column
was fabricated
of 2-1/2
fabrlcated of
col.umn wae
at the
the
ports installed
lnstalLed at
sampllng ports
screened sampling
with removable,
removable, screened
4 feet
feet in
ln length
Length wlth
of
representatlon
echemattc representation
Figure 27 shows
of
Figure
sholrs a schematic
feet levels.
levels.
1, 2,
2, and 3 feet
L,
the supporting
supportlng equipment.
equipment.
the column and the
the
the velocity
veloclty
from the
adsorbent from
separates the adsorbent
A 50-mesh
stalnless screen
screen separates.the
50-rnesh stainless
Waste flow
low column was
was
upftow
the upf
flow through
through the
dtaslpatton chamber.
chamber. Waste
head dissipation
clamp
screu clamp
adJustabLe screw
gPm per
an adjustable
maintained
foot with
wlth an
square foot
one gpm
at one
maintalned at
Per square
An
An
feed
tank.
head
from
the
constant
placed
influent
line
leading
from
the
constant
head
feed
tank.
placed on the
the tnfluent
ltne leading
head.
a
constant
provlded
to
wae
lnsure
overf
low
line
on
the
feed
tank
was
provided
to
insure
a
constant
head.
overflow llne on the feed tank
by aa Brosites
BrosLtes positive
reservoir by
was fed
fronr aa storage
fed from
storage reservoir
feed tank
tank was
Positlve
The feed
fed
tras fed
whlch was
pump. lhe
reeervotr which
The level
ln the
the storage
Btorage reservoir
level in
displacement
dlsplacenent pump.
ltas
controlled
the laboratory
laboratory
from a 275 gallon
bulk storage
was controlled
gallon bulk
outeide the
tank outside
storage tank
frorn
valve.
wlth a float
float valve.
witha
ports'
other sampling
sampling ports,
or the
the other
The
the column
column or
the top
top of
of the
from the
Ttre flow
flow from
gap
into aa
depending upon the
air gap into
through an
an air
schedule, passed through
dependlng
the sampling
eampl.ing schedule,
in the
the
pressure fluctuations
fluctuatlons
prevent siphoning
and pressure
funnel
order to
in
eiphontng and
to prevent
funnel in
ln order
column.
column,
granular carbon
the column,
lnto the
carbon into
Prior to
of
the granular
of the
Prlor
the introduction
lntroducclon
to the
Carbon
flnes.
aud fines.
dust and
to remove
remove any
any dust
it
backwaahed in
warm tap
water to
ln warm
tap water
lt was backwashed
granular
was the
only granular
the only
lt was
eLnce it
run, since
type
was chosen for
run,
lnltlal
for the
the initial
type A wae
the testing
teetlng
of the
quantlty at
the initiation
lnltiatlon
carbon
quantity
of
at the
ln sufficient
eufficlent
avall.able in
carbon available
schedule.
schedule.
carbon
the carbon
and then
then the
lrater and
The column wae
was partially
filled
with
partl.ally
wlth water
filled
Ttre
to
and to
partlcles
This allowed
to
and
stratlfy
to stratify
the particles
This
allorred the
fom.
was added
was
added in
|n slurry
slurry form.
fllled
to
to
was filled
The column was
ln the
the column.
column. The
washed further
they settled
settled in
as they
be waehed
further as
lf
for expansion
expanslon if
This
foot space
epace for
0.4 foot
allowed aa 0.4
feet.
nrls allowed
a depth of
of 3.6
3.6 feet.
posltloned
The
wae positioned
Ttre column was
necessary.
rras found
found necessary.
backwashing of
backwashlng
the carbon
carbon was
of the
aPparatus
the
water
was
run
through
the
apparatus
run
through
Tap
watelhtaa
apparatus.
in
the
experimental
apparatus.
ln the experlmental
-
-63-63-
Overflow Lin
Overflow
Li
Constant
Constant
Head
Tank
Head Tank
II
V.
and Collection
Tank
--
l
i a . 44Z_a..
2 I1/211
1 2 t t ddia.
Plexiglas Column
Plexiglas
Column
--__.- _v-_.
Gap
(Atr
6Air Gap
/
foot
1 4nto*
-
t'"'
3 foot
gallons
275 gallons
275
it
Waste
to Waste
o
If/f/f
'f/f
2 foot
foot
Sample
Sanrple
PParts
/
4
Needle
Valve
Float
Valve
Float Valve
-
IJ
1 foot
foot
Flow
Meter
Meter
Supply
sUPP1Y
Pump
Pump
Experimental Carbon Column
Column and
Diagram of Experlmental
Figure
27. Schematic
Schematic Diagram
Figwe 27.
Apparatus
Supporting
Supporttng Apparatus
50 Mesh Screen
Head
Dissipation
Chamber
-64-64-
rate with
slth
deelred rate
perurlt adjustment
flow to
to the
the desired
of the
the flow
and the
the column to
to permit
adJustment of
ttcheck
A
Monostat,
A
Monoctat,
outn the
eguipment.
the
the supporting
support{ng equipment.
the screw
screlr clamp and to
to "check out"
and
adJustments and
fl.ow rate
rate adjustments
sapphire
ball, flowmeter
was used
make coarse
ueed to
flowneter was
to make
coarse flow
sapphlre ball,
Final
Final flow
flow rates
ratee
qulck vieual
operatlon.
to
visual check of
the column operation
to allow
allow a quick
of the
graduate cylinder
cyllnder and
and aa
were
with
of aa graduate
,r"e of
$rere established
wtth the
the use
estebl{shed volumetrically
volumetrically
stop
etop watch.
fron this
thle
of materials
materiale from
The
of the
for the
the adsorption
adsorptlon of
Ttre capacity
capaclty of
the carbon
carbon for
greatly underestimated,
required the
the construction
waste
construction of
of
underestlmated, and hence required
waste was
was greatly
A second
eecond
carbon.
less carbon.
column which
which contained
addltlonal
an additional
contained considerably
conslderably less
glass pipe
plpe in
ln
diarneter Pyrex
Pyrex glass
made from
one inch
lnch diameter
column was made
frour a one foot
foot by one
reasonable
be attained
attained within
withln aa reasonable
order that
order
of the
carbon could
could be
that exhaustion
exhaustion of
the carbon
of waste.
$aste.
volurne of
time
period, and wlth
with a much
much smaller
throughput volume
time perlod,
snaller throughput
As the
progressed, lt
it
teetlng schedule
schedule progreesed,
the testing
provide
poesesslng
possessing a deeper bed depth
depth might
nlght provide
Thus,
three columns,
columns,
strength.
sertes of
of three
strength.
I"hus, a series
conatructed.
of approximately
was constructed.
of
approxlrnately 15
L5 feet
feet lras
became
became apparent
apparent that
that Ia column
column
grearer
waste
in
reductlon in waste
aa greater reduction
bed depth
depth
poeeesstng aa combined
combLned bed
possessing
Flgure 28.
28.
ln Figure
filter
is
shown in
ls shown
of the
the 15
foot filter
A schematic
represencation of
15 foot
schematlc representation
gl.ass pipes
pipes with
wlth dimensions
dftnenalonc
with Pyrex
Pyrex glass
The individual
columns were constructed
Ttre
lndividual
constructed with
Rubber
BtopPers
Rubber stoppers
tn length.
of 1-1/2
five feet
feet in
length.
of
diameter, by five
t-Ll? inches
ineide diameter,
inches inside
steel screens,
screenst
meeh stainless
stalnless steel
fitted
with recessed,
dlameter, 50
50 mesh
fltted erLth
receseed, 1/2
LlZ inch
Lnch diameter,
of
top stopper
etopper of
Each top
columne. Each
were placed
placed in
both the
bottom of
of the
the columns.
the top
and bottom
top and
tn both
the three
three coltrmns,
columns, plus
plus the
the bottom
bottom stopper
stopper of
of the
the flrst
first coltrmn,
column, wae
was fltted
fitted
the
locations.
these locations.
glass tees
at these
with
convenient
rrlth glass
to facilitate
convenient sampling
earnpllng at
tees to
facllltate
prohibited the
bed prohibited
the
quantlty of
foot bed
The
ln the
the 15
15 foot
contalned in
Ttre large
Large quantity
of carbon contained
purpose
The
sole
purpose
of
of
Ttre
sole
breakthrough condition.
condttlon,
loading
loadlng of
of the
to a breakthrough
the column to
different
at different
efflclency
this
column was
was to
establish values
values for
at
for removal
removal efficiency
thls colunn
to establtsh
of
hydraulic loading
rates, and to
obtain an overalL
overall estimate
estimate of the
the maximum
maximum
hydraullc
to obtain
loading rate8,
perlod
contact
the longer
be adsorbed
Longer contact period
amount
material which
which could
durtng the
amount of
of materlaL
adeorbed during
could be
provlded in
bed.
provided
deeper carbon bed.
ln this
thls deeper
column.
the15-foot
l5-foot .coiuinn.
Both carbons
tested and
andcompared
and BB were
were tested
conparedinlnthe
carbons AA and
gputper
per square
gpm per
square
per square
foot to
to 14.8
14.8 gpm
Hydraulic rates
ttydraulic
varylng from
square foot
from 11 gpm
raEes varying
the lack
of
lack of
A. However, the
carbon A.
foot
containing carbon
foot were applied
applted to
to the
the column containing
prevented
lncurred prevented
sufficient
head,
headloes incurred
the large
large headloss
head, combined
comblned with
with the
sufflcient
B.
per square foot
for carbon
gpm per
carbon B.
loading in
excess of
of 10 gpm
foot for
loading
ln excess
- Four
to establish
tests were
Research lindlngs
Findings Four isotherm
were conducted
conducted to
establish an
an
Rgsearch
lsotherm tests
prel.lminary tests
testg
These
Ttrese preliminary
adequate range of
dosage concentration.
concentratlon.
of carbon dosage
provide aa
6000 mg/i
mg/l would provide
indicated that
carbon dosages of
mg/l to
to 6000
of 100
100 mg/t
tndicated
that carbon
lsothern
representative
satisfactoty
distribution of
of data
data points
points necessary
necessary for
for a representative
isotherm
satlsfactory dlstrlbution
plot.
plot.
fro'm rhtch
data
which
data from
presenta COD,
Table
PBI, total
carbon and Tr*
T
BOD, PBI,
total carbon
Table 14
COD, BOD,
14 presents
Figures
Figuree
calcMated.
B
were
calcfiTated.
Freundlich
isotherms
comparing
carbons
A
and
B
were
A
and
eomparlng
carbons
Freundllch Leotherms
equatl.on.
Freundllch equation.
the Freundlich
present the
to the
data fitted
fltted
29,
31, and 32 present
to
the data
29, 30,
30, 31,
whlch
for which
lsotherm
teeE
Reliable
Tj,j
values
were
obtained
on
the
isotherm
test
for
on
the
second
Rellable Tpq values lrere obtaLned
factora
toxlclty
reductlon
and
the
subsequent
toxicity
reduction
factors
used, The
the subsequent
carbon AA was
wag used.
Ttre Tj
Tp4
eample
value
for
the
treated
sample
by
for
the
treated
which were
were computed
by dividing
the
the T1y
T
value
dlvtding
whtch
computed by
Table
15.
preseilfed
form
tabular
in
that
of
the
untreated
waste
are
presented
in
tabular
form
in
Table
15.
ln
that of the untreated waste are
r
-65-65-
1" di
Pyrex
)
I
to Waste
From Constant
Heed Tank
I
I
Flow
Meter
50 M
Scree
reens
Needle Vdve
lnflr.rentSample
Influent
Semple
Figure
Representationof
of One
Figure 28.
28. schematic
Schematic Representation
one-foot
-foot and Flfteen-foot
Fifteen-foot Deep
Deep Columns
colqarae
-66-
TABLE 14.
Isotherm data
TABLE
14 Isotherm
data obtained
carbon Aa
obtained comparing
comparing carbon
Aa with
with
c a r b o n B.b
carbon
B.b
Carbon A
A
Carbon
Cu,bon
qu$aEe
uuae
Residual
COD, mg/I.
m/L
Residual
BOD, mg/L
Residual
PBI, units
mg/L
00
100
100
250
250
5
00
500
700
700
1000
1000
2000
2000
6
000
6000
800
800
6zs
625
567
567
443
443
3
83
383
3
1
3100
245
245
zr6
216
420
420
3
30
330
270
270
240
240
700
700
t75
175
r44
144
t27
127
l 0 r 525
525
10,
lo, 125
I25
10,
9,925
9,925
8,
000
8,000
5 , 350
350
5,
1
,560
1,560
90
90
0
Residual
organic
carbon, ntg/L
185
185
Residual
toxicity
TLM,
0 .77
r156-175
5 6 -1 7 5
l3g
139
?.a
7.0
^'11.5
117
nI3
::'
--
-5 5 .7
55.
5 2 .1I
52
> 1155
>20
>20
>
20
>zo
>>zo
20
Carbon
Carbon
dosage
mg/L
COD, mg/L
0
100
100
250
250
500
500
700
700
t1000
000
2000
2000
6000
6000
821
8Zl
610
610
510
510
39s
395
328
328
274
274
zzo
220
212
212
Residual.
acarbon
aCarbon
bcarbon
bCarbon
Residual
BOD, mg/L
475
345
345
2 72
72
z225
z5
r188
88
t172
7Z
t3 7
137
127
127
Residual
PSI, units
1 0 ,300
300
10,
850
9,
9,850
9
"0 5 0
9,0.50
6 , 625
625
6,
2
950
2,, 950
r1,570
,570
5
500
00
Residual
organic
carbon, mg/L
Residual
toxicity
TLM,
0. 7
185
158.5
158.5
87.4
87.4
-lz
>
12
>tz
- -
> t1.2
2
6 4 .88
64.
52.9
52.9
--
4 6 .s
46.3
'
> 2200
>20
>20
> 2200
>20
>20
A - Pittsburgh
Pittsburgh Carbon
A
Carbon Company
Company SGL
x 30
8)<
30 meeh
mesh
SGL 8
A - Pittsburgh
Pittsburgh CarbQn
A
Carbon Company
Company CAL.
CAL l|x
12 X40
40 mesh
mesh
Conditions
Test Conditions
Temperature 50°C
50 o C
Temperature
period
Agitation Period -- 2Z 1/2
Agitation
hours
UZ hours
pH
untreated
pH untreated waste
waste - 7.?.1I
-67-67-
by carbon
carbon
TABLE
15. Reduction
Reduction inin evaporator
evaporator condensate
TABLE 15.
toxicity by
condeneate toxicity
adsorption.
adsorption.
olo
Toxicity
iduction
rcduction
(TRF)*
ffactor
a c t o r (TRF)*
0.
0 .7
--
2SOmg/1
250 rnglL
7.7
7.7
11
rl
70Omg/i
700
rnglL
74
7.4
1 0 .44
10
1 0 0 0mg
1000
mg/i
/l
9 .55
13
1 3 .55
3OO0
3000mg/i
mglt
11.8
ll.8
17
t7
6000
6 00 0 mg/i
rn g h
11
l l . 88
17
l7
(ra w waste)
0 (raw
w a ste )
*
*
Toxty
LM
h
ar1.1on
Carbon
dosage
d
osage
C'
'V
TLM,
of
Computed by
by dividing
dividing Tr.*
TLMofoftreated
treated by
by Tt
TLM
of untreated
untreated
Gomputed
tut
sample.
eample.
Test Conditions
Teet
Conditions
(pulverized)
Carbon type
A (pulverized)
type A
Carbon
l l 2 hours
e r i o d - - Z 1/2
Agitation
A g i t a t i o n pperiod--Z
hours
7
,
4
p H uuntreated
pH
waste-7.
4
ntreated waete1
--6688-
3.0
2,O
2.0
1
.5
1.5
1
.O
1.0
0.9
0.9
rl
0.8
3 o.z
k
rl
Io o . o
o.s
I 0.5
o
bo
I
a
o
.e
0.4
*
0
0..33
o
0. .22
o
.15
0.15
0. 1
COD, mg/i
mgll
C, Residual
Restdual COD,
A and
cnd B
B
Freundllch Isotherm
Adsorption o,n
on Cerbor
Carbon A
Figure 29. Freurdlich
Ftgrne
kotherm for COD Adsorptlon
- 69-69-
O Carbon A
3.0
X"o = 2.4
2.0
2.O
g Carbon B
)(co= 1'5
1.5
1
.5
1.0
1.0
0.
0. 09
c
0.01
08
s0.
20. o
8
0.07
o.
3o.06
Ho.os
8
0 .Q40 4
o
A
0
€o.03
o
: 00.. 0o2
b
E
)i
0.
o .iC
10
0.
0
o. 09
0.
0
0.08
o
.07
0.02
0. 06
0
0.
0.05
0.05
0.04
0. 04
0.03
o. 03
0.02
0.02
0.01
Restdual BOD,
Residual
BOD, mgll
mg/i
30.Freundlich
Figrue 30.
FreurdlichIsQtherm
leothermfor
Figure
on Carbon
Carbon A
forBOD
BOD Adsorption on
A and
andB
B
0
- 70-
/r
I
!;>o
o
Iio
g
l
['r,
g
F
!
g
g
g
8
N
tr
(!
C, Residual PB! Units in Solution
a
Figure 31. Freundlich Isotherm for PBI Adsorption on Carbon A and B
l
FI
0
E
0
ta
q
I
:a
p
EI
A.
d
,
tt
0
c)
d
rJ
c
3
fl
u
c
o
6
E
I
E
E
u
€
g
(,
I
E
o
6
EE
E
o Carbon B
o Carbon A
€
g
\
c,
h
-83
a
b0
lr.
cioi d N 6
ui
uoqr€Ctur/paqrospy
.f
.'i
tri
srlun lgd ,X
1.
:
{
;
oo
j
ro
a)
I
10.
9.
8.
UU
It
°
Fg
(td
o
-7L-71-
I
0 Carbon A
t.o
1.1
0.9
.0.
0.8
0.
a
o,7
0.
0.6
0.
o
0. . 5
.
o
o
rt
U
bo
E
E
g0
o
0. . 4
o
0.. 3
.20
tu
€
o
0
€
{
q
I
8
t-.
Io.I
bb Ø
o.
E 0.
o.
o.
X 0.
o.
0.
o.
0.
o.
0.
o.
0.
i
lo
0.
g
.10
o
0
20
30
& ' 5 0 50
40
6070
6 0 7 080
8 090
9 0100
100
Residuai'T@,
mg/l:
Residual
TOC, mg/i
Freundlich Isotherm
lsotherm for
for Total
Totel Organic
Organlc Carbon
Cerbon
Fi&ire 32.
32. Freundlich
gnd B
Adsorptioa on
Adsorption
on Carbon
Carbon AA and
B
i
I
a
I
S
200
--7272-
(Eq. 5)
and
5) and
equation (Eq.
Langmutr equatlon
the Langmuir
BOD data
data analyzed
analyzed wtth
COD and BOD
with the
COD
llnear
the
not
assume
aegune
the
linear
dld n6t
33 did
Flgure 33
ln Figure
graphlcal form
form in
presented in
preeented
ln graphical
alkylbenzene
of_varioue
various alkylbeuzene
adsorptlon of
for adsorption
end t{eber
relationship found
Morris and
Weber for
iouna by Morrls
relatlonsnfp
29
Flgute
wlth
33
Figure
Comparison of
with Figure 29
of Figure
Compartson
eolutLon.
su].fonates
from dtluie
dilute solution.
eut.fonatea from
lsotherm
Freundlich isotherm
the Freundllch
reeembles the
pLot closely
cLosely resembles
the Langmuir
tangmulr plot
reveals
that the
reveals that
can
curve can
portlon of
the curve
of the
The very
very steep
eteeP portion
forn.
when
ln inverted
lnverted form.
when examined
exanined in
flatter
wlth the
the flatter
fractlon with
unadsorbable fraction
the unadsorbable
to the
apparently
to
attrtbuted
apparently be attributed
eaelly
the easily
established wlth
with the
establ.iehed
the equilibria
equillbria
of the
piitfon
portion Ullng
being representative
of
representattve
wagt€.
the
tn
adsorbed
compounds
in
the
waste.
adgorbed compounde
not
data does not
the data
that the
appears that
lt appears
presentations it
graphlcal presentations
From
these graphical
From these
the
rhen
eguatton
by
the
Langmuir
equation
even
when
the
the
Langmuir
piedtcted
llneartty
the linearity
agree
with the
predicted
agree with
unadsorbable'
BOD
ae
and
BOD
as
unadsorbable.
COD
residual
certain
a
aaauming
data
certain restdual COD
adJusted by assuming
aita is
is adjusted
that
as that
such as
with
data such
wtth data
relationship
thte relationship
satisfying this
pocslUiffty
of satisfying
The
of
Ttre possibility
of
ln
llght
unspecific
in
light
of
unepeelfic
8o
are
wtrlch
tests, .ihich are so
CODtests,
obtained
BODand
and COD
Che BOD
with the
obtained with
overexteneiOn
ie
is
an
overextension
condenaates,
evaporator condensates,
of evaporator
content of
the
complex organic
organtg content
the comrplex
caPablllties.
the equation's
equationts capabilities.
of the
of
the operatlon
operation
teots the
lsotherur tests
batch isotherm
the batch
of the
Upon completion
completton of
Column
Resutce -- Upon
Teet Results
Column Test
of obtaining sufficient
columns
fof
f i s tcarbon
n1tf'ete
d . T t r e dwas
f f f 1 cinitiated.
u l t y o f o b t a l n lThe
n g c udifficulty
ff{clent
bed
foot carbon
carbon bed
pac1tyof the
four foot
the four
;;"-;-ro to nifi$ir"irhe,l€nt[rrs*adsorptive
waste
utilJethe.entiradsorptive @iaet'ty'of
column.
carbon column.
of aa smaller
smaLler carbon
prompted construction
of
constructton
wao
dlameter' was
lnch diameter,
by one
one inch
deep by
foot deep
one foot
Accordingly,
aa glass
glase column,
column, one
Accordlngly,
emaller
the smaller
of the
An
An advantage
adventage of
teats.
exhaustlon tests.
perform carbon
carbon exhaustion
acquired
to perform
acquired to
ln
evaluated
could
be
evaluated
in
B
could
A
carbon
both
carbon
that
carbon
column
was
that
both
carbon
A
and
carbon
B
carbon
gallon
eample'
275
composited
in
one
275
gallon
sample.
Ln
waete
eo,nrposited
unLform
using
aystem using uniform waste
dynamic system
a dynamic
both
for both
foot eolumn
column for
one foot
wlth the
the one
COD
data obtained
obtalned with
breakthrough data
COD breakthrough
conflrm
tests
These
column
tests
confirm
Ttrese
Flgure
34.
in Figure 34.
B are
illustrated
carbon A and B
in
are illustrated
carbon
indicated
carbon
BB
lndlcated
whlch
studles
batch isotherm
isobherm studies which
results
obtalned by batch
reaults obtained
A'
carbon
did
capacity
than
did
carbon
A.
than
capaclty
adsorPtive
more adsorptive
cent more
possessed
poeseseed 30-35 per
Per cent
the
operating
variables
and
the
varlables
baElc operating
the basic
forn the
Table
presenta in
tn tabular
tabular form
16 presents
iable 16
for
obtalned
the
data
obtained
for
data
the
from
calculated from
capacltles
resulting adsorptive
calculated
adsorptlve capacities
resultl.ng.
toxicity
expresses toxicity
35 expresses
Figure 35
B. Figure
and B.
column operation
using carbons
carbons AA and
operatlon using
column
tente
in
Mytilus
edulis,
in
terms
organl'sm, Mytll.us edulis,
bioassay organism,
the bioassay
results obtained
with the
obtal.ned with
results
'
factor.
reductlon factor.
of a toxicity
reduction
of
toxlcity
,
the
from the
taken
taken from
trealed effluent
effluent
Exploratory tests
conducted with
with treated
tests conducted
Exploratory
carbon
with
carbon
wl'th
contact
iddttional
to additional
port, and
column's four-foot
port,
contact
subJected to
and subjected
four-foot
columnts
indicate
thet aa
lndlcate that
to
appeared
column,
by
foot'deep
in
a
one
inch
three
foot
deep
column,
appeared
to
thiee
lnch
ln
A
time'
contact time.
higher degree
of removal could
could be aehieved
achieved wlth
with greate"
greater contact
degree oi
htgher
subetantlate
".torr"l
further substantiate
to further
wae assembled to
28 was
Flgure 28
ln Figure
shown in
15 foot
as shown
foot deep column
findlngs.
theee findings.
these
sections was
was charged
charged
column sections
foot column
flve foot
three, five
Initially,
each
the three,
of the
Qach of
Inltlallyr
3,
of
1, 3,
Hydraulic
loading
rates
ratea
of
1,
loading
Hydraullc
Lnchee.
of
54
depth of 54 inches.
to aa depth
with
wlth carbon
carbon BB to
ratea
of
loadlng
the
effects
of
loading
rates
the
effects
to
evaluate
were
chosen
gal/minlf1'2'
5, and 10 gal/mm/ft2 were chosen to evaluate
5,
beet
ls best
tests is
of tests
thie series
serlee of
of this
regults of
The results
removal efficiency.
efflciency,
on removal
36.
Figure
ln
explained
in
the
curves
shown
in
Figure
36.
explaLned ln the curvea eho\tn
three
the three
of the
contents of
the contents
lrere completed,
completed, the
After
uslng carbon
carbon BB were
After tests
tegts using
The
A'
carbon
volume
of
carbon
A.
of
volume
equal
with
an
repl.aced with an equal
columns
ind replaced
removed and
columng were removed
-73-
r
I
I
I
I
16
/
t155
It
/
6 r *14
€d
ril
u 1 313
o
b0
E
BODData
CarbonA
iIt t z 12
/
o
{tl
I
II
o
ill
g10
10
BOD Data
SOD
Data
B
CarbonB
Carbon
I
/
F
o
I
8e
o
u
U
CODData
CarbonB
I
I
I
bS
E ' 88
E
x-7
COD Data
/
CarbonA
7
X
1
d6
5.
/
I
,lj
3
I
I
0
0.002
0.002
Figure
Figure 33.
33.
I
0' {J()0
0.006
0.004
0.004
COD orBOD
or BOD
1/C,
l/C, mg/I
mg/l COD
u.
0.0u
Langmuir
Applications
BOD Data
Data to
to the Langmuir
and BOD
COD and
of COD
Applicetlone of
lsotherm
AdsorPion Isotherm
Adsorption
luangtg urunloC u1 Eulsso4C1OCluacred
B39RR
0
1
\
\'
0
\
22
3r:
'- (o tt)
o
Fl
\
\.
\
<lDlO
'''g
3€
a(J
!l
6r!
S
e
HO
'E
dE
u 33 ?
Weight Carbon A ------------- 53.1 g
Weight Carbon B ------------- 55. 6 g 2
Waste Flow Rate -------------- 1 gpm/ft
tl
o
b0
<cl
cg
oo
€n €t ( '
uc)
9p
-'b0
d.6
rt
.ts E
o. oI
b0
I
I
E
FI
(l
& dg
3
o
d
b0 Pc, h
tU
c) 3
tr
2
d
8
3
Io
!
0
34
3d
Or
F.
3
42
Average Influent COD ---------- 790-900 mg/i
b0bO
)l\
E.
x
24
{l
A
o
N
Carbon Column Dimensions ------- 1 inch dia. by 12 inch dp.
q
CI
rN
F
A
A
E
a
?lq
{,
bo
gH
lr.l
)
Throughput Volume, Gallons
Comparison of Carbon A and Carbon B in Column Application
i8
\"
1
ii .E
.go
Experimental Conditions:
ii
t
a
'fi.
Eo
3E
E<
9q
<,
cat
Figure 34
2
0
\,"
1t
0
o
0 CarbonE
CarbonA
p
10
-0
vb o
zo
30
-
Key
€€
UU
o
C)
//
/
\
isO
IL
60
::
90
-74-
Io\
o
H
(,
tr
.o
o
t.E
e6
--o
onl
r€
o
EU
FE
tr
g
H
g
o
U
g
a
bo
i;
TABLE 15. Comparison of the adsorptive capacities of carbons A and B obtained in a column application.
+,
r+{
o
o
g
.F{
o
t{
d
P"
H
o
O
u')
f'l
rl
E
t-t
Carbon type A
Weight carbon in column
Flow rate
uo{LH
iT"i,isl
(Y')
:
!xfrfiY:
;l
sl:ig.sEqlgSEtgsl;8fis;tT;s;:8
j
€l'gfr$sI l 'lI;s B'ElrsH;triH;i:r
'tt
ul
rul
*
rn-rNc|t-dN
s
-f
+,
p.
k
o
a
d
q)
.O
si
O
l+{
o
o
o
+J
U
d
p.
d
()
0)
"i
b
C{)
FR
tr)
tn
-r
tno
0. 7
H
O
?
A
H
t1
ro
ci
rn
c;
E
N
\.
N
N
\.A
.t{
s Hl \ 9
l\
B,EU; Ho
H'gFf€i
3$soshSo
:Filnitl;lt
,:
E s,"EEi;-E$H
T $f,Ei:3t;,{
s E;sleExi!3
*n fl fl
suniB{gg
go UE; U* s E
ilg Tl.,iT * fissan$*nF,s,i'
H! H8 yi E
:rnT "*rn
i@E
e1b
o\ O f-
U . td N l - l - ' - r r n
c.lI
tl F r.' r{ d o. P{# d
dl
,|r
rfi
\b0
.d
b0
a
o
€
.&
h
d.d
it -,
SRfi :
E
BR*
Li
O
31 gallons
17. 9%
70%
798-910 mg/i
25-31° C
1 gal/mm/ft 2(20. 5mL!min)
F
"O
HOJ
b0-'<6
55. 6 g
f;
ca
B
e
t(l
lr)
d
o
g
p
t<
d
o
u
-i
b0
.r
6!
tt
.lv
€*
PO+t
Hfg; I
E'Eo.ss
E
,o$o,-ra\
@o\
.d ci
0. 96
38
55%
-r
'F
I
t3
TE J
B'8e.8€
HHs I T'!
at 75% COD breakthrough
Carbon adsorption capacity obtained at breakthrough conditions
lbs/1000 gallons
mg COD/mg carbon
.5 ,r Cvro
5. 1
,l
Percent COD removed at beginning
Percent COD removed at termination
Waste throughput volume to 75% COD breakthrough
Percent at adsorbable COD being removed
Q)
55%
?
E
Raw waste COD range
{agl ' o
ru)
Temperature range
E
23 gallons
+r
Carbon type B
Weight carbon in column
Flow rate
si
70%
11. 6%
Nd
mg COD/mg Carbon
d
at 75% COD breakthrough
Carbon adsorption capacity obtained at
breakthrough, lbs.! 1000 gallons
o
(J
Percent COD removed at termination
Waste throughput volume to 75% COD breakthrough
Percent of adsorbable COD being removed
E
t
1 gal/mm/ft 2(20. 5 mL/min)
24-31°C
865-965 mg/i
d
H
Raw waste COD range
Percent COD removed at beginning
o
'{
P.
p.
.p
d
Temperature range
,o
o
E
€g
Fi
(d
+)
53.lg
vi
-4
-75-
d
o
\o
..q
b0
I
d
.d = t
I
(gga) .rorceg uopcnpeg,trlcgo;
I;
I
02
0
4
N
N
b0
Tr
c
!
p
9
(,
a
(l,
rct
g
6
o
I
o
o/
/
"lcl
o
I
I
I
I
I
{6
aft
SH
g.e
R.q
,A()€
ai-9
s€.5
NEF
Ngi
b
GI
E
81012 14161820222426283032343638404244
(,
E
ro€
d$
sfo
€c
NT
df
o
U
H
@o
(n
ro
-.O
?.5
H{
o
N te
€u
b0(|
t.g
Throughput Volume, Gallons
rD
(,,
tl
6l
14
,
x
3
b0
Figure 35. Comparison of Carbon A with Carbon B in Adsorbing Toxic Substances
6
Experimental Conditions
Similar to those described in Figure 22
Ia.
0'
-76-
I
o
tr
U
aff
.l
g
b
o
E
tn
(a
ii
--7777-
100
90
80
Key,
H 7 070
g
G
lrl
..!
!0
FI
-
1-
-- {-----+------e-
60
60
r
-
tglnlttz
.2
3 gpn/ftz
.2
s gpmtft2
l0 grm/ft2
lso50
0o
o
E
u4040
0,
Or
30
20
10
0
10
Feet
Dep'ttr,Feet
Column
ColumnDepth,
of
Efficiency of
tfie Efficiency
Loadlng Kate
Rate on the
Figure 36.
ofHydraulic
Hydraulic Loading
Effectof
36. Effect
CarbonBB
Uring Carbon
COD Removal
Removal Using
2
-78-78-
obtalngd
sfinlLar to
to those
those obtained
obtalned with
wlth carbon
were essentially
eeaentlalty similar
results
carbon AA were
reoults obtained
gpailtt2,
1S gpm/ft2,
loading rate,
rate, 15
B. An
An examination
of an
an additional
wlth
additlonal loading
with carbon
carbon B.
examlnatl.on of
by
head loss
decreaeedhead
lose afforded
afforded by
possLble with
the decreased
was possible
to the
with this
thla material
matertal owing
owing to
wae
glzed particles.
efflclency
partLetea. A
removal efficiency
of COD
CODremoval
A relationship
reLatlonshlp of
larger sized
the larger
preaented
exanlned is
ls presented
rates examined
loadtng rates
bed depth
hydraullc loading
versus bed
depth for
for the
the various
varl.oue hydraulic
Flgure
37.
in
Figure
37.
ln
plota that
capable
meterlals capable
thst materials
these two
two plots
of these
It
evident from
le evtdent
from either
It is
elther of
quite
earl.y
are
removed
of
by activated
belng adsorbed
actlvated carbon
carbon are removed quite early
adaorbed by
of being
ln
of the
the curve in
Examlnatlon of
the adsorbent.
adeorbent. Examination
thelr exposure
to the
during their
durlng
exposure to
increaae
almoet negltgtble
Figure
negligible increase tn
in
at 5 gpmfft2,
ehowe an almost
Figuri 36
36 obtained
obta{ned at
epu.lft2, shows
an additional
addltlonal.
traete through
paesage of
through an
of the
COD
the waste
rae obtained
obtained after
after passage
CODremoval
removal was
do indicate
lndlcaFe
retea do
other loading
loadlng rates
Even though other
hed. Even
feet of
of carbon
carbon bed.
five
flve and
and ten
ten feet
galned are
be gained
are slight
elLght
advantages to
to be
be obtained,
the advantages
additional removal
removal can
can be
obtalned, the
eddltlonal
best.
a
att best.
yteld
deep column
column yield
frqn the
the deep
Bioassays
perforned on
obtatned from
Bloaasays performed
on effluents
effluents obtained
be analyzed.
anatyzed'
could be
Tp1 values
values could
of Tth
numberof
erratic
mlnLmumnumber
reaulta so
ao only
only aa minimum
erretl.c results
of
removal of
on the
the removal
tlme on
residence time
Figure 38
Flgure
38 depicts
deplctg the
the effect
effect of
of column
column residence
rate8.
loadlng rates.
hydraullc loading
toxic eubstancec
substances obtatned
obtained at
at two
trro different
dtfferent hydraulic
toxtc
the
that the
wae noted
noted that
Adsorptl.on -- It
It was
Selective
Substance.Adsorption
of Toxic
Toxl.c Substance
Selectlve Nature of
eontact
whlch
earbon
ln
adsorption of toxic substances in Batch tests, in which carbon contact
yl.elded
provlded in
teeta, yielded
col.umntests,
Ln the
the column
tlme provided
opportunity !ra!r
was much
much in
of time
ln excess
excess of
opportunity
eelectlvcly
are
organics
Apparently
toxic
organics
are
selectively
tot(tc
ln toxicity.
toxtclty.
dramatic
drarnatic reductions
reductlona in
have
BODcontent
content have
adsorbed
and BOD
the COD
CODand
to the
contributing to
matertals contributing
adsorbed only
only after
after materials
eLteE.
adeorptl.on sites.
the available
avaflabLe adsorption
had an
to occupy
occupy the
had
an opportunity
opportunity to
removal,
toxlcity removal,
quatltatlve observation,
concernlng toxicity
obeervatton, concerning
A strictly
qualitative
A
strlctly
revealed
effluents free
of the
kraft odor possesaed
possessed a relatlvely
relatively
the kraft
free of
that effluents
revealed that
the
thet the
noted that
also noted
Along these
it was
was also
Al.ong
llnes, it
theee same
samelines,
toxlclty.
degree of toxicity.
low degree
odor
possessedaa slight
ellght odor
treated
effluents obtained
columne possessed
contect columns
frmr the
the contact
obtalned from
treated effluente
the
to the
opaqueappearance
appearenceto
an opaque
as
well as
whtch imparted
lmparted an
materlal which
ae colloidal
colloldal material
aa well
toxtclty.
poaseealng considerable
conslderable toxicity.
sample
etl1l possessing
ln addition
eddltion to
to still
sanple in
the extended
extended
powderedcarbon,
and the
carbon, and
The isotherm
which utilized
utlllzed powdered
tests whlch
the
lsotherm tests
golutione
produced
odorlesg
clear,
contact
experiment
with
granular
carbon
produced
clear,
odorless
solutions
granular
wlth
carbon
contact experiment
column
effl.uents.
poseessed
than
carbon
toxlcity
which
possessed
considerable
less
toxicity
than
carbon
column
effluents.
coneiderable less
whlch
tndeed contrLbuted
It
was surmised
colloidal materl.al
material eould
could have
have indeed
contributed
the colloldal
that the
It was
surmised that
research
the research
of the
tlrne limitation
llmitatlon of
and time
to
the scope
scope and
toxlctty, but the
resldual toxicity,
to the residual
The
relationship
relatlonshtp
the
observatlon.
quantLtatlve investigation
thle observation.
prevented
prevented quantitative
of this
lnvestlgatl.on of
glven in
39.
Figure 39.
ln Figure
found betreen
between COD
COD removal
ls given
and toxicity
toxlclty is
removal and
be
to be
proceas is
found to
lg found
Preliminary
unit process
Whenany
any unit
Evaluatlon -- When
Prel{rninary Economic
Economlc Evaluation
questlon
the critical
crltlcal question
wa8tes the
technically EeaifUfe
feasible for
treatment of
of certain
for'treatment
certaLn wastes
Eectrnfcilfy
gttll remains.
prellmlnary
at least
Least aa preliminary
was felt
felt that
that at
It was
of economics
remal.ne. It
of
economics still
treatment.
carbon treatment.
actlvated carbon
the cost
of activated
attempt should
made at
cost of
be made
eotebllehlng the
at establishing
attempt
ehould be
by
be reduced
reduced by
prevlouely that
readtly be
It
was shown
the COD
could readily
thet the
CODcould
shoen previously
It wae
carbon in
ln aa
gallona of
of activated
actlvated carbon
pounde per 1000
75
cent using
uel.ng 3.8 pounds
1000 gallons
75 per cent
cloeely approximates
approxlmatea
Using a waste flow
whlch closely
of 2.5
mgd, which
flow of
2.5 mgd,
Uslng
column application.
appllcatlon.
column
carbon
were obtained,
obtalnedr carbon
eanrplecwere
the dlscharge
discharge of
of the nlll
mill where
where the
waste samples
the waste
the
per day.
logeea
pounda per
day. Carbon
Carbon losses
of 9500
requirements vould
would be
be on
the order
order of
9500 pounds
on the
requLrenents
-79-79-
-
Key:
Key:
I gpmlttz
igpm/ft2
-{F
3 gpmlftz
3gpm/ft2
-
Ss gpm/ft2
ep-/tl
lOgpm/ft2
lQ gpnlft'
iS gpmfft2
1
c
g
E
lrt
FI
b0
E
z
O.
0..
o
o
0
u
U
ll
!,
O
5
a,
2
50
,lo
c.
0..
t#
5t015
Column
Depth, ft
Column DePtJr,
COD
Efficiency of COD
the Efficiency
R4te on the
Hydraulic Loading Rare
Figure
Figure 37..
37. Effect of Hydraulic
Carbon
Removal Using
Carbon
A
Using
-80-80-
cot depth
,to
40
3E
38
36
36
34
34
32
32
30
30
28
28
1Ofoot deph
26
26
24
24
d 2 222
:
d' 20
g
J 20
la
; 1 8 18
g
a)
Pa 1 616
o
&
q 1 4 14
E
a
3rz12
10
10
8I
6
I 15 foot depth
4
2
10gprn/ftz I
CarbonB
p l0 foot depth
/
6 5 foot depth
o
0
(TRC)
Faetor(TRC)
Toxicity
Toxtctty Reduction
Reduction Factor
Reduction
Toxiclty Reduction
Residence Tlme
Time on Toxicity
Column Residence
Ftgure
Figure 38. Effect of Column
-81-81-
I00
100
90
90
80
80
70
70
b0
F
.E
60
60
cl
E
50
J50
ID
d
E
U
u
'lo
40
E
G'
g
tu
A
30
30
20
20
10
l0
0
(TRF)
Factor(TRF)
Toxicity
ReductionFactor
Toxictty Reduction
(Data
Remwal (Data
COD Removal
toCOD
Redrrtlon to
Toxicity Reduction
Relcttonship of Toxicity
Figure
39. RelatIonship
Flgure 39,,
B)
A
and
Obtained
with
Both
Carbon
A
and
B)
Obtelned wlth Both
-82-82-
per cent
cent per
flve per
eboue five
to about
amount to
due to
attrition and
due
and reactivation
reactlvatlon losses
loeeee amount
to eitrltlon
P€r
a
coet
of
at
per
carbon
pounds
day
6f
makeup
Thus,
about
480
pounds
per
day
of
makeup
carbon
at
a
cost
of
reacttvetlon.
480
Ttrua,
reactivation.
would
be
requtred.
$285
be required.
$285
of
the treatment
treatnent of
for the
granul.er carbon required
requ{red for
of granular
Ttre
lnttl.al charge of
The initial
detern{ned
tlnea
and
realdence
baeed on
2.5
of condensates,
on loading
loadl.ng rates
rates and residence times determined
2.5 ngd
mgd of
condensates, based
wlth an
an
pounda for
for treatment
treatment with
to 47,100
471100 pounds
in
ln the
the laboratory
columnc, amounts
amounta to
laboratory columns,
pounds
cost
a
at a cost
pounde in
proceas for
491400 pounds at
of 49,400
21300 pounds
for ae total
total of
additional 2,300
addltlonal
ln process
reactlvatlng
structures' reactivating
costg of
of supporting
aupportlng structures,
Additional costs
of
of $14,800.
$14r800. Addlttonal
end
{netrunentatfon and
pumplng and
and valving,
valvlng, instrumentation
faclllttee,
furnace, carbon handllng
furnace,
handling facilities,
pumping
per
coct of
of $l00,000-$l25,000
capltal cost
control systems
systems are
are estimated
eatfinated at
at aa capital
control
per
$1001000-$1251000
approach
woutd approach
gallona. For 2.5 rqd
costs would
mgd capital
capltal construction
construetlon costs
nllll.on
million gallons.
costs on
on
treatment costs
preeentg aa breakdown
breakdownof
eatlnated treatment
of estimated
17 presents
$300,000.
$3001000. Table 17
basl.e.
a daily
dally basis.
a
TABLE
17
TABLE 17
ngd
2.5 mgd
of 2.5
Treatment of
for the
the Treatment
Estimated
Eetlmeted Costs
Costs for
Condeneates
Kraft
Evaporator Condensates
Kraf
t Evaporator
Item
Cost $/day
Capltal Investment
Investment
Capital
facllltlea
Plant facilities
carbon charge
Initial
charge
Inttlal
80
80
20
20
Operating labor
maintenance
Operatlng
labor and
end mal,ntenance
100
100
urlllrle8
Utilities
100
100
Garbon
Carbon makeup
makeup
285
2e5.
TorAL
TOTAL
585
585
gallons
Treatment
coat, $11000
Treatment cost,
$/1OOOgallons
0.23
o,23
treatment
that carbon
carbon treatment
appears that
lt appears
analyeLst it
Based
Based on this
thle rather
rather crude analysis,
tthen
gomertlat
feaslble when
be entirely
entlrely feasible
However, it
may be
lt may
by itself
expenel.ve. llonever,
1g somewhat expensive.
lteelf is
methode.
treatment methods.
other treatment
used in
with other
uaed
ln conjunction
conJunctlon wlth
-83-
BIBLIOGRAPIIY
BIBLIOGRAPHY
1
1..
phystce and
third
of surfaces,
eurfaces, Third
The physics
and chemistry
chenlstry of
Keetngton. The
Adam, Neil
NetL Kesington.
Adam,
p,
Orford, 1941.
435 P.
ed.
L941. 436
ed. London,
London, Oxford,
2.
2.
Some effects
effects of
of kreft
kraft mlll
mill
B r e t t . 1957.
a n d J.R.
1957, Some
Alderdice,
A
l d e r d l c e , D.F.,
D . F . , and
J . R . Brett
Reeearch
young Pacific
Fleherlec Research
of the
the Fisheries
Journal of
Salmon. Journal
Paclflc Salmon.
effluent
on young
effluent on
Board
Board of Canada
Canada14:783-795.
l4:781-795.
3.
3.
the examinaStandard
methods for
for the
examlnaStandard methods
Publtc Health
Assocfation.
Amerlcan
Health Association.
American Public
p.
520 p.
NewYork, 1960.
1960. 520
ed. New
11th ed.
and waste
waete water. llth
tion
of water and
tlon of
4
4.,
o r nitroso,
nitroso'
P e a r l - B e n 8 o n ,or
s t a n d a r d l z e d Pearl-Benson,
Barnes, C
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1 9 6 3 . A standardized
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sulfite
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egtirnatton
method recormended
TAPPI
46:347-351.
TAPPI
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T
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TAPPI
22.
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theory of
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Foams
Foame in
ln chemical
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the effect
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the
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Wtldltfe Service.
Service.
Fishery
p.
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total. effluent
3
9
:
5
9
9
5
0
3
.
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32,
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llquor
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Foam
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wegt.
35t545-549.
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34.
94.
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35.
35,
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Avoidance reactions
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Fish and Game
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Research
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RG
5045
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RG
5045
of
llealth
Research
Inst{tutea
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4O-.
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effluents
ln kraft
BODreduction
reductlon in
removaL and BOD
M. Color
Color removal
McCormick, James
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Oregon
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New
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1961. Wood
p.
product. Washington.
I{ashlngton, 23
23 p.
type of product.
53.
53.
usefulness of
method
new rapid
rapld method
of a new
Ttre usefulnesg
Van
Van Hall,
Hall, C.E.
C.E. and
and V.A.
V,A. tenger.
tenger, The
Preprints
of
Preprtnts
of
In:
In:
water
analyete.
for
total
carbon
determination
in
water
analysis.
determlnation
ln
for total carbon
Waste
Water
Chemlstry,
papers presented before the
Division
of
Water
and
Waste
Chemistry,
papers
of
Dtvlsion
and
lhe
1963.
Chemical Society,
Ohlo, January
L4-L6, 1963.
January 14-16,
American
Amerlcan Chenlcal
Soclety, Cincinnati,
Ginclnnatl, Ohio,
p . 93-97.
93-97,
p.
54.
54.
The
of kraft
kraft
1950.
the effect
effect of
and M.
M. Katz.
Katz. 1950.
Van
Anderson, and
Van Horn,
Horn, W., J.B.
J,B. Anderson,
pulp mill
TAPPI
33:L09-2L2.
pulp
rntll wastes
on fish
flsh life.
TAPPI 33:109-212.
lrastes on
1ife.
55.
55,
by inpol.lutton control
tntfater pollution
control by
1963.
B.C. Mil1er.
Warner,
Warner, ILL.
H.L. and
Miller.
1963. Water
and B.C.
plant measures.
plant
meaBures. TAPPI
TAPPI46:260-266.
46226O-266.
A study
of constituents
constltuents
A
etudy of
pulp mill
wastee to
to fish.
Corflsh. Corm111wastes
of kraft
kraft pulp
for the toxicity
toxictty of
responsible for
(Oregon State
and Game
Game
p. (Oregon
of Fish
Fiah and
41 p.
Dept.
State University,
Unlversitl
DePt. of
vallis, 1961.
vallla,
1961, 4L
U.S.
report
on
U.S.
report
on
of Chemistry.
Complete progress
Management -- Dept.
Management
Dept. of
Chemistry. Complete
Progreso
5710. )
Public
5045 and
and RG
RG 5710.)
RC 5045
Grante RG.
Healch Service
Servlce Research
ResearchGrants
Publlc Health
56.
!{arren, Charles
N. Marvell.
Harvell.
Charles E.
E. and
and Elliot
Elllot N.
56., Warren,
methods
of
of methods
Ttre development
devel.oPment
1958.
1958. The
putp mill
waete disposal.
dieposal.
mlll waste
for
using bioassays
of pulp
bloaseaye in
control of
ln the
the control
for uelng
TAPPI 4l:2llA-2l6A.
rAPPI
4L:2LLA-2L6A.
l{erren, C.E.
P, Doudoroff.
Doudoroff.
C.E. and
and P.
57.
57. Warren,
58.
Toxic effects
of
1960.
effecte of
1960. ?oxtc
Washington State
Fisheries
of Flsherles.
IlaehLngton
State Department
Department of
(Research Bulletin
Bulletln
264
p. (Research
trout,
264 p.
pollutants
organic pollutants
on young salmon
salmon and
and trout.
organlc
N
o
.
5
)
.
No. 5).
- 878759.
59.
deEerminethe
the nature
nature
Prellmtnary studies
co determine
Webb,
studlee to
Webb, William
Will.tarn E.
E. 1958.
1958. Preliminary
pulp mill
Masters
naste. Dlastere
kraft pulp
mlll. waste.
of
principal toxic
toxlc constituents
constltuents of kraft
of the prlnclpal
Univereity. 53
53 numb,
numb.leaves.
leavee.
Corvallis, Oregon
OregonState University.
thesis.
theels. Corvallie,
60.
60.
Determination of
waste
earbon in
ln waete
of carbon
Weber, W.J. and
Weber,
and J.
Carrell Morris.
Morrts, DeterrnLnatlon
J. Carrell
l{ater PolluJournal of
of the
the Water
Polluwaters by
by high-temperature
wet oxidation.
oxldatton.
Journal.
hlgh-temperature wet
1964.
tion
Control
Federation
36(5):573-585.
L
9
6
4
.
tlon Control Federatlon 36(5):573-585,
61.
61.
toxlc compounds
compounde
kraft
Identification of
of certain
certain toxic
in
l{luan,
ln kraft
Wiman, R.E.
R.E. 1962.
L952, Identlf{catlon
46
numb.
Unlveralty. 45 nunrb,
OregonState
Srate University.
wastes.
wastea. Ph.D.
Ph.D. thesis,
thesia. Corvallis,
Corvallla, Oregon
leaves.
leaveg.
62.
62,
denelty
temperaturee and
and density
Sea water temperatures
Zerbe, W.8.
W.8. and
and C.B.
CB. Taylor.
Taylor. 1953.
1953. Sea
and Geodetic
GeodetLc
It.S. Department
Coast and
reduction tables.
reductlon
Departmentof
of Commerce,
tablee. US.
Connrerce,Coast
(Spec{al Publication
21 p.
p. (Special
No. 298).
tfaahLngton, 21
Publlcetlon No.
298).
Survey. Washington.
Survey.
63.
63.
Equilibria
on carbon.
carbon.
_______________.
for adsorption
adeorptlon on
and capacities
capacttlee for
Equiltbria and
-.
EngineerfJournal
f i r i c a n Sof
o c the
1 e t yAmerican
o f C 1 v t t ESociety
n g l n e e rof
a , SCivil
a n t E aEngineers,
r y E n g l n e e Sanitary
ring
lng Division
Dtvlslon 90(SA3):79-106.
1964,
90(SA3):79-106. June
June 1964.
64.
64.
from solution.
_______________.. Kinetics
on carbon
carbon from
solutlon.
Klnettcs of
of adsorption
edeorptlon on
Sanltary EngineerEnglneerEngineera, Sanitary
Journal
Amerlcan Society
Soclety of
of Civil
Ctvll Engineers,
of the
the American
Journal of
Aprll 1964.
L964,
ing
lng Division
Divlelon 89(SA2):3l-59.
89(SA2)r31-59. April
65.
65.
fro'rn secondary
senage
_______________.. Removal
secondary sewage
of organic
organlc compounds
compoundafrom
Removal of
A
paper
preeffluent
@
r a n u 1 a using
r r e g e ngranular
e r a b 1 e aregenerable
c t l v a t e d c e r activated
b o n . A p a p ecarbon.
rpre.
Anerlcan
l{agte Chemistry,
Chemlatry, American
sented
Water and
and Waste
the Division
Divlsion of
of Water
sented before the
L963.
Ohlo. January
January 13-18,
13-18' 1963.
Chemical Society
meeting, Cincinnati,
Chenrlcal
Soclety meetlng,
Cinclnnatl, Ohio.
- 88-
APPENDIX
APPENDIX
AP?ENDI.X
APPENDIX
STUDIES
RETENTION
flrIprES
4ETENrroN.
loee toxicity
toxtclty
effluente lose
that kraft
kraft ntl,l
bslleved that
ls believed
Introduction
mill effluents
Introductlon -- It
It is
pertod
tlme.
of
for
a
allowed to
to stand
atend for a period of time.
and allowed
when mixed
men
nfiAA with
dth saltwater
caltwater and
bactertal
dua
to
{e
thte toxic
toxlc loss
loac is due to bacterial
|.f, this
It
not clearly
underatood if
la not
clearly understood
It is
rrsaltlng out"
theae
of these
or aa combination
comblnatlon of
outtr effect,
degradment,
ef,fect, or
degradment, the
thc so-called
ao-called "salting
or
other unknowns.
unknownS.
or other
lagoon
to simulate
elmrlate lagoon
ettemPt to
an attempt
ueed here,
here, is
{s an
as used
The
Statl.c retention,
retentlon, as
The Static
dtludynamtc diluretentl.on rrlthout
storage whieh
which is
percent waste retention
without dynamic
lc defined
defl.ned as percent
storege
dl.lutlon
le continuous
contLnuoug dilution
dynamlc system
ayetem is
the dynamic
tlon
time, Conversely, the
tion wlth
with time.
an estuary.
egtuary.
ln an
of water
water in
ttdal exchange
exchangeof
with
wlth time,
tlme, similar
elnllar to
to aa tidal
to, aecertatn
ere to.
experlmente are
The purpoee
purpose of
ascertain l.f
if concentratlon
concentration
of these
theae experiments
Ttre
Alaot
time. Also,
wl.th time.
degradnent with
onthe
tha rate
rate ofof degradinent
of
wastes has
an effect
of the
the wastes
has an
effect on
P.B.I.
B.O.I).r P.B.I.
betweenB.0.D.,
correlatlon between
to
positive correlation
detetuine if
tf there is
la a pocltlve
to determine
between
A comparison
cmparleon between
bloaeaay. A
by the
the musgel
ae evidenced
evtdenced by
and toxicity
mussel bioassay.
and
tox!"city as
to
needed
ls
tystem
flush
tldal.
the simulated
lagoon
storage
and
the
tidal
flush
system
is
needed
to
and
the
eirnrlated lagoon
treatment.
nethode
of
two
paraueters
between
the
relate
degradment
of
the
parameters
between
the
two
methods
of
treatment.
ralate degradment of the
glaae jars
3-ga11onglass
were 3-gallon
contalner3 were
Materials
kraft retention
retentl.on containers
Matertale -- The
Ttre kraft
Jarr
by saltwater
caltnater
These
were
connected
by
nere
glaac aerators.
Ttreee
aerators.
frttted glass
;A[I[-pFdth
equipped with fritted
wlth
10
lltera
(photo
fllled
to
The
jars
were
filled
to
10
liters
with
t).
ltre Jara were
leeched latex
tublng (Photo 1).
tatex tubing
w111
Slx
Six
effluents.
kraft will effluents.
of strong
atrong kraft
ranple of
a diluted
eonpoalte sample
dlluted 7-day
7-day composite
year
of the
the year
tlmes of
varloue times
different
at various
of wastes
waetea taken
teken at
eanplee of
dlfferent composite
compoalte samples
tesE
the static
stetlc test
tn the
concentrattonc in
atudy. The
Ttra concentrations
used throughout
thle study.
were
eere used
throughout this
percent.
0.5
percent
and
percent,
L
percents
3
jars
were
10
percent,
5
percent,
3
percent,
1
percent
and
0.5
percent.
were
1,0
5
Percentr
Jare
saltwater
ppt, including
the saltwater
lncludlng the
25 ppt,
at 25
wag maintained
maintalned at
The
all cases
ln all
caeec was
sallnlty in
Ttre salinity
blank.
blank.
(Uyttlus edulis)
whtch
edullg) which
mussel (Mytilus
Bay rmrsael
wlth the Bay
Bloasaayr were
vere conducted
conducted with
Bioassays
outllned
the procedure outlined
to the
aciordlng to
were collected,
and spawned
spawnedaccording
cleaned and
were
collected, cleaned
(1965).
Breege (1965).
by Dimick
Dlmlck and
and Breese
by
waetee
the wastes
ttere run
run on
on the
P.B.L. were
Procedure
bioassays
B.O.D. and
and P.B.I.
bloaacays B.O.D.
Procedure -- Initial
Inlttal
solldat
Total
and
volatile
solids,
and
volatlle
Total
the
mflt.
frora
recelved from the mill.
as soon
was received
8s
soon as
es it
it was
calculated.
were also
also calculated.
pf, and
flowa were
pH
and total
total mill
mtll flows
after
daya after
to 33
33 days
from 33 to
Time
teets ranged
ranged from
perlods of
of, subsequent
aubaequent tests
Tlme periods
at
least
wae
tested
In
all
cases
each
concentration
was
tested
at
least
In all ca8e8 each concentratlon
teet.
the initial
tnttial test.
four
times.
four times.
aerated
and aerated
room temperature
tenperature and
The
at room
were held at
etud,ler were
retentlon studies
Ttre retention
frorn
each
w€re
removed
of larger.
container
mls. or
larger were removed from each contalner
of 500
500 mis.
Altquots of
ollghtly.
slightly. Aliquots
unto unthe salinity
sallntty to
When
evaporation
ralee the
would raise
I{hen evaporatlon would
varlouc tests.
tests.
for
for the various
untll
was
added
ltater was added until
favorable
biological concentrattons,
concentrations, distilled
dletllled water
favorable blologlcal
of the
the
componentsof
volatlle components
Ttre volatile
ppt. was
agaln reached.
reached. The
was again
of 25
25 ppt.
a salinity
eallnlty of
subjected
was
aubJected
the
effluent
where the effluent was
nlll where
at the
the mill
waste
to
Ue lost
loet at
co be
waste were
were assumed
ascrlmedtemPeratures.
to
vigorous mtxlng
mixing and
and elevated
etevated temperatures.
to vtgoroue
I
I
o-,
riw
of
those of
to those
proeedures for
are identical
identlcal
The
to
study are
for the
the semi-dynamic
eeml-dynamlc study
The procedures
every 2
changed every
First the
wastes were changed
the wastee
Firet
trro exceptions.
exceptlons.
the static
with two
the
static wlth
Secondly,
at 3_40C.
3-4oC. Secondly,
storage at
held in
tn cold
cold storage
to
fronr a stock
etock container
contalner held
to 3 days from
tflow-throught
ellghtly
the
concentrations of
of wastes
wastes in
system were slightly
ln the
the 'flow-through'
the concentratlons
percent kraft
of 20 percent
Example, the
highest concentratlon
concentratIon of
kraft wae
was
Example,
the highest
different.
different.
percent' etc.
Each
Each
percent and
etc.
to 10
turn the
the 15
15 to
10 percent,
diluted
to 15
and in
ln turn
dlluted to
15 percent
the cold
change
of waetes
wastes constltuted
constituted aa fresh
fresh etarting
starting Jar
jar ofof kraft
kraft from
fromthe
cold
chenge of
!.n
waa
achleved
eyatem
flow-through
In
this
sense
a
semi-dynamic
flow-through
system
was
achieved
in
eemi-dynamlc
room. In this Bense
$lth
fresh
ealtwater
been
had
tn
contact
which
the
minimum
concentration
had
been
in
contact
with
fresh
saltwater
whlch the mtnlmum concentration
which accumulated
eccumulated
bacterlal
fauna which
The bacterial
fauna
perlod of
maxLmumperiod
of time.
ttme.
over
over the
the maximum
changes.
durlng concentration
concentratlon changes.
was not
not removed
removed during
on the
sides of
of the
the jars
the sides
Jars was
(egge
gameEe8(eggs
mature gametes
obtalning mature
The Bay mussel
mussel bloassay
bioassay consisted
conalsted of
of obtaining
lhe
either
with either
to spawn
spann with
stl.mulated to
mussels whlch
which were stimulated
fron adult
adult mussele
spern) from
and sperm)
(Photo 2).
each
from each
Aliquots
Altquote from
2),
KCLor
or N114Cl2.
Ntt4C12. (Photo
of KCL
O.2 molor
motor solution
solutlon of
a 0.2
for
sultable for
concentrations suitable
to concentrations
kraft
diluted to
vessel were taken
taken and
and diluted
kraft storage
storage vessel
test
test
Ihe individual
lndlvidual
museiet. The
for the
the muséel.
limits for
determining
mean tolerance
deternrlnlng mean
tolerance limits
egge,
of eggs,
whlch consisted
conslsted of
dishes
contained a total
mis of
solution which
total of
of 100
100 mlg
of solution
dlshee contained
added
sperm were added
One
of eggs and
and sperm
One ml
rnl each of
toxlcant and
and saltwater.
saltwater.
sperm,
sperm, toxicant
the toxicant.
toxicant.
occur in
ln the
would occur
fertllizatlon
to the
the test
test dishes
dishes so that
that fertilization
to
the 48
48
(Photo 3)
prevent evaporation
during the
evaporation during
The
were stacked
to prevent
etacked (Photo
3) to
Ttre dishes
dishes lrere
dlsh
each dish
After
pertod at
After incubation,
tncubatl.on, each
temperature.
at room
room temperature.
hour
hour incubation
incubatlon period
vieual. separasePeraln the
the visual
atd in
to aid
received
drops of
of neutral
neutral red
red stain
Btain to
eeveral drops
recelved several
from anomalies
anomalles wl.th
hinged
tion of
of normat,
normal, shelled
shelled straight
hinged larvae
with no
larvae from
straight
tion
(Photo
shell
normal and
abnormal larvae).
larvae).
of normal
and abnormal
she1l (Photo 4 of
unblased
(Photo 5)
an unbiased
facllltate
built (Photo
to facilitate
devlce was
was built
5) to
A
an
A sampling
sampltng device
la
dlsh is
The
solution
from
the
test
dish
from
test
the
dleh.
The eolutlon
30 ml.
ml. aliquot
from the
the test
teet dish.
allquot from
The
conconThe
added to
to it.
it,
A.F.A. added
jar
poured into
and A.F.A.
kllltng
cyll.ndrical killing
lnto a cylindrical
Jar and
poured through
through
lnunediately poured
tents are
are mixed
mixed up
up and down
with a plunger
plunger and immediately
down with
tentg
a funnel
flaek,
the counting
counting flask.
emptying into
lnto the
funnel emptying
ftrgt 150
ernbryoa
the first
150 embryos
placed under a dissecting
mlcroaeope, the
This
dlssectlng microscope,
Ttrle is
ls placed
percent normal
nornral larvae.
tarvae.
the percent
counted and tallies
to determine
determine the
talll.ee are
are recorded
recorded to
counted
dishes in
ln
Control dishes
mussel. Control
The
is
hlnged mussel.
is a shelled
shelled straight
otralght hinged
crtterla
the criteria
was
percent or
better normal
normal larvae
larvae was
which
or better
was 50
50 percent
actuat count
count was
whlch the
the actual
proportionalty
$rere proportionally
dlshee were
The remaining
percent,
test dishes
adjusted
to 100
Ttre
remainlng test
100 percent.
adJusted to
blologlcal
This nethod
method eliminates
the actual
actual biological
elimlnates the
This
calculated
to the
the control.
control.
caLculated to
gametes of
of the
the
on the
the gametes
difference
between the
toxlcant on
of the
the toxicant
the effects
effecte of
difference
The
Ttre adjusted
adJusted
pute all
samescale.
eeale.
bloassays on
on the
the same
test
animals and puts
all bioassays
test animals
normal larvae
larvae
plotting
by plotting
the percent
Th1
the
determlned by
Ls then
then determined
Tlal value
value is
Percent normal
TLm
in
this
instance
this
instance
fia1
ln
taken.
lt
was
versus
the
concentration
from
which
it
was
taken.
from
which
concentration
veraus the
percent
of
the
embryoe
refers
to
the
theoretical
concentration
where
50
percent
of
the
embryos
where
50
concentratlon
refers to the theoretical
abnormal
percent
are
elther
have developed
normally
and
50
percent
of
the
embryos
are
either
abnormal
the
of
embryos
developed nornally and 50
or dead.
or
dead.
data sheet,
sheet,
on aa data
Physical
information
was recorded
reeorded on
biologlcal
lnformatlon was
Phyeicat and
and biological
gptcal
solid
total/volatile
data and
weekly flow
flow data
and total/volatile solid
Table 88 appendix.
appendLx. Typical neekly
Tables 99
be found
on Tables
will be
found on
data whlch
which help
help to
the
wastee will
the wastes
to characterize
characterlze
date
and
appendix.
and 10
10 appendix.
4,
tests 4,
and tests
Series AA and
be treated
ae Series
Discussion
treated as
will be
2, and
and 33 will
Tegts 1,
lr 2,
DLgcusslon -- Tests
in
conrnon
group
characterlstics
has certaln
certain characteristics
in common
B. Each group has
Sertes B.
ina 66 as
is Series
5 and
of simplicity.
sfurplicity.
for the
the sake
sake of
treated as one for
shall be treated
and therefore
therefore shall
A-3
A-3
(Ftgure 3) lost
percent of
The B.O.D.
B.0.D. in
{n Series
80 percent
of its
oxyger
Tte
Serlec A (Figure
lost 80
lts oxygen
percent
demand
after three
of retention.
demand in
concentrations of
lower
tn concentratlons
of 5
three days
daya of
retentlon.
lower after
The 10
much slower
not reach
reach the
The
l0 percent degraded
degraded at
slower rate.,
It did
dld not
the
at aa much
rate., It
psrc€nt of
same
of degradment
until. after
sam€ percent
degradmentuntil
after 12
daya of
of storage.
storage. The
the initial
{nltlal
12 days
percent of
B.O.D. of
ppm. and
B.0.D.
of the
thc 10
wac 38.3
and 90
of this
10 percent wastes
wastes was
38.3 ppm.
90 percent
thia
was removed
after 20
20 days
of retention.
B.O.D. values
was
The
reuoved after
daya of
actuet B.0.D.
valueg are
are
retent{on.
the actual
listed in
llcted
ln Table 3 appendix.
appendl.x.
(Ffgure 6)
(Table
Comparing
Coqarlng the
the B.0.D.
B.O.D. data
data of
6) and
of Series
Sertea B,
B, (Figure
and (Table
pattern of
wlth that
percent degrad6 appendix),
appendtx), with
Serlaa A, the
degradthat of
of Series
the same
of percent
sarnepattern
ment Le
ntent
is seen.
of
degradlng
The 10
percent Jar
of
kraft
degrading
at
a
slower
rate
86etro the
10 percent
kraft
at
a
alower
rete
Jar
untll 20
daya of
practtcally all
20 days
of storage,
when at
of the
until
atorage, when
at this
thla time,
all of
the
ttlne, practically
B.O.D. yas
B.0.D.
was removed
removedfrom
fron the
ayetem.
the system.
(Table 22 appendix)
(Figure 2)
The
Pearl-Benson Index
of Series
2) (Table
appendtx)
Ttre Pearl-Benson
Index of
$erlee AA (Figure
percent
decreased
dec.reaaedat
et aa slower
but reached
slower rate
B.O.D., but
rate than
than the
the B.0.D.,
reached the
the same
aamepercent
The
loss
of
P.B.I.
level
of
level of
of degra&nent
degradment after
10
and
20
days
retention.
after 10 and 20 daya retentlon.
P.B.I.
The loas
Results
la
is apparently
apparently not
not effected
effected by the concentrations
of KME
KllE tested.
tested. Regultr
concentratlons of
from the
becauge it
the 0,5
0.5 percent
percent KME
XME have
have been
been disregarded
doubtful
dlsregarded because
lt is
ts doubtful
that
technlques and
accurate
that the
the techniques
and equtpment
equipment used
used in
measurement is
ls accurate
ln P.B.I.
P.B.I. meaaurement
(Table
(Ftgure 5)
Series
at
at the
the lower concentrations
of kraft.
kraft.
B1 P.B.I.
5) (Table
concentratlone of
Serles B,
P.B.I. (Figure
After
5 appendix)
appendlx) degraded
degraded at
A. After
at aa much
much slower
el.ower rate
than in
ln Series
Sertes A.
rete than
30 days
days retention,
50 percent reduction
was noted.
noted.
retentlon, only aa 60
ln P.B.I.
P.B.L. was
reductlon in
wlth concenAgaln there
nas no
Again
there was
no significant
dtfference in
of P.B.I.
P.B.I. with
asncenslgntfleant difference
ln loss
loss of
tration.
tratl.on.
Mussel
Namely,
Mussel TI.'ta of
of Series
Narnely, the
Serles A led
led to
to some
unexpected resultá.
resulte.
the
someunexpected
toxicity
with retention
toxlclty increased
rate of
decreaced
lncreaged wlth
retentlon time
tlme and
and the
the rate
of toxicity
toxlclty decreased
with
wlth concentration.
That is,
at the lower concentrations
toxictty
concentration.
concentratl.ons the
that
ls, at
the toxicity
general
at a faster
In
lncreeeed at
faetet rate
In general
increased
rate than
than the
the higher
hlgher concentrations.
coneentrations.
approxftnately an
there
was approximately
80
percent
increase
in
toxicity
after
20
there was
after
20 days
daya
an 80
lncreeee ln toxiclty
have
retention
of
KME.
Several
hypothesis
as
to
why
this
happened
have
retentton of KME, Several hypothesls e8 to why thla happened
been
been advanced,
advanced, but we
we do
do not know
know the
Other investigators,
the answer.
anslrer, Other
tnvestlgatora,
phenomenonhave
obeervlng similar
aimLl.ar phenomenon
breakdown of
of organic
observing
organl.c
have attributed
attrlbuted it
lt to
to aa breakdown
rnaterl,al and
material
and aa release
releaae of
of metabolites.
metabolLtes.
During
months of
pulp production
productlon when
Ilurlng the
the summer
of pulp
when the
waste samples
aunmer months
the waste
sanplec
practlced,
were
taken for
for this
belng practiced.
were taken
thfs series,
mlll operations
operationa were
were being
serfes, several
several mill
Flrst, aa mercuric
First,
was betng
being used.
mercurlc sliinicide
chelatsllntclde was
used. Secondly, a calcium
calciurn chelatplpe to
tng conrpound
Eo the
ing
compound was
was introduced
lnto the
and also
also aa copper
the
tntroduced into
the wastes and
copper pipe
wagte
of these
waste sampling
statlon was
wae inadvertently
lnadvertently used,
these facfaceampllng station
ueed. Any, or all
all of
tors could have
Shelltors
have had
had catastrophic
on the
the mussel
muesel embryos.
catastrophlc results
results on
enbryoa. Shellneed
fish
mercury and
and of
of course
sensltlve to
to mercury
and copper,
copper, and
couree need
extre[el.y sensitive
fteh are extremely
calcium
to
These
calctum for
unllkely to
for shell
ehell disposition.
dleposttlon.
These same
same compounds
compoundsare unlikely
B.O.D. or
the
effect
effect the
the B.O.D.
or F.B.I.
degradment. Therefore, we
we feel
feel that
that the
P.B.I. degradment.
unusual chemical
probably contributed
to the
the
unusual
chemlcal factors
factora of
of the
the raw
raw wastes
waates probably
contrlbuted to
obeerved toxic
observed
toxlc increase.
lnerease.
Comparing
Serlee BB TLm
data with
wlth that
Serlee A,
A, aacomplete
reverConparlng Series
1Lmdata
that of
of Series
co'npletereverbeen changed
sal of
eal
of toxicity
However, the
had been
also. The
toxlclty is
le noted.
noted. However,
the waste
changedalso.
Ttre
lraste had
been elimifactors which
wtrlch we
se felt
had been
factors
felt responsible
for the
the toxic
Lncrease had
ellmlresponeLble for
toxic increase
nated. That Is,
nated.
mercuric cllmlcl.de
slimicide was
was dtocontinued,
discontinued, the
the calclum
calcium
Le, the
the mercurlc
chelating
changed to
of a different
formula
chelatlng agent
egent changed
forunrla and the
the copper
to one of
dlfferent
the
line replaced
replaced wtth
with one
In
llne
one of
addltlon to
to these,
of stainless
In addition
theee, the
atalnless steel.
ateel.
pereent with
strong
strong waste
waste was
was diluted
wlth wash
waehwater.
water.
dtluted approximately
approxlmately 17
17 percent
A-4
A-4
(Table 4 appendix) shows
degraded much
muchslower
elower
Figure 4 (Table
Flgure
toxlclty degraded
ehowethat
that the
the toxicity
(Flgure
(Flgure 6),
than
the
P.B.I.
than the B,O.D.
B.0.D. (Figure
but
slightly
faster
than
the
P.B.I.
(Figure
6),
el.lghtly faster
percent of
20 days
days of
of retenretenafter 20
About 80
80 percent
of the
the toxicity
toxlclty was
5).
5). About
was lost
loetrafter
the rate
rate of
of
tion. The
do with
wlth the
of Kraft
Kraft had
to do
tlon.
concentratton of
had little
Xtre concentration
ll.ttle to
below the
were below
the
toxicity
toxlclty degradment.
degradurent. The
Ttre lower
lorer concentrations
tested were
coneentrotlons tested
graph aa TLm.
necessary to
values
valuea necessary
to graph
TIa1.
baeed on
on the
the mean
meanof
of the
the
Flgurec
Figures 7 and
and 88 are theoretical
theoretlcal curves based
These curves
lnaamuch
lmportant inasmuch
sample
means at
sarple saans
at all
all concentrations.
culr/es are important
concentratlons.
Ttreae
dlfferenie
th€ supporting
as the
eupportlng data reveals
reveals that
that there
there is
ta no
no significant
slgnlflcant difference
wlth the
the
betneen the
teat€dr with
between
degra&nent of
of KME,
KME,and
and the
concentratlons tested,
tha degradment
the concentrations
pereent to
to 10
10
0.5 percent
exception of
of B.0.D.
B,O.D. The
from 0.5
exceptlon
Ttre concentrations
concsntrattons ranged
ranged from
porcent and
percent
approxlmates the
the
and the
of the
the mean
meanof
the sample
earnplemean
meenvalues
values closely
cloaely approximates
glve
percent
woul.d
of the
mesns
curve of
5
percent
jar.
It
was
felt
that
these
means
would
give
the 5
Jar. It was felt that theee
pLotting the
plcture
the 55
a more
more realistic
picture in
degradrnent,than
than plotting
reallstlc
tn terms
terua of
of degradment,
percent
polnt
the
Becauae, each
currres represents
represente the
percent values
alone. Because,
on the
the curves
valuec alone.
each point on
nean
mean results
resulta of
of fifteen
flfteen separate
separate tests.
te6ts.
of degraddegredthat the
rate of
A
A comparison
the rate
conrparlson of
of Figures
Flgures 77 and
and 88 illustrates
llluatretes that
greateet percent loss
ment of
both series.
losa of
nrent
of B.0.D.
B.O.D. is
elmllar in
ln both
serles. The
lhe greatest
ls similar
P.B.I.
follows a
P.B.I, follows
B.O.D. occurring
firet 33 days
daye of
B.0.D.
occurrlng in
ln the
of retention.
retentlon.
the first
general
general degradment
degradment trend,
but ln
in terms of
of total
total percent
percent reductlon
reduction end
and
trend, but
There wea
was
also
also rate
rate of
of degradment, ltit ls
is lees
less than
than that
that of
of the
the B.O.D.
B0.D. Ttrere
percent greater
greater loss
degradedmore
more
lt degraded
a 40 percent
of P.B.I.
P.B.I. in
and it
loae of
ln Series
Serlee AA and
wlthln the
The rneJor
major loss
rapidly than
occura within
ths
raptdly
SerLes. Ttre
of F.B.I.
P.B.I. occurs
than in
ln the
the BB Series.
loea of
first
flrat 10
daya of
10 days
of retention.
retentton.
data is
ts absolutely
abeolutely
because the
the data
The
llhe toxicity
toxl,clty curves oppose
oppose each
other because
each other
wastes.
polnts up
of kraft
kraft wastes.
conflicting. This
up the
the vast variability
verlablllty of
eonfllctlng.
Thls points
Emphasis
as evldenced
evidenced
be centered here on the fact
fact that
toxl.clty, aa
Emphaelashould be
that toxicity,
B.O.D. and
and P.B.I.
P.B.I.
by the
of B.0.D.
by
bloassay, is
lndependentof
the mussel
nussel bioassay,
ls completely
conrpletely independent
wlth
and
should
not
be
related
to
or
confused
with
them.
not
be
to
and
confueed
them.
related
A
syotemB
A brief
brl.ef comparison
betreen dynamic
retentl,on systems
conparlson between
dynanrlc and
and static
atatlc retention
degradnent of
reveals
of kraft
kraft
overall degradment
reveals 8ome
sone interesting
lnterestlng changes
changee in
ln the overall
gtatlc retenof static
retenwlth the
wastes. A
weates,
A dynamic
dynaurictest
the same
test with
eane effluent
effluent sample
sampleof
was in
operation
etudy wae
in operatlon
tion
used. thte
This rflow-throught study
tlon 6 of
of Series
SerLes BB was
ras used.
A bacterial
fauna was
was established
bacterlal fauna
establtshed
one month
month before test
were taken.
one
sarylee were
taken. A
test samples
approxtmate
wlth
an
Bay
on
somewhat
simulating
the
Bay
with
an
approximate
on the
the sides
of the
almulatlng
the
al.des of
the jars
somewhat
Jars
dynam{c
Figure 9 shows
that the
the dynamic
days. Flgure
percent tidal
€very 22 days.
ahowe that
50 pereent
tldal flush
flush every
tn the
the static
than in
etatl.c
test
more in
at aa faster
faeter rate
test decreased
decreased more
ln toxicity
toxlclty and
and at
rate than
rate
The B.0.D.
B.O.D. and
P.B.I. disappeared
at an
an excellerated
system. Ttre
atrd P.B.I.
dlsappeared at
excellerated rate
Bystem.
$tastes and
kraft wastes
and the
the
also.
were run
on other
other kraft
aleo. Several exploratory
tests were
run on
exploratory tests
been omitted
omltted
qulte similar.
Ilowever, this
data has
has been
were quite
thls data
results
reeulta were
elml.lar. However,
param€ter8 were
elmultaneously.
w€re not
not run
because
because tests
on all
of the
the parameters
run simultaneously.
teets on
all of
It is
our contentlon
contention that
that ln
in terms of,
of degradment,
degradment, aa flow-through
flow-through ayetem
system
It
te our
than lagoon
lagoon
qul.cker and
waetee than
of wastes
indicates a quicker
more complete
co'nplete treatment
creatment of
lndlcatec
and more
type storage.
typc
Btorage.
Sunnnary for
for Retentlon
Retention Studies:
Suruury
Stud{es:
Concentrations of
of strong
kraft m111
mill effluent
effluent up to
to 10 percent
percent
1.
etrong kraft
1. Concentratlons
volume does
not effect
effect the
degradment of
of the
the toxlclty
toxicity (vla
(via
by vol.rnne
does not
the degradsrent
bloaasay) or
P.B.I..
mussel
ntresel bioassay)
or the
the P.3.1..
A-5
A-5
2.
2 . The
rate of
of B.O.D. degradment
degradnent is
by concentration.
Ttre rate
ls effected
effected by
concenttratl.on.
the concentration,
The
The higher
hlgher the
concentratlon, the
B.O.D. is
the slower
alower the
the B.0.D.
lg removed.
removed.
Tte
The greatcat
greatest percent
percent drop in
ln B.0.D.
B.O,D. occurs
dayc
occura in
tn the
the first
flret four
four days
of
o
f storage.
storage.
3.
3.
ls completely
Toxlctty is
completely independent
B.O,D. and
Toxicity
lndependentof
of B.O.D.
P.B.I, and
and P.8.!.
8nd
should not
not be
be related
greatest percent
ahould
related to
to them.
percent drop
them. The
Ttre greatest
drop or
or increase
lncrcere
of toxicity
toxlclty occurred in
ln the
of
the first
f,lret 10
of retention.
1.0days
days of
retention.
beare no
P.8.1.
P.B.I, bears
no direct
d{rect relationship
relstlonshlp to
B.O.D. as
to B.0.D.
lts rate
rate of
of
as its
degra&nent
degradment and
and percent
percent of
of degradment
degredurent display
dlaptay wide
wlde fluctuations
fluctuatlonc with
wl.th
greateat percent
varl.ous kraft
percent drop
various
kraft effluents.
eff,luentg,
P.B.I.
The
Ttre greatest
drop in
ln P.B.I.
occur8 in
occurs
ln the
the first
f,lrst 10
daye of
10 days
of storage.
etorage.
4.
4.
gnd at
B.O.D.,
B.O.D.r P.B.!.
P.B.I. and
and mussel
more and
muegel Tlare decreased
decreaaednore
at aa faster
faster
rete under
under simulated
stmulated tidal
rate
or lagoon
ttdal flush
flush systems
lagoon
syatems than
than in
ln static
stattc or
type retentl.on.
retention.
type
5.
5.
potentlatly sensitive
6.
6. The
btoacray is
The bioassay
La ae potentially
nethod of
of
aensltlve and
and reliable
relLable method
expressing mcan
mean toxicity
expreeelng
toxlclty values.
valuea. Nevertheless,
Neverthelega, much
remal,nsto
b€
much remains
to be
learned about the
the mueeel
learned
mussel and
and its
lts requirements
requlremencs especially
ln the
the
eapeclally in
ilatandardtl
phasec, This
embryonic phases.
embryontc
Ttrts knowledge
knowledge in
tn conjunction
wlth aa "standard"
conJunctton with
and constatently
and
consistently reproducible
must in
reproduclble synthetic
cynthetlc seawater
Beaweter is
te aa must
Ln order
order
perfect the
to
the mussel
bloaeaay. Further
to perfect
mueeel bioassay.
mandatory as
Further research
ss
reaearch is
la mandatory
pollutlon biologist.
Lt wt1l
to an
blologlet.
it
will lead to
an invaluable
tnvaluebl.e aid
for the
narlne pollution
ald for
the marine
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Mean
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Index at
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each oonoentratlon
concentration for
for
MeanPear].
Pearl Benson
2t 3.
L, 2,
Statla
3.
Static Reteutlon
Retention Sttdtcg
Studies 1,
flne
Time
Test #
Test
#
0
0
I
1
2
2
3
3
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770
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270
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226
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Tabl.e
Table 55
Studles
Index for
for Statla
Static Retentlon
Retention Studies
Mean Pearl Benson
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at each
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13
Table 8
8
Static
Retention Study #6
Sta.ttc Retention
*6
T = 55
Tz
January
1966
January 12,
L2,1966
Englneering Test
Engineering
Nunber -Test Nr.unber
I1
_iSpecial Biological Test Niber
Cone
-
No.
No.
('M
No.
%
fl.JJ1
flN1
An
5Q
138
92.0
12
128
125
5Q
5Q 110
43
5Q.
0
5Q_
85.4
22
92.8
83.4 25
90.7
No.
TIM
At41..
100.0
r
Disi
Deicription of
l0 Jtir
Q
EE
5% Jar
ts
BB
Waste Treathent
i_
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2
J_ 1.0
3% Jar
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1% Jar
5Q..
73.4 40
28.7 17
0
150
79.8
0.85
31.22
0.0
Date, Time,
KME
Tlure, Location
Location KME
0
Sample Was Taken Dec.31, 1965 to
0
150
..
Jan. 6, 1966 "Strongt' Wastes
Toledo H 31, Toledo, 0 egon
137
- 8
pH
p H -=
8.2__.2
U.V, lapht ticated
Filtered
Salinity (Actual)
Tenperature
Mj. Salinity
Fresh
Chilled
Color (packets)
Respawned
Yes
SaltWater
No
Yes
L0O. 0
1
2
later
No
.1
_,
)isti.lJed
5
6
l.0
2.0
O
150
128
Q_ 119
Q
Q
Q
1
1_
0
0
Q
85,4
79.4
73.4
22.0
0
0
22
31
93.4
40
869
80.3
150
150
24.1
0.0
0.0
llO.75_
Sperm
Yes
J No
J______
Femaie4.Naled
Spawning Induced byKCl 2ns,/iiter
Coni ci
.1
1
2
Test Organism Used - Mytllus edulis
6
Time, Date of Fertilization,
lzatlon Test
4:)0_pm, Jan.12, 1966
Type of Test - 48 hr. Bioassay
Q
-
Q
2
3
150
Q_
5Q
Cow
21 ± 1°C
Temperatuie of fnubation
ncu.batlon 21°C
jQ 19_
5Q_
15
41.05Q
O
j 59
.5
.,0
150
Q
l2
12
1)_
43
0
0
137
135
134
130
32
86.7 20
82.7 26
82.0 27
70.7 44
28.7 iai
O
0
0
150
1.4 13
90.0 15
89.4 16
73.4 4O
21.4 118
LO0.O
94.
____
0.85
81.5
33.1
0.0
0.0
100.0
0.75
98.5
97,8
80 3
23.4
Dissolved Oxygen at
Start
/irdsh
Solution in
Mi.
Ml of
of Solution
ln
- 100
Embryo
&n
o Dish
Dish 1O0
0. P. I.
"Low Salinity
Salinitrr in
I Bay due to
Heavy Rains, water taken on
High tide.
Ctd.:
CODE
C0DEFOR
FORABBREVIATIONS:
ABBREVIATIOIIS:Ctd.:
An:
An:
EE
)ilution
-25.8
20°C
13°C
24,8ppt
Ova
0va
Yes
No
White
91.4 1
____ _____ _____ ______
No::nall
Counted;
N1.: Normal;
Counted; Ni.:
Adjusted
Anomalies;
Adj:
:
Ad.Justod
Adi
Anonalles;
IJ
A-14
A-1.4
Table 9
nStrongrr Effluent
Effluent -Total and Volatlle
Volatile SoLlds
Solids in
Total
ln Toledo "Strong"
100
100 mis.
mls.
- 5/20
Composite
Composlte Sample
Sample 5/14
S/Ltr 5/2O
8ng. Static
$tatlc Retention
Eng.
Retentlon Study #2
#2
rrStrongrr KME
100 m1s
mis dried
r.rt. 6 100
KME
Dish
Dlsh wt.
dried "Strong"
Dish
Dlsh wt.
r.rt. empty
enpty
(l 14)
fa)
(L
Welght of
Weight
Residue
KMERosldue
of 1(ME
C
Dlsh wt.
a.fter' 2 hr.
Dish
@ 60F
600° C
wt. aftex
hr. Burning
Burnlng @
gg, jilojj
98.50635
98.36195
98.36t95
0.14440
O.1l+UO = Tot].
To'bal.Solids
Solids
98.42840
98.l+281+o
Weight
lleight of
of KME
KMEResidue
Residuo
0.07'795
o,gl7g5
Diffeieice between
Differerrce
betueen residuos
residues
0.06645 := VolattLe
Sollds
Volatile Solids
0.06645
rrStrorrgn KME
KME
Dash
Dlsh wt.
r,rt. A 100
L00 mis
mls dried
dried "St.rorig"
Dish ut.
vt. empty
empty
(no
(no mark)
mark)
Weight
Weight of
of KNE
KMEResidue
Residuo
after 22 hr.
Dish wt.
hr. Burnlng
Burning @
@ 6000
600°CC
wt. after
91.8280
91.8280
91.6857
9t.6857
0.1423
O.LI+23i Total
Solftls
Total Solids
gr.75355
91.75355
o.wl,A5
Weight of
lJeigtrt
KMEResidue
of K
Residue
0.cY7445
Diffex-eiice
between resiclues
Differerrce between
residues
O.C6785: Volatile
0.06785
Sollds
Volatile Solids
A- 15
A-15
Table
Table 10
10
Toledo Mil.1
Mill I'leekly
Weekly Flow
Flow Data
Data for
for
Toleclo
(5/14-5/20)
1r1y-5/zO)
Eng. Static
Statlc Retentlon
Eng.
Retention Stucly
Study #2
#Z
Date
Date
Total
Total H20
H20
Eff.
Eff. to
to
River
Rlver
Clear
CLear Eff.
Eff.
SEL
sEt
5/14/65
5/u/65
Lt1795
11,795
61691
6,690
3,340
l ftro
5,105
5]o5
5/15
5/r5
12,028
L2rCQ$
lrrQ3
4,023
3,760
31760
8,005
8r005
5/16
5/16
11,818
11r818
6r7l+I
6,741
4,104
/+tl0t+
5,77
51477
5/17
5/L7
12,803
12r603
8r466
8,488
3,888
31888
lur3r5
4,315
5/18
5h8
r)rraz
13,102
7,706
7 17C/o
l+r32O
4,320
5,496
5r&%
5,'19
5he
LLrTl+C
11,740
6rr59
6,158
4,104
L|IOI+
6,980
6rggo
5/20
5/20
12,819
12,gtg
6,140
6rr45
3,560
3 1560
61679
6,679
Avg.
Avg.
12,300
12r300
61563
6,563
3,725
)1725
5,950
5r95o
A -l 7
-
1
---
-
_.
I;
a
V
o
I
H
a
-
S
A -1 9
H
*
$*
*
*u
*
d
T{
tr
0
tsl
a
{J
r{
t)
rl
I,..
xo
+t
tr
.rl
H
o
rl
+t
I
'd.
9,5
H
II
{J
Crl
rDO
c, ul
t{ ttl
0r5
P{ :E
I
Iu.uu..uu.wa..a. r
l.-22
I
$
.-
...........
uusauu.0
Ftguro 7
Serles Ae Thooretlcal curves based on the nean
of sampLemeans at aLl concentratlons of the flrst
3 tests, comparing 8.0.D., P.B.f. and mussel 1l1ors.
0
0
Days Rotention K.M.E.
A-26
A-26
1I
TABLE11
TABLE
at
Salt\rater at
ln Saltwater
Degradment in
Albany
Albany Mlll
Mill Wastee
Wastes Degradment
p p t Salinity
p t and
a n d 25
2 5 ppt
Saltntty
1
155 p
ppt
BloSea
15
forttfled wtth
15 ppt
ppt fortified
with BioSea
p
p
t
t o 25
S
a
l
l
n
l
t
Y
to
ppt
Salinity
35
Control
Control
17. KUE
1%
IGIE
27
27.
37
37.
fl
"
rt
"
Control
Control
0.5% Kt[E
0.57.
KME
1.02 tl
1.07.
3 . W . "I t
3.07.
tf
6.O7.
6.07.
"
'
Natural Seawater
Seawater
Sallnitv Natural
25 ppt
ppt Salinity
_il
92.07. Normal
92.07.
Normal Larvae
Larvae
82.7
82.7
75
76.0
T l a * 21 .75
76.0
TLm
34.7
34.7
Control
93.47. Normal
93.47.
Normal Larvae
Larvae
17.
KME
1Z KllE
rl
27. "
27.
tl
37. "
37.
90.0
90.0
77.4
77.4
32.4
32.4
82.7
82.7
80.7
80.7
73.4
73.4
36.7
36.7
Control
Control
0.5% KHE
0.57.
KME
tl
1.07.
1.02 "
rl
2.07; "
2.07.
fl
3.O7. "
3.07.
rl
6.v1. "
6.07.
80.0
80.0
80.0
80.0
!.7
T16, r 2.7
TL
0
.0
0.0
f i * ' * 22 . 77
TLm
74.7
747
58.0
58.0
33.3
33.3
0.0
0.0
TABLE 12
12
TABLE
Natural Seawater wlth
with
Bl.oSea versus
verous Natural
BioSea
l.tastes #4
statlc
Retentton Wastes
Static Retention
dllutlon
Natural Seawater dilution
Natural
B
l o S e a dilution
dllutlon
BioSea
Control
Control
0
. l z Kt
0.17.
KNE{ E
0
. 2 5 7 . t"t
0.257.
1 . 0 7 . "i l
1.07.
3 . O 7 . t"t
3.07.
92.77 Nornral
92,77.
Normal Larvae
Larvae
9 1 .4
91.4
91.4
91.4
TLr' a 1.95
!.95
TLm
8
6.0
86.0
0.0
0.0
Control
Control
0.17. KME
0.17.
KME
0.57.
o.57.
"
n
"
t
'
2.07.
2.O7. "
1.07.
r.0z
80.07.
Normal Larvae
Larvae
80.0% Normal
80.0
1.2
76.7
76.7 TLm
r ln - 1.2
4g.7
49.7
0.0
0.0
TABLE
TABLE 13
13
wlth Albany
Albany
Saltwater with
BloSea versus Natural
Natural Saltwater
BioSea
Wastee
M l 1 1 Wastes
Kraft
K r a f t Mill
BloSea
KllE
BioSea in
ln KME
Control
17.
KNE
IZ KME
27.
27.
37.
37.
47.
47.
67.
67.
rl
"
rl
"
rl
"
ff
"
74.67. Normal
Normal Larvae
Larvae
74.67.
66.6
66.6
6o.7
60.7
50.7
50.7
36.0
35.0
0.0
0.0
KllE
in KNE
Real Saltwater
Sattlrater in
Control
17.
KNE
I% KHE
fl
27.
27.
"
fl
"
37
37.
rl
"
47.
47.
rl
"
67.
67.
7.37.
Normal Larvae
Larvae
7.3% Norrnal
6.7
6.7
5.3
5.3
2.7
2.7
00
0
.0
0.0
0.0
A-27
A-27
A test
of havlng
having a reproductble
reproducible synthetlc
synthetic
teet showing
showtng the
the importance
lmportance of
posslble
bioassay
bloaosay medium
manner it
was possible
Ls seen
aeen on
on Table
medlum is
Table 13.
13. By this
thts manner
lt was
gamete viability.
guallty or
This
to determlne
dlfferences in
of gamete
to
determine differences
water quality
ln water
or of
vlabtllty.
Thls
poor quality
qualtty and
domonstratee that
table
clearly demonstrates
table clearl.y
that the
was of
and
the real
real. seawater
of poor
seswater was
consequently it
consequentl.y
lt was
waa the
nater and
whlch was
was responsiresponsLthe water
and not
not the
the toxicant
toxlcant which
ble for
The
water further
ble
for the
bloaseay.
further subeubthe mortality
mortal.tty in
Ln the
the bioassay.
Ttre synthetic
synthettc water
stantiated
stanttated the
fact that
that healthy,
healthy, normal
nornal gametes
teat,
th€ fact
gameteswere
the. test,
vrereused
usedinLnthe.
but they
they could
not develop
but
could not
develop normally
normaLly in
in the
the real
real seawater.
seawater.
tn the
the toxitoxlTable
Table 12
12 is
ls aa comparison
comparlson of
BtoSea versus
of BioSea
versus real
real. seawater
eeawater in
percent kraft
#4,
Serlee
cant
of
Static
retention
#4,
Series
cant taken
taken from
fro'n the
the 10
of
10 percent
kraft jar
Stattc
retentlon
Jar
B.
B. Here the
better
was apparently
eynthettc dilution
dilutlon water
wafer was
apparently of
of slightly
the synthetic
cllghtly better
quallty than
The
of the
the
the real
uoed in
bloassay.
TIa, of
quality
than the
real seawater
seawater used
tn the
the bioassay.
ltre TLm
BloSea wa8
1.2.
BioSea
was 1.95
and that
that of
of the
was 1.2.
1.95 and
the real
real seawater
se&water dilution
dl.lutlon was
because
also because
The
for BioSea
BloSea shall
be ommitted
at this
thls time
tine also
The formula
formula for
shalt be
onrnrltted at
the data
data is
and though
the
are encouraging,
encouraglng,
ts inconclusive
lnconcluslve
though most of
of the
the results
resutts are
In
there are
be explained.
In
there
are some
undesirable fluctuations
that
fluctuat{ons
sone undeslrable
that cannot
cannot be
explatned.
addltlon to
blological results
reeults
addition
to this
thls there
there are
are many
the biological
many factors
factors effecting
effectlng the
Some of
of BioSea which
of these
these
we are
Some
of
whlch we
are learning
learnlng about
about and
and investigating.
lnvestlgatlng.
quantlty of
are
of chemlcals
chemicals ueed
used in
the formulatLon
formulation and
and
quallty and quantity
are the
the quality
ln the
water
quallty of
of the
the water
the order
order in
the
tn which
whleh they
they are
are compounded.
Aleo, the
compounded. Also,
tho quality
Evidence
be important.
in
which the
dlssolved appears to
lmportant.
ln wtrlch
the salts
ealts are
are dissolved
to be
dlsttlled
produces better
better results
than distilled
suggests
auggeats that
thst aa local
tocal spring
eprtng water produces
reeults than
year.
obtalned
Excellent larvae
water at
of the
water
et certain
tlmes of
Excetlent
larvae have been obtained
certaln times
the year.
percent real
uslng a mlxture
of BioSea
BloSea and
using
mixture of
and 10
10 percent
real seawater.
seanater.
of ababarray of
Experiments
saltwater
have led
led to
to an
an array
Experlments with
wlth artificial
artificlal
ealtwater have
accordlng
been
Some
of
these
anomalies
have
been
classified
according
of
normal
normal larvae.
Some
anomalles
classlfied
lanrae.
theee
presently ten
are known. Chemical
Chemical and
to
peculiarity and presently
to their
thelr pecullarlty
types are
ten types
we
lraste
lf we
phyalologlcal
physiological research
in
this
area
may
lead
to
waste
treatment,
treatment, if
reeearch tn thle area may lead to
Another
interestintereetcould discover
how the
organism was
belng damaged.
damaged. Another
could
dtscover how
the organism
wae being
pure BioSea,
normally,
devel.op normally,
ing observat{on
observation is
lng
le that
that in
BioSea, some
may develop
ln pure
some embryos
embryos may
dlshes.
practlcal.ly
but
bottom of
of the
but they
dormant
they lie
dormant on
on the
the bottom
the culture
culcure dishes.
lle practically
When
named, Ichthopterian
When aa small
of a compound,
enall amount
arnount of
compound, tentatively
tentatlvely
Ichthopterian
acttvl.ty
chloride is
BioSea formula,
activity enhanced
enhanced and
and
chloride
lnto the
the BioSea
fornula,
ls introduced
lntroduced into
synthels synthemany
This
compound
many of
of the
normally.
the veligers
veligerg swim
swim normally.
lhls activity
actlvlty
compound is
However, the
genus Sebastotes
the comsized
from fish
flah scales
ecaleg of
of the
Sebastotes sp.
etzed from
the genus
S.,
pound has
are
or purified and
been chemically
and results
results are
hae not
not been
chemi.cally identified
laentt?i3E-iiffir?1ed
inconclusive.
lnconclusLve.
Summary
Sumnar_y--
f'standardft and
eeawater
It
lmperatlve that
that a "standard"
and reproducible
reproduclble seawater
1.
It is
ls imperative
pollutlon studies
because the
the
be found,
marlne pollution
are to
to advance,
found, if
lf marine
studieg are
advance, because
quallty of
ln
\rater used
used in
of extreme
quality
the water
the test
teet is
le of
extreme importance
lmporrance in
of the
ln the
the
evaluation of
of waste treatments.
the evaluatlon
treatments.
physiologlNatural
and
intrinsic
and physiologiseawater apparently
apparently contains
contains intrinsic
Natural seawater
developnecessary
for
normal developcally
active
compounds
or
trace
elements
necessary
for
normal
active
compounds
or
trace
cally
elemente
ment
of
shellfish.
ment of ehellflsh.
2.
2.
A promising
embryonic use Ln
in
promising synthetic
for embryonic
synthetl.e seawater,
sultable for
seawater, suitable
presentLy being
KMEis
being developed.
developed.
bioassays
bloassays with
with KME
Ls presently
3.
3.
A _ 28
28
A4.
phystologlcal activity
4.
A physiological
actlvlty compound
A
conrpoundfor
for Bay
Bay mussele
boen
mussels has been
aynthestzed
fron mar{ne
fish scales,
synthesized from
marine fish
scales, but
but its
its structure
structure and
and other
other
charactertetLcg have
have not
characteristics
not been
been identified.
ldontlfled.