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United States
Environmental
Agency
Water
EPA
Protection
Office of Water
Regulations and Standards
Criteria and Standards Division
Washington, DC 20460
EPA 440/5-88-004
April 1989
Ambient Water Quality
Criteria for Ammonia
(Saltwater)-1989
AMBIENT AQUATIC LIFE WATER QUALITY CRITERIA FOR AMMONIA
(SALT WATER)
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
ENVIRONMENTAL RESEARCH LABORATORY
NARRAGANSETT, RHODE ISLAND
NOTICES
This report has been reviewed by the Criteria and Standards Division,
Office of water Regulations and standards, U.S. Environmental Protection
Agency, and approved for publication.
Mention of trade names of commercial products does not constitute
endorsement or recommendation for use.
This document is available to the public through the National Technical
Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.
i i
FOREWORD
Section 304(a)(1) of the Clean Water Act of 1977 (P.L. 95-217
requires the Administrator of the Environmental Protection Agency to
publish water quality criteria that accurately reflect the latest
scientific knowledge on the kind and extent of all identifiable effects on
health and welfare which might be expected from the presence of
pollutants in any body of water, including ground water. This document is a
revision of proposed criteria based upon a consideration of comments
received from other Federal agencies, State agencies, special interest
groups, and individual scientists. Criteria contained in this document
replace any previously published EPA aquatic life criteria for the same
pollutants.
The term "water quality criteria” is used in two sections of the
Clean water Act, section 304 (a)(1) and section 303 (c)(2). The term
has a different program impact in each section. In section 304, the
term represents a non-regulatory, scientific assessment of ecological
effects. Criteria presented in this document are such scientific assessmerits. If water quality criteria associated with specific stream uses are
adopted by a state as water quality standards under section 303,
they become enforceable maximum acceptable pollutant concentration in
ambient waters within that state. Water quality criteria adopted in
State water quality standards could have the same numerical values as
the criteria developed under section 304. However, in many situations
States might want to adjust water quality criteria developed under section
304 to reflect local environmental conditions and human exposure patterns
before incorporation into water quality standards. It is not until
their adoption as part of State water quality standards that the criteria
become regulatory.
Guidelines to assist the States in the modification of criteria
presented in this document, in the development of water quality standards,
and in other water-related programs of this Agency, have been developed by
EPA.
Martha G. Prothro
Director
Office of Water Regulations and Standards
iii
ACKNOWLEDGEMENTS
Don C. Miller
(saltwater author)
U.S. Environmental Protection Agency
Environmental Research Laboratory
South Ferry Road
Narragansett, Rhode Island 02882
David J. Hansen
(saltwater
coordinator)
U.S. Environmental Protection Agency
Environmental
Research
Laboratory
south retry Road
Narragansett, Rhode Island 02882
iv
CONTENTS
Foreword. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .iii
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. iv
Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Acute Toxicity to Saltwater Animals . . . . . . . . . . . . . . . . . . . . . . .7
Chronic Toxicity to Saltwater Animals. . . . . . . . . . . . . . . . . . . . . . . 14
Toxicity to Aquatic Plants . . . . . . . . . . . . . . . . . . . . . . . 17
Other Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Unused Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
National Criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
v
TABLES
1.
Acute Toxicity Of Ammonia to Saltwater Animals. . . . . . . . . . . . .32
2.
Chronic Toxicity of Ammonia to Aquatic Animals . . . . . . . . . . . . . . . . .39
3.
Ranked Genus Mean Acute Values with Species Mean AcuteChronic Ratios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .43
4.
Other Data on Effects of Ammonia on Saltwater Organism. . . . . . . 45
vi
INTRODUCTION*
in aqueous solutions, the ammonium ion dissociates to un-ionized ammonia
and the hydrogen ion. The equilibrium equation can be written:
H2O + NH
+
+
NH3 + H3O
(1)
+
The total ammonia concentration is the sum of NH 3 and NH 4 .
The toxicity of aqueous ammonia solutions to aquatic organisms is
primarily attributable to the un-ionized form, the ammonium ion being less
toxic (Armstrong et al. 1978; Chipman 1934; Tabata 1962; Thurston et al.
1981; Wuhrmann et al. 1947; Wuhrmann and Woker 1948). It is necessary,
therefore, to know the percentage of total ammonia which is in the un-ionized
form in order to establish the corresponding total ammonia concentration
toxic to aquatic life. The percentage of un-ionized ammonia (UIA) can be
*
calculated from the solution pH and pK a , the negative log of stoichiometric
dissociation,
% UIA = 100 [ 1 + 10
*
a
(( p K
- pH)
-1
]
(2)
The stoichmetric dissociation constant is defined:
+
K
*
a
[NH 3 ] [H ]
(3)
+
[NH 4 ]
where the brackets represent molal concentrations. Ka
*
is a function of the
temperature and ionic strength of the solution.
*
An understanding of the "Guidelines for Deriving Numerical National
Water Quality Criteria for the Protection of Aquatic Organisms and Their
Uses” (Stephan et al. 1985), hereafter referred to as the Guidelines, and the
Response to public Comment (U.S. EPA 1985c), is necessary in order to
understand the following text, tables, and calculations.
Whitfield (1974 developed theoretical models to determine the pK a
the ammonium ion in seawater.
*
of
He combined his models with the infinite
dilution data of Bates and Pinching (1949) to define general equations for
*
the pK a of ammonium ion as a function of salinity and temperature.
Whitfield’s models allow reasonable approximations of the percent unionized ammonia in sea water and have been substantiated experimentally by
Khoo
et
al.
(1977).
Hampson's
(1977)
program
for
Whitfield’s
full
seawater
model has been used to calculate the un-ionized ammonia fraction of measured
total ammonia concentrations in toxicity studies conducted by EPA and also in
the derivation of most other acute and chronic ammonia values which
contribute to the criteria. The equations for this model are:
% UIA = 100 [ 1 + 10 (X + 0.0324 (298-T) + 0.0415 P/T - pH)]
-1
(4)
where
P = 1 ATM for all toxicity testing reported to date;
T - temperature (°K);
s
X = pK a or the stoichiometric acid hydrolysis constant of ammonium ions in
saline water based on I,
I = 19.9273 S (1000-1.005109 S)
-1
(5)
where
I = molal ionic strength of the sea water;
S = salinity (g/kg).
The Hampson program calculator the value for I for the test salinity (Eq. 5),
s
finds the corresponding pK a , then calculates % UIA (Eq. 4).
2
Ze
&
?d:Cr
f3CZZ:s
temperat-dre.
30th
L_?e fractim
cmtr31
In ammnia
ionic
czrrelste
g0sltrq;ely
(1977)
hydrogen
is desirable
frcm the themdynamic
sa~ll,
presmably
changes
in activity
coefficients
the pH(NES) scale
scale
by 0.02 pi4 unit
at 10 q/kg.
electrcd8
electrode
type
Amwniwn
salt
(Whitfield
solutions
decline
may k
strong
of test
shifts
are
pH is a major
source
buffers
us0 in toxicity
fortuitously
the error
junction
a&
1977).
in the
is
potential
tillero
by
(1986)
to the free hydrogen
0.045 unit
ion
at 20 g/kg and 0.075
is a proprty
,+ 0.03 pH unit
toxicity
anraia
witf!
of the
salinity,
timb,
and
is difficult.
tests
but are slow to teach
declines
the seawater
the bufferod
in
‘While the ph(F)
an error
potential
by artabolism
oc klou
(ph(~))
1985).
acidic,
@! typically
rrqlified
toward
vater
scale
their
Culkrson
1%
In contrast,
of the liquid
salinity,
using
these seawater
pf4 relative
jmction
et al.
pn in salt
Conmqwntly,
akm
at 30 g/kg
used and may vary
water.
conducted
to uverestimata
The residual
reference
Controlling
(Bates
‘,ia t
does contribute
although,
due to a coqensation
fourd
unit
sta&point,
;.i!
correlated.
in sea water.
pi with Ems buffers
amnnia,
fact3rs
calibrated
source, precluding
from a central
of 1 un-ionized
p.allty
ion sea water
scale
zre
-nLa.
(NBS) buffers.
of ammnium ion hydrolysis
calculation
water
Bureau of Standards
of
2n-lznlztd
the pH is nonaally
used the free
Calibration
~~ss;c;atr=n
is rnversely
masurermnts
testing.
mc:a
*drth
their
are not available
:f
mania,
testing,
National
iegree
sf c,C.c three
of lm-ionized
toxicity
strength
Rho0 et al.
I -,".e
rnfluent:al
*-he least
Sallr.lt’(,
'-6‘.qerr*-q..bb..
-..---
of
during
test
equilibrium
state.
toxicity
organisms.
in ammia
3
tests
and the
eqrience
in degree
toxicity
in sea
tests
Also,
pH (7.8-8.2)
Inconsistency
of variability
equilibrium
of control
studies
~swc:ally
ir:
sea
;acer.
.i
-
$4
:.I
3f ‘-?.a ?;H3 effec:
~sesc:sat:on
~~7;:
‘,‘ar:.mce
zncent:at:m
kmld
:esuir:
of abut
,n
a
f 25% at pi 8 and
25’C.
A nuder
of amlytlcal
ammnia
totaL
Once total
solution
scthods
concentrations
amxxi3
-A
hmnia
aquatic
toxicity
me us4 in the literature
nitrogen
may not necessarily
total
-fired
tasts
toxic
the resmin&r
if
ma
in 0th~
calculatsd
total
II
kwr*
used
approach
9
units.
ud
or total
9
doamnt,
bar&
of forms in the
but msy be ths author*s
-a
all
reported
expressed
og MffL,
valuer
citad
that
in this
ma
&y authors
only
teqsrrture,
par
th8
s
ma,
ad
along
as reported
to mq/t
or if
m W.
19861,
dtnity
(1977)
fail
easo in
are given
total
arm consistently
conc8ntrations
for
or ccmvortsd
mmthad (e.g.,
j#I,
anmania
is the principal
as iag MI+,
dommnt
toxicity
quntitative
ma
report&
by a unique
reported
umnia
calculated
(MQ)$O,.
urkionized
Xl authors
to alculatm
Scam literature
trations
data
caac8ntrrthn
prakm
since
concentratims
vdrr
ma,
CaaporPdrumdintho
of this
ad
ths author ( s 1 provided
reported
of the
Ept3+4,0c -la-
in terms of me/L m-ionizad
and coqmrison,
form.
in a variety
man un-ionized
aammnia.
data havw been l xorrsmd
discwrion
CM k
of tha terms M3,
bore ace NXqCl, PU14M3 ad
Throqimt
and Healey 1984).
such as NH3, NHq+, M13-N, MIqoLI, NITqCl and
others.
way of expressing
of
expression.
have been reported
literature,
detemunat&on
and teqerature
of NH3 present
equilibrium
conc8ntration.s
(Richards
and the pti, salinity
concentration
on the aammia-seamcer
for direct
in aquamm solutioru
is measured,
date.
are available
they
the
codition8
proparr.
This
drriwd.
to providr
with
sufficient
MI3 CQeymPer, t-r-
if
papers were not US& but are clteci
rnfomat1on
obtained
are
UliSSlng rn published
by footnotes
so indicated
:n some :nstances
papers on expermental
correspondence
througtl
Iunder “‘Jnused Sata”.
with
conditions
data obtained
authors;
was
in this
manner
from U.S. EPA, CRL,
and are available
Narragansett.
of criteria
A number
ammnia
as an aquatic
review
domnents,
pollutant
ace available.
Thatcher
(19731,
Colt
Licbann
(19601,
McKee and Wolf (19631,
published
suamarirs
factors
affecting
toxicity
and Armstrong
of ammnis
ammnia
Lloyd
and Herbert
(19621,
Warren
(1962).
Literature
review
(19801,
reconmmndatfons
European
Inland
Academy of Sciences
Research
1985a),
Council
U.S.
willin-
TM ctitoria
quality
using
iqruved
justified,
(U.S.
a
arid Willingham
for
procdurer
national
et al.
herein
mia
which
including
Visek
by ifdabaster
may include
(19681,
and
relating
and Lloyd
(19701,
National
(19741,
National
(1976,
Agency
1980,
(19661,
Administration
(1979).
prwious
saltwater
because these new criteria
information.
may k
of ammmia
information
Protection
supersede
and additid
criterion
(19761,
of Engineering
Control
have
by Kinno ( 1976 1, Lloyd
Conmission
U.S. Environmntal
presented
EPA 1983a),
AC-
Water Pollution
criteria
water
Advisory
and National
federal
(19761,
have been published
(1975)
conmqwnces
of aaamnia toxicity
Pbheries
(19791,
and Swift
Hanpson (19761,
reviewe,
and physiological
with
Becker and
atxl Tsai
(19761,
Literature
Lloyd
( 19791,
(19711,
have been publish&
(19611,
to criteria
Eplet
Steffenr
toxicity.
and books dealing
Armstrong
(19811,
toxicity
organisms,
to aquatic
articles
replaced
not only
aquatic
were derived
Mmmver
adequately
by a sit*sp=ific
sit+speific
life
criterion
criterion
~37ce~trat~ons
ad
sita-specific
durations
of all4
exmedencer
saltwater
specific
March
mxing
lake8.
water
for
more recent
of averaging
(U.S.
infocmatfon
informtim
bodies
criteria.
for
periods
this
ha8 bmn
and sita-spcific
This criterion
ePA 198Sb).
There water
quality
‘J.S. EPA, L983bi , mt
zone cons:deratlons
may require
T!w latert
documnt
included.
war coducted
frequencies
doe8 not apply
developmnt
coqreheruive
also
to
of site
literature
in June,
1986; sonm
ACUTE TOXICITY TO SALTWATER ANIMALS
The acute toxicity of ammonia to saltwater animals has been studied in
.crustaceans, bivalve mollusks, and fishes. Acute values are summarized in
Table 1 for 21 species in 18 genera. The winter flounder, Pseudopleuronectes
americanus, represents the most sensitive gems, with a Species Mean Acute
Value (SMAV) of 0.492 (Cardin 1986). Fourteen (eight fish, five crustaceans
and one mollusc) of the remaining 17 genera have Genus Mean Acute Values
within the order of magnitude of that for the winter flounder. The three
most tolerant species are mollusks. The SMAVs are 19.1 mg/L for the Eastern
oyster, Crassostrea virginica, 5.36 mq/L for the quahog clam, Mercenaria
mercenaria, and 3.08 mg/L for the brackish water clan, Rangia cuneata.
Except for these mollusks, there is no phyletic pattern in acute sensitivity
to ammonia. Fishes and crustaceans are well represented among both the more
sensitive and the more tolerant species tested.
Few consistent trends or patterns are evident in the acute toxicity
values cited in Table 1 with respect to biological or environmental variables. Contributing to this, in part, is test variability. This is evident
in multiple tests with the same species, even when conducted under closely
comparable conditions. Variability in acute toxicity values for ammonia may
reflect differences in coalition of the test organisms, changes in the
exposure conditions during testing, particularly pH, and variance incurred
through calculation of un-ionized ammonia concentrations. As noted in the
Introduction, pH has a strong influence on the concentration of un-ionized
ammonia in water, such that a variation of ± 0.1 pH unit during the test my
result in ± 25% variation in the NH 3 exposure concentration. The NH 3
exposure concentrations are calculated values dependent on accurate
7
measurement of exposure pH.
always
detect
potentially
However, pH monitoring during a test may not
significant
pH
excursions.
Also,
non-systematic
errors on the order of ± 0.03 pH unit may also occur with seawater pH
measurements due to variation in the liquid junction potential between and
within electrode pairs. In addition to these sources of error,
interpretation of test results should consider known replicability of
toxicity tests. Intra- and inter-laboratory comparisons of acute toxicity
test results using saltwater species show LC50s may differ by as much as a
factor of two for the same chemical tested with the same species (Hansen
1984; Schimmel 1986). In light of all these sources of variability, LC50s
for un-ionized ammonia are in this document considered similar unless they
differ by at least a factor of two.
Few marked differences are evident in the acute toxicity of ammonia with
respect to differences in life stage or size of the test organism. Yolk-sac
larval striped bass (Morone saxatilis) seem slightly less sensitive to unionized ammonia (LC50s - 0.70 and 1.09 mg/L) than 9 or 10 day old post-yolk
sac larvae (LC50s - 0.33 and 0.58 mg/L) (Poucher 1986). Juvenile striped
bass also seem less sensitive than post yolk-sac larvae (LC50s range from
0.91 to 1.66 mg/L) in tests by EA Eng. (1986) and Hazel et al. (1971). Acute
values for striped mullet (Mugil cephalus) suggest a factor of two decrease
in sensitivity (LC50 - 1.19 vs. 2.38 mg/L) to ammonia with increase in weight
from 0.7 to 10.0g (Venkataramiah et al. 1981). Larval grass shrimp
(Palaemonetes pugio) appear to be more acutely sensitive (LC50 - 1.06) (EA
Eng. 1986) than juveniles and adults (LC50 - 2.57) (Fava et al. 1984),
although the contrasting life stages were tested at different salinities. A
s l i g h t d e c r e a s e i n t h e a c u t e s e n s i t i v i t y o f E a s t e r n o y s t e r s , Crassosrtrea
8
.-&4&i 7’ a-‘j I :S e’/:dent
fec**neeq
. 13 &
. . . V”.
52 elm (LCSO - 24 to 43 rng/L)
iiffercnC*
in amte
28 to 32 run quahog clams,
3evcrai
data sets
tenperaturc
animals.
Few differences
in tests
conditions
.
salinities
(Hcrcenarra
Similar
life
1.47 to 3.41 mq/L (CardIn
mg/L (EA Ehg. 1986).
factor
At pM 7.0,
2.2 (Cardin
of
at 31 g/kg
salinity).
baryllina)
tested
1986)
similar
vith
LC5Os for
theu
salinity
unly).
ranging
salinity
(m
reported
at 30 g/kg salinity
bm fishes
three
spined
tested
1986) Mch
at low a&
stickleback
Q/kg;
0.97
high
salinities
(Gasterosteus
Hmmwr,
mgfi
(Menidia
of 2 1cn-m at
at pl4 7 and 9, the
casprrring
flow
throuQh
juvwniles
wnidia)
at pH 8
the 0.98 19% value
with
( 1964 1.
Acute
by ~uol
aculeatus),
9
silwrsider
0.54
to 1.24 mqF at 9 to 10 g/kg
~11
by Fava et al.
O.SO ad
at 11 Q/kg than at 31 g/kg
(Meniclia
correspandr
by a
to 1.94 me/L at 19 g/kg
tcspmxiwly,
from
salinity
a factor
relatiw
higher
silwrsidr
Athntic
NH3
0.92 to 1.68
at a 1~
inlamd
(Puucher 1986).
slightly
and 1 20.C hava MI3 US08
m.
larval
for
of 1.7 a& 1.5,
(by a factor
test valws
and at 14 to 18 g/kg,
the LCSO - 0.88 mg/t,
larva8 an
salin$ty,
2.82 to 2.87 mq/L; at 30
2S’C are approximately
and 1.77 mqF at 30 g/kg salinity
LCSOs at four
- 0.23 me/t at II
Acute values
sf
inf?ucncc
pH and teqerature
At 10 to 11 e/kg
the LCSO was lmmt
(KS0
at pH 8 Md
I1 en<g salinity
1986);
and Srna 1975).
at different
have owrlappinq
at pH ) 7.8 and 2S.C.
rciattd
of t!!c
toxicity
Stages ti
bahia)
-3
of ammnia to saltwater
toxicity
in acute
a--d ;:
4.7 to 5.2 35 and
(Epifanio
LCSOs range from 1.04 to 3.19 mq/L; at 20 9/kg,
g/cg,
15.rno~L,
NO site
1 permit an evaluation
are evident
(Wsidopsis
in tests
L975).
mercenarla)
and pH on the acute
with
wids
and 5rm
t
to afmmma .kdas seen Sctwetn
in Table
salinity,
salinities
zp~fano
Sensltivrty
. --, -3.5
,&.=b
1’ m
et al.
valws
overlap
(1971).
LCSOr range~from
for
For the
2.09 to
- . ‘5 33,:
3: ACJrCx:=tel*/
appr:xzrately
are 9.91
34 g/kg.
(EA mg.
salinity;
mst
lawal
str~ged
saltwater
at similar
factor
has little
animals
silwrsids
pH Md
tested.
caimity
Acute values
kryllina)
tested
for
1986).
(Qprfnodon
The LCSO for
varieqatw)
32.S*C,
3.5 mq/t
(Norone
saxatilis)
ttmrmally
differ
1986).
tested
srxl diffsr
approximstely
34 g/k0
salinity
(Hszsl
sticklebsck
(Gssterosteus
sensitivity
to NF$ at 1S.C (-0
approximately
sensitivity
aculratus)
11 9/kg
salinity,
vas about
2 tims
LCSO - 1.68 Md 2.7 arq/t;
by less
larval
there
than a
at
shmpshmd
for juvsnile
war little
m
at
bsss
at
wtmn trstsd
1971).
miranow
stripd
by less than a factor
et al.
and
the LCSO is 1.7 meft
at 1S.C aruI 23.C avwrlap
ulinity
teqeratures
at 2S*C, 2.79 aryt;
Acute valws
11 e/kg
acclimated
the LCSO is 0.98 w;
acclimated
approximately
1971).
of axmmnia
thermally
salinity)
at 13.C is 2.10 aq/L;
(Patcher
toxicity
at three
LCSOs are 1.7s and 1.77 mg/L; and at 32.S'C,
(Paxher
et al.
tested
at 18*C,
, ~52s
?L ?.bg
!!iazel
on the acute
(8.0 pH; 31 g/kg
species
3:
k-ass ??crme saxa::lisi
34 g/kg
influence
(Nsnidia
For this
of 2.
.m,',
1986) and 1.83 to 1.58 .nq/L at aoprcxlaately
.
also
inland
tS*C,
ilic,cI ;-,-Jcntle
3.r.d 1.58 ‘I: 3. j
0.75 Wd 1.4 rag/L at approxmately
reqerature
with
11 ; ‘<ri jal:.?.::~
With three
of 2 at
spined
difference
in
- 2.75 mg/L) and 23.C (LCSO - 2.09 me/t)
but in tssts
greater
at lS°C,
at
at approximtely
the higher
LCSO m 4.35 ad
34 9/kg,
taqorature
5.6 nrqF)
(at
t-z.1
23T,
et al.
1971).
S8vw8l
anwnia
data
suqg#t
rrlatlonship
LCSOs of acute
sets
tht
is
not
tssts
r
*-ha effect
.a tha
conrir;tent
comhctec!
data
of pii on th
on frmhwatw
spuies.
bebeen
at different
10
toxicity
spociss,
Text Table
pii cordftions.
of un-ionitsd
tha
ptCt=icity
1 summrizrs
Results
ars
at
Text
Table
1.
Acute Toxicity
of l&b-ionized
mia
to the Prawn (Hacrobrachium
rosenber ii),
Hysid (Rysidopis
I&ld),
- .--_
m-+L
hrva1
Inland
Silverside
(Henidia
bebeina).
and Juvenile
Athntlc
51 vlers&
(nenidia
=nidTai,
at chtteLtibit
_c_pli Corditions.
m~ici ty expressed as US
rg tw3/L.
Flew-through
test resultsunderIined,
amn teqxrdtule
and salinity
conditiorY
iadicated.
-
---_-.-_
Pram
Hyrid
~hl-mstrong
et al.
PH
6.5-6.9
28.C,
12 g/kg
(Cardin
(Car&n
1978)
1986)
24.5’C,
llq/kg
1986)
lElr Enq.
1986)
ZS’C, 31 g/kg 20°C, 31 g/kg
Athntlc
( Pouch@c
(LA thy.
1986 1
l!m)
25“C, 31 g/kg 22”c, 9.5 g/kq
- ---___
0.38
1.64
7.0-7.4
7.5-7.9
Inland
Silverside
( Douche c
1986)
25T, 11 q/kg
0.95
1.18
1.47
0.40,
0.92,
0.93,
i-36
1.3
1.04,
3.19
2.76,
8.5-8.9
9.0-9.4
1.70, 2.49
Z.Qe, 3.41
1.40
0.77
0.88
0.76
1.51,
1.75
0.75,
1.05,
---
l.).!
0.97,
1.10,
1.01,
1.24
1.41
1.08
1.68
1.16
2.02
1.77,
0.91
0.97,
1.0
8.0-8.4
-
0.49
1.21
-
11
;egresacecf
?reclda
any
-zy ‘,7e :eTrwr3~**-0
-4- - p.d
‘-*“i _- ~~F.dlt~XS
jai ’ _..-
fra
X509
variabillcy
var:ability
:nccrlaboratOrj
-A
specrcs,
the pram
(Cardin
acute
!Annstrong
was consistent
from the aysid
(Henidfa
decreases
in acuto
increase
in aeuts
response
of jwenilo
sensitivity
Atlantic
(EA Eng.
saltwater
fishes
o-tic
regulatory
l xtwzml
teqor8turm
relationships
toxicity
Ia
tested
inland
differ
silverside
as pH
at pH 9.0,
with
mysib
A furthst
contrast
1985) a& my
contrsst
mnidia),
which
cuxmtratfanr
in ths
tort
toxicity
toxicity
bssic
could
exists
with
the tesporus
reflect
tww
havm a twwfold
an tha acut
tith
In
ham a nearly
of pfI on aamnia
physiology
with
pH over
of
in these
tsro
of several
differencss
inflwncs
in
response
their
of ovw a rsngm of pit, rrlinity
caditiau.
EPA bslimaa
theso
a msrksd
and ionic
to elsvatsd
ad
is also
response
to aarponia
silversids
l ffut
The inflwnce
(Erickson
sensitivity
(Mnidir
little
1986).
fisher
freshwater
Larval
at ptr 7.0,whilo
silversib
the range of 7.0 to 9.0 having
ammonia
inlard
at #I 7.0.
senritlvity
This
!pH 7.0)
of 21 in 31 g/kg salinity,
(> factor
wster,
5.3
inverCebra:e
T?m twu fishes
to pfi.
acute
by autk.cr
the qmid
from ths mysid responss
sensitivity
in 11 Q/kg salinity
decrease
respmse
‘-3
2) at luu pH for
factor
pH values.
salinity.
do S~CYWincreassd
increased
contrast,
than at hiqher
differ
(>
1978) and for
at low bed high
from 8 to 7, but
appreciably
et al.
and prawn in their
bryllina)
are Listed
For t!!c cm
to .mJ is greater
sensitivity
!pH 6.83)
also
nay be cecqnlred.
1986; EA Eng. 19861,
rupidr
fold
LYCSC scurces;
2f c,le :ps:j
that
for
factors,
in salt
t)w data
un-iahod
wtmn acting
water.
available
anrnia
al-,
Therefore,
on all
wrtst
are insufficient
has a cmsistmt
a water
12
quality
qulity-toxicity
to
that bny of
canclti
rarjor
dqmd-t
inflwna
01 m3
fmctfm
ms
The 18 avaihblt
mg mfL
Gentis Zean Acute values
Pseudoplcuronectes
fcr
of less
saltmter
t!!an 100.
:o 19.102 mg “H3fi
Acute values
are available
rang0 of Species
for Crassostrea,
he
genera
is less
than a factor
of 1.2;
in the remaining
factor
of 4.5.
&ighty-eight
percent
of the Gem
within
a factor
of ten and 71 percent wre
for Pseudopleuronectes.
NH~
was obtained
calculation
1-r
using
procedure
than Species
?l~l
in the GA&lines.
of ficn
of
in Table
This valw
Mean Acute Value of 0.492 nq/L for winter
13
they differ
Acute Valw
the Gefnas Hean Acute Valws
described
genus,
Hean Acute Values
a factor
in
two of these
Mean Acute Values within
A saltwater
a factor
more than one species
for
thr l e genera.
valw
range from 0.492
wre
tha acute
of 0.465 mq
3 and the
is slightly
flounder.
by a
CHRONIC TOXICITY TO SALTWATER ANIMALS
Chronic toxicity tests have been conducted on ammonia with twelve
freshwater and saltwater species of aquatic organisms (Table 2). Of the ten
freshwater species tested, two are cladocerans and eight are fishes. The
details of the results of the freshwater tests are discussed in the “Ambient
Water Quality Criteria for Ammonia - 1984” (U.S. EPA 1985a). In saltwater, a
life-cycle toxicity test has been conducted with the mysid, Mysidopsis bahia,
and an early life-stage test has been completed with the inland silverside,
Menidia beryllina (Table 2).
The effect of ammonia on survival, growth and reproduction of M. bahia
was assessed in a life-cycle toxicity test lasting 32 days (Cardin 1986).
Survival was reduced to 35 percent of that for controls and length of males
and females was significantly reduced in 0.331 mg NH 3 /L. Although
reproduction was markedly diminished in this concentration, it did not differ
significantly from controls. Lengths of females were significantly reduced
in 0.163 mg/L, but this is not considered biologically significant since
reproduction was not affected. No significant effects on mysids were
detected at 0.092 mg/L. The chronic limits are 0.163 and 0.331 mg/L for a
chronic value of 0.232. The Acute Value from a flow-through test conducted
at similar coalitions (7.95 pH, 26.5°C, 30.5 g/kg salinity) with M. bahia is
1.70 mg/L which results in an acute-chronic ratio of 7.2 with this species.
The effect of ammonia on survival and growth of the inland silverside
(Menidia beryllim) was assessed in an early life-stage test lasting 28 days
(Poucher 1986). Fry survival was reduced to 40 percent in 0.38 mg NH3/L,
relative to 93% survival of control fish, which is a significant difference.
Average weights of fish surviving in concentrations > 0.074 mg/L were
14
significantly less than weights of controls, an effect which persisted as the
concentration of ammonia increased. No significant effects were detected in
silversides exposed to 0.050 mg/L. Thus, the chronic limits are 0.050 and
0.074 mg/L for a chronic value of 3.061 mg/L. The acute value, derived as
the geometric mean of flow-through tests with this fish at full strength sea
water between pH 7.0 and 8.0, is 1.30 mg/L, resulting in an acute-chronic
ratio of 21.3.
Acute-chronic ratios are available for ten freshwater and two saltwater
species (Table 2). Ratios for the saltwater species are 7.2 for the mysid
and 21.3 for inland silversides. These saltwater species have similar acute
sensitivities to ammonia, with LC50s near the median for the 21 saltwater
species tested. The acute-chronic ratios for the freshwater species vary
from 1.4 to 53, so they should not be directly applied to the derivation of a
Final Chronic Value. Guidance on how to interpret and apply ratios from
tests with freshwater species to derive the freshwater criterion for ammonia
has been detailed in U.S. EPA 1985a which should be consulted. This document
concludes that: (1) acute-chronic ratios of freshwater species appear to
increase with decrease in pH; (2) data on temperature effects on the ratios
ace lacking; and (3) acute-chronic ratios for the most acutely and
chronically sensitive species are technically more applicable when trying to
define concentrationa chronically acceptable to acutely sensitive species.
Therefore, mean acute-chronic ratios were selected from freshwater tests with
species whose chronic sensitivity was less than or equal to the median
conducted at pH > 7.7. These included the channel catfish, with a mean
acute-chronic ratio of 10; bluegill, 12; rainbow trout, 14; and fathead
minnow, 20. The mean acute-chronic ratios for these four freshwater and the
15
two saltwater species are within a factor of 3.
The geometric mean of these
six values, 13.1, which divided into the Final Acute Value of 0.465 mg/L
yields the Final Chronic Value of 0.035 mg NH 3 /L.
16
TOXICITY TO AQUATIC PLANTS
Nitrogen in the saltwater environment is an important nutrient affecting
primary production, the composition of phytoplankton, macroalgal and vascular
plant communities, and the extent of eutrophication. Ammonia is an important
part of nitrogen metabolism in aquatic plants, but excess ammonia is toxic to
saltwater plants (Table 4). Limited data on mixed populations of saltwater
benthic microalgae (Admiraal 1977) show that ammonia is more toxic at high
than at low pH (Admiraal 1977). This suggests that toxicity may be
+
primarily due to NH 3 rather than NH 4 .
Information on the toxicity of ammonia to saltwater plants is limited to
tests on ten species of benthic diatoms and on the red macroalgal species,
Champia parvula. A concentration of 0.247 mg NH 3 /L retarded growth of seven
species of benthic diatoms (Admiraal 1977). A concentration of 0.039 mg/L
reduced reproduction of Champia parvula gametophytes; no effect was observed
at 0.005 mg/L (Thursby 1986). Tetrasporophytes of C. parvula exposed to
0.005 to 0.026 mg/L for 14 days reproduced less but grew faster; no effect
was observed at 0.003 mg/L.
17
OTHER DATA
A number of researchers have studied the effects of ammonia under test
conditions that differed from those applicable to acute and chronic test
requirements as specified in the Guidelines (Table 4). Animals studied
included rotifers, nemertine worms, echinoderms,
polychraetes, and fishes.
mollusks,
arthopods,
Concentrations affecting the species tested are
generally greater than than Final Acute Value and are all greater than the
Final Chronic Value.
Among the lower invertebrates, Brown (1974) found the time to 50 percent
mortality of the nemertine worm, Cerebratulus fuscus, exposed to 2.3 mg NH 3 /L
is 106 minutes.
In the rotifer, Brachionus plicatilis, the 24-hr LC50 is 20.9
mg NH 3 /L, the net reproduction rate was reduced 50 percent by 9.6 mg/L, and
the intrinsic rate of population increase was reduced 50 percent by 16.2
mg/L (Yu and Hirayama 1986).
I n t e s t s w i t h m o l l u s k s , t h e r a t e o f r e m o v a l o f a l g a e (Isochryris
galbana) from suspension (filtration rate) was reduced > 50% during a 20-hr
exposure to 0.16 and 0.32 mg NH 3 /L in juvenile and adult quahog clan
(Mercenaria mercenaria) and to 0.08 mg/L in juvenile eastern oysters
(Crassostrea v i r g i n i c a ) ( E p i f a n i o a n d S r n a 1 9 7 5 ) . T h e r a t e o f c i l i a r y b e a t i n g
i n t h e m u s s e l , M y t i l u s e d u l i s , is reduced from 50 percent to complete
inhibition in < 1 hour by 0.097 to 0.12 mg/L (Anderson et al. 1978).
Excretion of ammonia is inhibited in channeled whelk (Busycon
canaliculatum), common rangia (Rangia cuneata), and a nereid worm (Nereis
succinea) exposed to sublethal concentrations of 0.37, 0.85 and 2.7 mg/L,
respectively (Mangum et al. 1978). The authors conclude that ammonia crosses
the excretory epithelium in the ionized form, ad that process is linked to
18
Na
+
and K
+
ATPases.
In the common bloodworm (Glycera dibrachiata), Sousa et
al. (1977) found no competition exists between NH 3 and oxygen in binding
hemoglobin.
Ammonium chloride (about 0.01 mg NH 3 /L) exposure of unfertilized eggs
of the sea urchins, Lytechinus pictus, Strongylocentrotus purpuratus, and S.
drobachiensis increased the amount and rate of release of “fertilization
acid” above that occurring post-insemination (Johnson et al. 1976; Paul et
al. 1976). Exposure of unfertilized sea urchin (L. pictus) eggs to NH 4 Cl
resulted in stimulation of the initial rate of protein synthesis, an event
that normally follow fertilization (Winkler and Grainger 1978). Activation
of unfertilized L. pictus eggs by NH 4 Cl exposure (ranging from 0.005 to 0.1
mg NH 3 /L was demonstrated by an increase in intracellular pH (Shen and
Steinhardt 1978; Steinhardt and Mazia 1973). Ammonia treatment activated
phosphorylation of thymidine and synthesis of histones in unfertilized eggs
of the sea urchin S. purpuratus (Nishioka 1976). Premature chromosome
condensation was induced by ammonia treatment of eggs of L. pictus and S.
purpuratus (Epel et al. 1974: Krystal and Poccia 1979; Wilt and Mazia 1974).
Ammonium chloride treatment (0.01 mg NH 3 /L) of S. purpuratus and S.
drobachienris fertilized eggs resulted in absence of normal calcium uptake
following insemination, but did not inhibit calcium uptake if ammonia
treatment preceded insemination (Paul and Johnston 1978).
In exposures of crustaceans, the 7-day LC50 is 0.666 mg NH 3 /L for the
copepod, Euclaanus elongatus, while 38 percent of the E. pileatus died after
7 days in 0.706 mg/L, (Venkataramiah et al. 1982). No sargassum shrimp
(Latreutes fucorum) died after 21 days in < 0.44 mg/L (Venkataramiah et al.
1982). The EC50 bared on reduction in growth of white shrimp (Penaeus
19
erght&y
:-.:ee
a6cPr
- --.
se t L f e rJ s J
X50
3elistraty
et
from mter
i;hen
iCallinec:es
1377).
al.
of 28 g/kg
inhibited
ammnia
salinity
0ccJrred;
Wickins
(1976)
and decreased
in pH seen in 964our
cosenbergii)
is also
(Table
4) (Armstrong
NH3 at
pli 6.83
not as great,
et al.
1978).
7.60 was reduced
with
in 0.63 q/I,
this
ammonia
mrtality
water
for
the
at 1.7 mg/L to
prawn,
growth
of un-ionized
the prawn
from tests
was
lasting
24 a&
the decrease
mre
in acute
1.7 at pli 8.34.
of
of the pram,
amnxlia
with
(Nacrobrachim
three t-8
wro
Prams
by a factor
growth
mved
1976).
Abuve pn 7.6,
only
of low pH was seen with
with
in toxicity
in data
than at 7.6.
declining
(Wickins
tests
exhibited
iRte
of
from 1700 minutes
test
decrease
bemeen
2.e
(MMqum et al.
to SO percent
decreased
at 0.12 mq/t
doublinq
a
.
anmr~canus 1
sapidusj
net acid output
the timr
In a six-ueek
at 3.4 mqyL.
‘Hanurd
of 5 g/kg,
ater
*dlcxer.s 13’5
of excess NH4Cl to the luu salinity
found that
me relationship
increase
to
rosenberqii,
ceduced 32 percent
crabs
blue
addition
excretion
,tlacrobrachiuan
560 minutes
:S 2, ‘2 x, L
!zcster
rate
prawn,
px~sure
1s 1. ‘3 3-g/L f3c 9,~ XmierrcM
excretion
1976).
xee,qs :f
which after
144 hours
sensitive
to
toxicity
was
A similar
effect
seven days at pti
and at p&4 6.83 by 0.11 mcyt (Armstrong
et al.
1970).
Few “other
fishes
(Table
chinook
salma
(Harider
ad
salnun
Mortality
(S8lm
-of
data”
4).
III three
(Qltorhync)nrr
Allen
tit)
an the effects
are available
1963).
wr*
the Atlantic
mg/L than the 43 pmcent
saltwater
The 24-h
0.11s
control
canqd
LCSOS frcn
fraa
(Mnidia
mortality
20
in
1.1s to 2.19 mg W3/L
bm tests
and 0.28 me/L (Alabaster
silverside
on dtwator
lasting 24 hours, tha LCSOS for
tarts
tshawytscha)
of ma
with
Atlantic
et al.
mnidia)
MS higbr
a 28day
early
1979).
in 0.44
life-stage
test
21
UNUSED DATA
Studies conducted with species that are not resident to North America
were not used (Alderson 1979; Arizzi and Nicotra 1980; Brown and Currie 1973;
Brownell 1980; Chin 1976; Currie et al. 1973; Greenwood and Brown 1974;
Inamura 1951; Nicotra and Arizzi 1980; Oshima 1931; Reddy and Menon 1979;
Sadler 1981; Yamagata and Niwa 1982). Other data were not used because
exposure concentrations were not reported for un-ionized ammonia and/or data
on salinity, temperature, and pH necessary to calculate NH 3 concentrations
were not available (Binstock and Lecar 1969; Linden et al. 1978; Oshima 1931;
Pinter and Provasoli 1963; Pruvasoli and McLaughlin 1963; Sigel et al. 1972;
Sousa et al. 1974; Thomas et al. 1980; Zgurvskaya and Kustenko 1968). Data
of Hall et al. (1978) were not used since the form of ammonia reported in the
results is not stated. Data were also not used if ammonia was a component of
an effluent (Miknea 1978; Natarojan 1970; Okaichi and Nishio 1976: Rosenberg
et al. 1967; Thomas et al. 1980: Ward et al. 1982). Data reported by
Sullivan and Ritacco (1985) were not used because the pH was highly variable
between treatments. Data from a report by Curtis et al. (1979) were not used
because the salt tested, ammonium fluoride, night have dual toxicity. Data
reported by Katz and Pierro (1967) were not used because test exposure time
and salinity cited in the summary data table and appendix do not agree.
Results of a field study by Shilo and Shilo (1953, 1955) were not used since
the ammonia concentration was highly variable. The Ministry of Technology,
U.K. (1963) report was not used because the ammonia toxicity data were
previously published elsewhere and the relevant information is cited in this
document. References were not used if they relate more to ammonia
metabolism in saltwater species than to ammonia toxicity; e.g., Bartberger
22
and Pierce, Jr. 1976; Cameron 1986; Girard and Payan 1980; Goldstein and
Forster 1961; Goldstein et al. 1964; Grollman 1929; Hays et al. 1977; McBean
et al. 1966; Nelson et al. 1977; Read 1971; Raguse-Degener et al. 1980;
Schooler et al. 1966; Wood 1958.
Publications reporting the effects of
ammonia as a nutrient in stimulation of primary production were not used,
e.g., Byerrum and Benson (1975).
23
SUMMARY
All
of
the
following
concentrations
are
un-ionized
ammonia
(NH3)
because
+
NH 3 , not the ammonium ion (NH 4 ), has been demonstrated to be the more toxic
form of ammonia. Data used in deriving the criteria are predominantly from
tests in which total ammonia concentrations were measured.
Data available on the acute toxicity of ammonia to 21 saltwater animals
in 18 genera showed LC50 concentrations ranging from 0.23 to 43 mg NH 3 /L.
me winter flounder, Pseudopleuronectes americanus, is the most sensitive
species, with a mean LC50 of 0.492 mg/L. The mean acute sensitivity of 88
percent of the species tested is within a factor of ten of that for the
winter fluunder. Fisher and crustaceans are well represented among both the
more sensitive and more resistant species; mollusks are generally resistant.
Water quality, particularly pH and temperature, but also salinity,
affects the proportion of un-ionized ammonia. With freshwater species, the
relationship between the toxicity of un-ionized and pH and
temperature is similar for most species and was used to derive pH and
temperature dependent freshwater criteria for NH3. For saltwater species,
the available data provide no evidence that temperature or salinity have a
major or consistent influence on the toxicity of NH3. Hydrogen ion
concentration does increase toxicity of NH 3 at pH below 7.5 in some, but not
all species tested; above pH 8, toxicity may increase, decrease, or be little
altered as pH increases, depending on species.
The chronic effects of ammonia have been evaluated in tests with two
saltwater and ten freshwater species. In a life-cycle test with a myrid,
adverse effects were observed at 0.331 mg NH 3 /L but not at 0.163 mg/L. In an
early life-stage test with inland silverribs, adverse effects were observed
24
at 0.074 mg/L NH 3 but not at 0.050 mg/L.
Acute-chronic ratios are available
for 12 species and range from 1.4 to 53. Ratios for the four most sensitive
freshwater species, tested at pH values greater than 7.7, and for the two
saltwater species tested, range from 7.2 to 21.3.
Available data on the toxicity of un-ionized ammonia to plants suggests
significant effects may occur in benthic diatoms exposed to concentrations
only slightly greater than those acutely lethal to salt-water animals.
Ammonia at concentrations slightly less than those chronically toxic to
animals my stimulate growth and reduce reproduction of a red macroalgal
species.
The key research needs that should be addressed in or&r to provide a
more complete assessment of toxicity of ammonia to saltwater species are:
(1) assess reported pH-toxicity relationships and test other species by
conducting additional acute toxicity tests using flow-through techniques and
continuous pH control both with and without pH acclimation; (2) determine the
effects of water quality variables on acute-chronic ratios by conducting
Life-cycle and early life stage tests with saltwater species; (3) investigate
temperature influence by additional acute toxicity tests with species that
can tolerate both low and high temperature extremes; (4) test the effects of
constant total ammonia exposure and cyclic water quality charger to mimic
potential tidal ad dial shifts in salinity and pH; (5) test the effects of
fluctuating and intermittent exposures with a variety of species; and (6)
investigate the total of other water quality variables on ammonia toxicity:
e.g., dissolved oxygen and chlorine; and (7) investigate the contribution of
NH 4
+
to the toxicity of aqueous ammonia solutions to better resolve how the
25
ammonia criterion should be expressed if pH dependence continued to be
demonstrated.
26
NATIONAL CRITERIA
The procedures described in the “Guidelines for Deriving Numerical
National Water Quality Criteria for the Protection of Aquatic Organisms and
Their Uses” indicate that, except possibly where a locally important species
is very sensitive, saltwater aquatic organisms should not be affected
unacceptably if the four-day average concentration of un-ionized ammonia does
not exceed 0.035 mg/L more than once every three years on the average and if
the one-hour average concentration does not exceed 0.233 mg/L more than once
every three years on the average. Because sensitive saltwater animals appear
to have a narrow range of acute susceptibilities to ammonia, this criterion
till probably be as protective as intended only when the magnitudes and/or
durations of excursions are appropriately mall.
Criteria concentrations based cm total ammonia for the pH range of 7.0
to 9.0, temperature range of 0 to 35°C, and salinities of 10, 20 and 30 g/kg
are provided in Text Tables 2 and 3. These values were calculated by
Hampson’s (1977) program of Whitfield’s (1974) model for hydrolysis of
ammonium ions in sea water.
Three years is the Agency's best scientific judgment of the average
amount of time aquatic ecosystem should be provided between excursions. The
ability of ecosystems to recover differ greatly.
Site-specific criteria may be established if adequate justification is
provided. This site-specific criterion may include not only sits-specific
criteria concentrations, and mixing zone considerations (U.S. EPA, 1983b),
but also site-specific durations of averaging periods and site-specific
frequencies of allowed exceedances (U.S. EPA 1985b).
27
Use of criteria for developing water quality-based permit limits and
for designing waste treatment facilities requires the selection of an
appropriate wasteload allocation model. Dynamic models are preferred for the
application of those criteria (U.S. EPA 1985b). Limited data or other
considerations might make their use impractical, in which case one should
rely on a steady-state model (U.S. &PA 1986).
IMPLEMENTATION
Water quality standards for ammonia developed from then criteria should
specify use of environmental monitoring methods which are comparable to the
analytical methods employed to generate the toxicity data base. Total
ammonia may be measured using an automated idophenol blue method, such as
described by Technicon Industrial System (1973) or U.S. EPA (1979) method
350.1. Un-ionized ammonia concentrations should be calculated during the
dissociation model of Whitfield (1974) as programmed by Hampson (1977). This
program was used to calculate most of the un-ionized values for saltwater
organisms listed in Table 1 and 2 of this document. Accurate measurement of
sample pH is crucial in the calculation of the un-ionized ammonia fraction.
The following equipment and procedures were used by EPA in the ammonia
toxicity studies to enhance the precision of pH measurements in salt water.
The pH meter reported two decimal places. A Ross
electrode with ceramic
junction was used due to its rapid response time; an automatic temperature
compensation probe provided temperature correction. Note that the
responsiveness of a new electrode may be enhanced by holding it in sea water
for several days prior to use. Two National Bureau of Standards buffer
solutions for calibration preferred for their stability were (1) potassium
28
hydrogen phthalate (pH 4.00) and (2) disodium hydrogen phosphate (pH 7.4).
For overnight or weekend storage, the electrode was held in salt water,
leaving the fill hole open. For daily use, the outer half-cell was filled
with electrolyte to the fill hole and the electrode checked for stability.
The electrode pair MS calibrated once daily prior to measuring pH of
samples; it was never recalibrated during a series of measurements.
Following calibration, the electrode was soaked in sea water, of salinity
similar to the sample, for at least 15 minutes to achieve chemical
equilibrium and a steady state junction potential. When measuring pH, the
sample was initially gently agitated or stirred to assure good mixing at the
electrode tip, but without entraining air bubbles in the sample. Stirring
was stopped to read the meter.
The electrode was allowed to equilibrate so
the change in meter reading was less than 0.02 pH unit/minute before
recording.
Following each measurement, the electrode was rinsed with sea
water and placed in fresh sea water for the temporary storage between
measurements.
Additional suggestions to improve precision of saltwater pH
measurements may be found in Zirno (1975), Grasshoff (1983), and Butler et
al. (1985).
29
Salinity
E!!
270
17s
110
69
191
121
a.0
a.2
ii
18
19
12
i::
a.8
9.0
if3
4.6
2.9
2;
3.3
2.1
7.0
7.2
7.4
7.6
7.8
131
77
83
52
::
::
f's
5:4
3.5
2.3
1.5
Salinity
7.0
7.2
7.4
7.6
7.8
291
a.0
a.2
a.4
8.6
a.8
9.0
:8
19
12
:;
ld
7.5
5::
183
116
73
200
12s
79
so
:::
7.4
7.6
7.8
:*i
a:4
ii*:
9:o
312
196
12s
79
50
31
20
12.7
8.1
5.2
3.3
208
13s
8s
54
62
:s
23
1s
9.4
5.8
ii
16
ii04
4:2
2.7
2;
1.7
1.1
2
1.6
148
94
S8
if
it'7
::"o
S:6
::i
1.7
::i
29
19
12
2;
:*i
0:92
0.67
2:
1.4
0.98
0.71
0.52
fd
18
:i
12
24
:t7
PS
4:8
:*i
::ii
ii::7
K4
0.69
:*:
1:s
1.0
:*:
ohs
64
::
1s
9.8
i'9
S:6
44
27
17
11
7.1
21
13
a.3
5.6
3.5
:::
o’%
0:56
0.44
20 g/kg
ix
::
1s
::;
q/kg
92
87
54
Salinity
7.0
7.2
10
137
:::
i::
-
6.2
t:;
1.7
1.2
:3
17
1:9
0.73
o.s4
21
14
a.7
5.6
3.5
2.3
1.5
l.L
0 .77
0.56
0.44
- 30 g/kg
102
64
:"s
16
10
6.7
4.2
2.7
1.8
1.2
30
71
::
21
if3
:-ii
2:o
1.3
0.94
23
::
1s
9.4
i35
s:4
3.5
2.3
1.6
6.0
3.7
2.5
1.7
1.1
0.81
0.58
0.36
i!AS
0156
Salinity
pH
7.0
7.2
7.4
7.5
zi
012
0.4
8.6
9"::
41
26
17
10
6.6
4.1
2.7
1.7
1.1
0.69
0.44
29
18
12
7.2
4.7
2.9
1.8
1.2
0.75
0.50
0.31
20
12
2:
::i
1.3
0.81
0.53
0.34
0.23
Salinity
7.0
7.2
7.4
7.6
2:
a.2
8.4
8.6
8.8
9.0
if
18
11
6.9
X
1.8
1.1
0.72.
0.47
30
21
if
7.5
4.7
3.0
ii'1
5.3
:*s
0:7e
0.50
0.34
:::
1.3
0.84
0.56
0.37
0.24
Salinity
7.0
7.2
7.4
7.6
87::
8.2
8.4
:I:
9.0
47
29
:s
7.5
22
2
::1
3::
PO'
1:9
k:8
0.50
f-f
ohs
0.53
0.34
i!7
S.6
2:
1.4
0.90
0.59
0.37
0.26
-
10
g/kg
;:;
1-i
F7
5.3
3.4
1:s
0.97
0.62
0.41
0.27
0.18
0.13
:::o
0.07
0.56
0.37
0.25
0.17
6.6
2;
1.7
ki9
0.44
0.29
0.20
0.14
0.10
xl
1.8
1.2
0.75
0.47
0.31
0.21
0.15
0.11
0.08
3.1
2.0
1. 2
9.a4
0.53
0.34
0.23
0.15
(1.11
0.08
0.07
- 20 g/kg
14
9.0
5.6
i:;
i*:
1:s
0.94
0.59
0.41
0.26
0.18
-
6.6
4.7
3.0
:*;
:::
1.7
t.606
0:44
0.20
0.19
0.13
;::2
0.47
0.30
0.20
0.14
0.10
:*i
0178
0.50
0.31
0.22
0.15
0.11
0.08
7.2
5.0
4:;
:-;
113
0.81
0.53
0.34
0.23
0.16
0.11
1:6
3.1
2.1
1.3
3.84
0.53
3.34
0.21
0.15
,3 .?2
3.38
0.137
30 g/kg
11
1s
9.7
5.9
6.6
4.1
3.1
1.7
:*:
1:6
:::2
0.41
0.27
0.19
31
ii*:9
a:44
0.30
0.20
0.14
:*;
0:75
0.50
0.31
0.22
0.15
0.11
0.08
3.4
2.2
1.4
0.90
0.56
0.37
0.25
3
1
0::;
0.09
0.07
Char.
Lc-‘5a
0‘
cc-50
tag/L
MY-J)
-_--_-_--_
---
gw
--
Imp
( cl
---_
S8l
tg/kgt
---
J. 95
20.2
9.1
J JO) 96
20
a1
a .b-15
J.lOI. 94
20
11
J.lO0. II
20
21
J. -to4.21
20
11
..d-
b.2
20.5
24
WY4Cl
. .w=
4 a
20.1
14
8.01
21.4
28
4.01
22.4
10
b
bdUl
YY4Cl
t
1 .a4
4)-bA
ma
YY4Cl
11-17
-1
YY4C
10-11
mm
YY4c.i
I.l-5..=
YY4CI
4.*-4.4
24-4,‘
c
1
E
4.7-5.1
ma
YYIC
bdult
bdul
t
L
.a45
9
IY4Cl
B.SAb
.a54
Q
MY4CI
@.b14
IY4CI
1 .Ob
1.92
JO. 4
10
4.1
19.)
14.4
J.OC
21.2
lb.0
l.Sb
19.4
14.6
c
b
Ibrve
lb-10
l rn
YY4CI
a.51
)uvoer
1.
WbltCl
0.21
b
l-5
deym
Old
b
YYIC
1
a .4Q
32
Char
I4et hods
LC-50
(-q/L
or
MY-b)
cc-50
- ___--__- ---_
py
T*mp
(
-_
S*l
cl
lY/k9)
----
---
b
YYICl
0.92
YY4Cl
1.00
YY4Cl
0.16
YY4CI
I .Sl
WY4Cl
1.91
19.4
11.7
J.92
19.4
1I.b
I.99
19.4
14.5
4.4b
a1 .a
lb.0
l.b(
I.92
20.b
15.b
YYICL
0.2b
b.O41.12
rY4Cl
0.50
4.97.0
a5
31
YY4Ci
0.54
‘4:
7.2
a5
bl
YY4CI
1.18
7.7
25
10
UY4CA
1.44
7.48.1
24
I1
UY4CL
L .78
1.90.0
UY4Cl
b.IS
7.00.2
a5
10
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2.0
7.90.1
a5
a0
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2.0)
‘).90.1
as
a0
IY4Cl
1.47
1.74.0
I5
bl
8Y4CI
1.49
1.48.1
a5
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a. 94
7.49.1
as
b
b
b
b
24
II
*.I
l .r
l
33
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2b.
5
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YYdCl
J.41
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a.92
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J 91.a
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9 o9.a
15
10
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as
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4.2
19.1
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IYICl
a. lb
YYICl
a.86
lY4Cl
a.06
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b.10
4.41
aa
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d
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11
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9.1
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l-50I.75
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A.‘.=
‘).95‘).9b
a1
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1.1
9.9JI.94
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2.75=
2.857.97
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5.‘IC
O.OL0.1)
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BY4Cl
4.15
[email protected]
15
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l u4c1
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8.08
ai
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10
lY4Cl
1.1s
4.14
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0
10
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4 .a(.a
10.0
a5
9
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c
L&I.
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0‘
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Slrrpbd
Muqlb
l ullbt,
C.~h~lU~
LC-50
tap/l.
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QC cc-54
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----
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4 c1
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Sal
I9/kY
---
YHbCl
5.H
1 .bJ
J.99
Al
0
10
J
10
10.0
q
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5.n
a. 14
a. 00
al.
al.4
a4
a1.4
a4
1
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roaocbathur
Irl.:~~h,
hbrpbdub
0.1
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YY4Cl
0.n
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Plbaobobd
loaocamthus
I~lotr~L,
htrptdua
6.4
9
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5.n
0.914
I
Imd
dsua.
sc1~oropr
tun4baso4
S.M
0.545=
a II4.a
a5-ar
oc~llalua
IY4Cl
5.n
0.14
1.9b
10
1.01
I0.b
1.50
IO.
1.9b
10.0
9.0
1.9b
JO.1
9.1
4.00
14.0
9.1
0.00
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10.2
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9.9
01
10-10
b
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pbnrdbb
srlv.rmbdo.
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l mrrdrb
9
4.5
b
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lo
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5.1
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~ur*r11.
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s.Jt
1.a1
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5.n
1 . 1e
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YYICl
+.I
b.91
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S.I
1.24
10.4
b
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aerrdra
bb~raSbbd4.
l errdra
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Noa1dia
611v.r~14.,
araidra
1
10.1
b
b
l 1Lvormrdo.
rtlentrc
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l mrrdra
b
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b
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srluerarda.
l ~aldaa
b
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tteardib
l
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b~lv~r~1d*.
a.abdia
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s.n
1.0
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aeardba
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l
l rlvor*rd=.
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l IlV.#Sld..
l *ardba
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mmrdr,
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b
a.5
al.
1
10.2
1.21
4.94
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i
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i
0.94
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19
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15.0
11
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tirlvrrb1d..
b*ryllIafi
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l
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rt.n
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4.91.1
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nntc
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cc-50
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I El
15.5
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YIl4l.l
14 .a
IU
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YYIC
15
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5
JO
16.5
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IS .o
YY4Cl
14
YYlCA
II
YY4CI
>b
lY4Cl
15.5
YYICI
14.5
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11.5
WYIC
5
L
36
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cnq
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CA
faq
IYIb
4
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cnq
l98b
4
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IYIb
9.a
chmr
I4olhuJs
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l-c-50
0,
cc-50
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rrnp
t Cl
----
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YHICI
rt,fl
2.79
1 bJ.9
IlH4CJ
rt.n
1.5
I b7.9
YU4CJ
rt.n
1. JO
a.o-
25
JO
11.5
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11.5
7 5b? bl
15
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1.59-
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a.1
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1.25
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1 .bS
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S,M
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s.n
a. 15
nn4cl
1.1
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1 .Oba.11
15
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15
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1.4
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1.04
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37
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b,..
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luoltlodr
LC-50
oc EC-50
lnq/L
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tarp
4 Cl
----
JaIV*
1 day
old
YU4CL
s.n
a.5)
I Y0.1
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5
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larva
1 day
YY4CJ
5.n
0.51
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1 5
II
old
larva
A day
WY4CJ
S.N
0.44
KSa.1
J.5
II
old
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38
CArdrIb
------
IYIb
-
----_
- _._.
.
5y.c
-------
I*K
Nathad
------
RM
-rYcstlY*Tcll
SPCCIES
LC
l.O1.5
0.199-0.0411
0. JO4
Lc
9.09
0.)14-O.li5
0.521
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1.6
14.2
0.5J-O.lb
0.6)
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l.blb-lb
17.b20.0
0.94-l
CIA
b.lb.9
4
0.4024-0.004
0.00~1
ELS
b. Bb.5
4
0.0012-0.0024
0.0011
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0.0111-0.04J9
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1.01
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01
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value
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1 b7.0
0.OlJ-0.146
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4.0011
0.090
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a.411
0.0111
0.
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IS
1.54
0.11
2.5L
0.11
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4.101
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J
LC50
knuraal,
W.
1977.
~oltrance
crf estuarinc
Senthic
of ammma, mtrrte
13n, xtrate
concentrations
.wr.
Bfol.
diatoms
to hiqh
13n and or~~0phosphatc.
:307-315.
43(4)
Ahbaster.
J.S., D.G. Shurkn,
and G. Knowles.
1979.
The effect
of
dissolved
oxygen and salinity
on the toxicity
of wxmmia to snmlts
salmon, --Salnm salar
of
L.
J. Fish
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Bid.
Alabaster,
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Semnd Ed. J. AL&stcr
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TM effect of ammonia on the growth of juvenile
R. 1979.
Dover sole, Solea solea (L.1 and turbot Scophttulms maximus (L.).
Aquaml ture Vi27 :231-309.
Alderson,
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Rapid assessiwnt
usinq the fingernail
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‘WRCRes. iep. Go. 133; Mater Rarourcrr Center, Lbiversity
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Urbana, IL: 11s p.
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Effects
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Ultrastructural
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Ultraaicrorcupy
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Annstrung,
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Interaction
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to cmstacea and aspmts of its
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Armstrong,
D.A.
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Biennial Cmstacmn
Nitrogm
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aammia
Bartberqer, C.A. a& S.A. Pierce,
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Biol.
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Hydtogm ians and ti
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The Fat*
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the-c
of ?osril
e\lol CO in
PIWIt=, N-Y., N. ? .
R.G. UK! G.D. Plnchlng.
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Acidic
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48
amine8 and related
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Jactfic
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Okranclogiyr
photosynthmis
Cl., Chaetocwor
1968.
m
effect
of ma
acdatim
ad
pi-t
sp.
ami Prorocmtmm
8(l) :90-30.10
59
a
nitrogwn
in Scrl8tonana
micans
EM.