903979003
U.S. ENVIRONMENTAL PROTECTION AGENCY
r
L
r
L
MIDDLE ATLANTIC REGION- III 6th and Walnut Streets, Philadelphia, Pennsylvania 19106
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EPA 903/9-79-003
CARBONACEOUS AND NITROGENOUS
DEMAND STUDIES OF THE
POTOMAC ESTUARY
(Summer 1977)
Annapolis Field Office, Region III
Environmental Protection Agency
Joseph Lee Slayton
E. R. Trovato
-------
DISCLAIMER
The mention of trade names or commercial products in this
report is for illustration purposes and does not constitute endorsement
or recommendation by the U.S. Environmental Protection Agency.
-------
TABLE OF CONTENTS
Page
Tabulation of Tables iii
|
Tabulation of Figures iv
I. Introduction 1
II. Conclusions 4
III. Procedure 6
IV. Oxygen Demand in The Potomac River Samples
A. Biochemical Oxygen Demand - Carbonaceous
1. General Discussion 7
2. Standard BODs Test 7
3. CBOD/First Order Kinetics 8
4. Thomas Graphical Determination of
BOD Constants 10
5. Temperature Effect Upon Reaction Rates 14
6. Nature and Distribution of CBOD 19
B. Biochemical Oxygen Demand - Nitrogenous
1. General Discussion 27
2. Bacterial Growth Requirements 28
3. Lag Phase and Growth Characteristics 29
4. Stoichiometry of Nitrification 30
5. Nitrification Kinetics 43
6. Nature and Distribution of NOD 43
V. Oxygen Demand in the Potomac STP Effluent Samples
A. CBOD 51
B. NOD 51
C. Loadings Characteristics 54
-------
TABLE OF CONTENTS (con't)
Page
References 67
Appendix:
A. N-Serve/NOD Determinations 69
B. Alternative Methods 70
C. Study Data 72-84
11
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TABLES
No. Page
1. Station Locations 3
2. Thomas Graphical Determinations of k^g, and Lo,
for river CBOD's 12
3. Thomas Graphical Determinations of k^Q, and Lo,
for river BOD's 15
4. Chlorophyll a_ vs CBOD 26
5. NOD2Q vs (TKN-N x 4.57) 32
6. Thomas Graphical Determinations of k^Q, Lo, and r
for river NOD's 44
7. Ratios of NODs/BODs and NOD20/BOD2Q 48
8. Thomas Graphical Determinations of kio> Lo, and r
for STP CBOD's 52
9. Thomas Graphical Determinations of k^g, L0, and r
for STP NOD's 55
10. Summary sheet of % [NOD2o/NOD Ultimate] for STP's 60
11. STP Loadings of CBOD20> NOD Ultimate, and BODs 61
12. Proportion of Total STP Demand Expressed as NOD 63
13. N02-N Concentration and the Resulting NOD Error 65
14. Potomac River Long-Term BOD Survey Data 72-84
111
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FIGURES
No. Page
1. Study Area 2
2. Depletion Curve for BOD and CBOD 17
3-8. BOD2Q. CBOD2Q and NOD20 vs River Mile Index (RMI) 20-25
9. Plot of NOD2Q vs (TKN-N x 4.57) 35
10, 12-16. Plot of NOD20 and (TKN-N x 4.57) 36, 38-42
11. NH3-N, N02-N, N03-N and TKN-N vs RMI 37
17. NOD Depletion Curves 46
18-20. BOD, NOD, and CBOD Oxygen Depletion Curves 57-59
IV
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I. Introduction
During the summer of 1977 an intensive survey of the middle reach
of the Potomac River (Figure #1) was undertaken by the A.P.O. All
samples were collected under slack tide conditions. As part of this
work, 20-day B.O.D. analyses were performed on selected stations
(Table #1) to help define the major oxygen demand inputs and establish
their effect upon the river. The fraction of the B.O.D. associated
with nitrogenous oxygen demand was determined using an inhibitor to
nitrification. To afford a more meaningful intrepretation of the
results, a discussion is included on the B.O.D. test; nitrification;
and the nature and action of the inhibitor employed.
-------
Figure 1. Study Area
Potomac Estuary
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Table #1
Station
Number
P-8
P-4
1
1-A
2
3
4
5
5 -A
6
7
8
8-A
9
10
10-B
11
12
13
14
15
15-A
16
Station
Number
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
Stations
for
Long Term
BOD/NOD
X
X
X
X
X
X
X
X
X
X
Stations
for
Long Term
BOD/ NOD
X
X
X
X
X
X
X
X
Station Name
Chain Bridge
Windy Run
Key Bridge
Memorial Bridge
14th Street Bridge
Hains Point
Bellevue
Woodrow Wilson Bridge
Rosier Bluff
Broad Creek
Ft. Washington
Dogue Creek
Guns ton Cove
Chapman Point
Indian Head
Deep Point
Possum Point
Sandy Point
Smith Point
Maryland Point
Nanjemoy Creek
Mathias Point
Rt. 301 Bridge
Treatment Plant Name
Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
RMI
0.0
1.9
3.4
4.9
5.9
7.6
10.0
12.1
13.6
15.2
18.4
22.3
24.3
26.9
30.6
34.0
38.0
42.5
45.8
52.4
58.6
62.8
67.4
a, RMI*
18.4
5.9
11.1
12.4
12.8
20.0
22.3
24.5
Buoy Reference
C "1"
FLR-23' Bell
C "87"
N "86"
FL "77"
FL "67"
R "64"
FL "59"
N "54"
R "44"
N "40"
N "30"
G "21"
N "10"
C "3"
The RMI's are approximate since the STP's are often located on ewbayments
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II. Conclusions
1. CBOD of the Potomac River samples followed first order kinetics
with an average ke=0.14 day~l.
2. In August, a significant increase in CBOD, between Gunston Cove
and Possum Pt., correlated (r=.94) with an algae bloom of
Oscillatoria.
3. NOD of Potomac River samples between Hains Point and Ft. Washington,
(peak NOD area) followed first order kinetics with an average
ke=0.14 day"1. The exceptional samples had significant lag times
resulting in S-shaped or consecutive S-shaped D.O. depletion
curves. These samples were limited to the algal bloom area and to
samples from the Chain Bridge area which had low NOD2Q (2.0 ppm average).
4. In general, the NODj- represented about one-third of the BOD5 of the
river samples and therefore, estimates of CBODs from 8005 values
are prone to error unless a nitrification inhibitor is employed.
5. The CBOD2Q represented 68% of the river demand2Q-
6. The CBOD of the STP effluents followed first order kinetics with
an average ke=0.17 day~l.
7. The CBOD2Q represented 31% of the STP effluent demand20-
8. The NOD for the STP effluents had a significant lag time resulting
in S-shaped or consecutive S-shaped depletion curves. This lag time
was probably an artifact, since nitrification in the receiving
waters was immediate.
9. The NOD20 observed for river samples did not significantly differ
from (TKN-N x 4.57) which suggests:
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II. Conclusions (con't)
a. Nitrification was essentially complete after 20 days
of incubation.
b. The nitrification inhibitor 2-chloro-6 (trichloromethyl)
pyridine (common name nitrapyrin), gave accurate NOD results.
c. The NOD observed was due to autotrophic bacteria since
the inhibitor was specific for Nitrosomonas spp.
10. The relation CBOD2o =1.85 CBOD5 held consistently for the Potomac
River samples and, with the use of nitrapyrin, short term experiments
may yield adequate estimates of ultimate demand via the relation:
UBOD =1.85 CBOD5 +4.57 (TKN-N).
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III.Procedure
BOD: The BOD test employed was that outlined in Standard Methods
APHA 14th edition*. Dilutions were made for the S.T.P.
samples using BOD bottles, that were within ± 1% of 300 ml,
as volumetric flasks. S.T.P. samples were diluted with APHA
dilution water; seeded using 1 ml per bottle of stale raw-
settled S.T.P. influent; and dechlorinated. All samples were
purged for 15 seconds using purified oxygen and a Fisher gas
dispersion tube to obtain an initial DO of 10-15 ppm.
DO: All dissolved oxygen measurements were made using a YSI BOD
probe #5750 and a YSI model #57 meter. These were calibrated
against the Winkler (azide modified) method*.
Nitrification: The nitrification inhibitor (Hach Chemical Co. #2533)
was dispensed, using a powder dispenser, directly into the BOD
bottles. This allowed quick and uniform additions of the
inhibitor. Two bottles were filled with each sample; one
received the inhibitor and represented CBOD and the uninhibited
bottle expressed total BOD. The NOD was determined by difference.
Nitrogen-Series: TKN-N was analyzed by the automated phenate method-'-.
The N02~N + NO^-N was analyzed by the automated cadmium
reduction method*.
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IV. Oxygen Demand in the Potomac River Samples
A. Biochemical Oxygen Demand-Carbonaceous
1. General Discussion
Biochemical oxygen demand is a bioassay procedure concerned with
the utilization of oxygen in the biochemical oxidation (respiration)
of organic material. This test is one of the most widely used
measures of organic pollution, applied both to surface and waste
waters. The BOD test has been relied upon in the design of waste
treatment plants and to establish standards for effluent discharges.
One of the primary disadvantages of this test is that as a bioassay
it reflects biological variability. The test is not a relatively
simple assay whereby pure strains of bacteria interact with a well-
defined media, but involves monitoring a complex and changing
population of microorganisms (bacteria, protozoa, fungi, algae, etc.),
as they respire in a changing mixture of organic matter. Interlaboratory
studies have established its precision on synthetic samples to be
± 20% at 2i 200 ppm BOD . The accuracy of the test is difficult to
assess since the results obtained for "standard solutions" vary
markedly with the seed employed .
2. Standard BODg Test
The standard method of BOD measurements, adopted by APHA1,
is a five-day test at 20°C in the dark. The five-day incubation period
was selected to maximize that portion of the oxygen demand associated
with heterotrophic respiration (oxidation of carbon compounds)
and, at the same time, minimize the oxygen demand of autotrophic
organisms, primarily nitrifying bacteria. The basis for this method
-------
IV- Oxygen Demand in the Potomac River Samples (con't)
selection rests upon the generally observed 10-15 day lag in oxygen
uptake associated with the growth of nitrifying bacteria in sewage
samples. This assumption was found to be erroneous for Potomac
River samples.
The standard BODr test was designed to provide the biota with
the macronutrients and oxygen necessary for growth, such that the
rate of utilization of organic material will be limited only by the
amount and nature of the organic material present. In comparison
to a long-term test of 20 or 30 days, the short-term test is more
severly dependent upon the number and type of biota introduced (seed)
and the temperature of incubation. These factors will affect the
kinetics of respiration. In essence the standard 8005 test ^or
sewage effluents was not designed to give accurate rate estimates,
but its use as a best estimate remains because of the absence of an
alternative. BOD tests of river water involved no dilution nor seeding
and may have the best correlation with actual river rates, since the
least manipulation of the sample is involved. Because the kinetics
of the process are largely avoided when measuring plateau values,
which are not measureably affected by seed conditions or temperature
value between 4 and 20°C , the ultimate oxygen demand has been cited
as a more practical parameter for judging the potential pollution load .
5. CBOD/First Order Kinetics
The kinetics of the carbonaceous BOD observed during this study
were first order. The observed oxygen utilization fell off exponentially
with time, and approached an ultimate asymptote. The first order
-------
characteristic is thought to be the summation of many different
reaction rates of the gamut of material expected in waste and river
samples.
The expression relating the remaining oxygen demand L, at time
t is given by:
-dL = k Lo equation #1
dt
such that the rate at any instant is proportional to the amount of
BOD yet to be expressed. Lo is the intial remaining oxygen demand (at t=o)
or ultimate demand and k is the deoxygenation rate constant, day
Rearranging and integrating equation #1
L
= k / dt
where tQ = 0,
= -(In L-ln Lo) = kt
or In L = In Lo - kt equation #2
The - kt term can be expressed as In e~kt, since In ex = X, and equation #2
becomes
In L = In Lo + In e"kt
or the familar expression
L = Lo e~ equation #3
However, the BOD test actually involves the measurement of oxygen
consumption rather than the amount left to be depleted, so a new variable
-------
10
y (oxygen depletion) is introducted such that
y = Lo -L
and substitution into equation #3 yields
y = Lo (l-e~kt) equation #4
The average ke value reported 5 for the Thames River STP effluent
samples was 0.234 day"1 which results in
y/ - (1.eC-234)(S))
/Lo
or Lo = 1.45 y
or BOD ultimate = 1.45 x BOD5
It should be cautioned that the equivalent expression
y = Lo (l-10"klt) equation #5
is often employed with k=k'x2.303
The observed Potomac River samples' CBOD^ and CBOD2Q data, included
in Table #2, gave the following best fit function:
CBOD2Q = 1-85 CBOD5
with a correlation coefficient of 0.945 based upon 53 data pairs.
4. Thomas Graphical Determination of BOD Constants
All data points (6 or 7 readings per sample over the 20 day
incubation period) were also used to give the best available estimate
of k^g and L by using the Thomas Graphical Determination^'?. This
method relies upon the observation that the relation (l-10~kt) is
_T
very similar to 2.3 kt [l + C^-3-) kt]
6
such that by using equation #5
y = 1^2.3 kt [l + (^) kt]"°
-------
11
or
1 (2.3k)2/3 t equation #6
(2.3L0k) * (6LQ)1/3
A plot of f ^/\^" vs t yields a linear relation with slope
m = (2.3k)2/3 and intercept b =
,1/3
C2.3kL0)
BOD k^Q and L values can be determined from equation #6 as follows
(2.3k)2/5 slope
C6L0)1/3
m =
b
m
b
(2.3kL )*/3 intercept
(2.3)2/3 x (2.3)1/3 x k2/3 x
or
k = 2.61m
b
Also since b = ( 1 ^ 1/3 it follows that Lo= 1
I 2.3klJ
2.3b3k
The end result is that the two variables L0and k^g are related to
a close approximation to y and t by two simple equations which
allow their solution.
To facilitate the calculation of Thomas constants, a computer
program was written to compute the k^Q and LQ.
The results are compiled in Table #2. The average (n=43) k-^Q
value observed for river CBOD's was k^g = 0.062 days'-'- or ke = 0.14 days"*,
The correlation coefficients (.30-. 99):
y = L0 (l-10-kt) * 2.3kt (1+ 2^3l!) "
6
suggests first order kinetics. The value predicted by the
Q
Dynamic Estuary Model (DEM) for the deoxygenation rate constant,
kp, of CBOD's at 20°C was 0.17 days"1.
-------
TABLE # 2
CBOD RIVER
12
DATE - STA
THOMAS GRAPHICAL DETERMINATION
July 27 -
Aug. 3 -
Aug. 24 -
P8
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
0.070
0.049
0.057*
0.065
0.062
0.035*
0.053
0.073
0.069
0.051
0.058
0.067
0.056
-
0.041
-
0.001*
0.065
0.020*
.071
.018*
.066
.066
.083
.055
.060
.055
.057
.059
.078
.067
.075
.066
.065
.052
.032*
.032*
.012*
5.41
6.76
8.67
6.51
8.40
11.78
8.80
6.85
6.69
7.99
3.85
5.62
4.67
_
10.18
_
15.60
5.61
7.91
4.39
10.51
7.04
5.93
5.98
7.31
8.26
7.02
6.43
6.15
4.68
4.46
6.19
9.28
8.66
10.40
20.93
23.78 -
22.38J~
1 lag phase
1 lag phase
1 lag phase
1 lag phase
8/24 bloom
300 ppb chloi
CBOD 5
3.0
3.0
5.2
2.6
4.4
5.3
4.2
4.0
3.8
3.8
1.8
3.0
2.3
3.0
4.0
3.1
3.0
1.9
2.3
3.0
3.7
3.2
3.5
3.6
3.9
3.2
2.9
3.1
2.6
2.2
3.6
5.2
4.3
4.6
7.6
6.6
2.8
CBOD2Q
5.0
6.0
8.2
5.9
7.6
9.7
7.9
6.2
6.2
6.9
3.5
5.1
4.1
5.1
8.9
6.4
5.1
4.6
4.1
5.1
6.6
5.2
5.3
6.5
7.8
6.4
6.2
5.8
4.3
4.2
5.7
8.6
8.0
9.4
15.4
17.3**
9.0**
_
Algae major contributor
-------
TABLE # 2 (con't) CBOD RIVER 13
THOMAS GRAPHICAL DETERMINATION
DATE - STA k10 Lo CBODs CBODzO
Aug. 31 - P8 .058 4.17 2.1 3.8
1 .061 4.65 2.4 4.3
3 .014* 13.80 1 lag phase 3.2 5.7
4 3.8 6.5
5 .053 7.59 3.7 6.7
6 .091 8.17 5.2 7.2**
7 .062 10.00 5.1 9.2
8-A .050 12.54 5.2 11.1
10 .055 12.98 6.3 11.9
11 .059 9.48 4.6 8.7
Sept. 8 - P8 .043 5.25 2.0 4.5
1 .069 4.91 2.6 4.5
3 .056 5.31 2.5 5.0
4 .081 8.01 4.8 7.4
5 .056 9.76 4.8 8.8
7 .071 4.80 2.6 4.5
8-A .065 6.35 3.2 6.1
10 .018* 14.66 1 lag phase 3.9 7.3
11 .035* 8.72 * 3.1 6.9
* Not included in calculation of average kjQ due to their exceptionally
low correlation coefficients and lag periods in growth
** Deleted from calculation of CBOD5/CBOD2Q
k!0 :
n = 43
average = .062
s.d. = .010
-------
14
The total BOD for the river samples (Table #3) also followed
first order kinetics with correlation coefficients over the range
of (1.000 to .156) with an average (n=50) kjo of 0.054 day"1.
This rate corresponds to an expression of 47% of the ultimate BOD
after 5 days such that: BOD2Q = 2.1 x BOD5
An oxygen depletion curve is included in Figure #2.
5. Temperature Effects Upon Reaction Rates
Any statement concerning the observed B.O.D. reaction rates
should take into consideration the potential error due to fluctuation
in the incubation temperature. If it is assumed that over a narrow
range biochemical reaction rates tend to increase, as do strictly
chemical reactions (endothermic), with increasing temperature,
then the effect of temperature upon the rate of these reactions may
be approximated by the Arrhenius equation^: k = Ae" '
were A is the frequency factor or pre-exponential factor (time );
Ea is the activation energy, (energy/mole); T is temperature in
°Kelvin and R is the ideal gas constant (energy x temp x mol ).
Taking the natural log:
-Ea
In k = + In A
RT
and differentiating with respect to temperature:
d In k = d In A - d Ea_
d T d T RT
d T
but A, Ea and R are all constant with respect to T.
or: d In K = -Ea d T'1 = Ea_
d T R d T RT2
-------
TABLE # 3
BOD RIVER
15
DATE - STA
July 20
July 27 -
Aug. 3 -
Aug. 24 -
TA
P8
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
kio
.037
.032
.058
.027
.049
.. 036*-
.040
.058
.048
.051
-.023*
.047
.060
.057
.047
.059
.041
003*
.053
.023
.105
.081
.063-
.079
.080
.045
.030
.049
.039
.042
.045
.047
.072
.081
.063
.059
.049
.011*
.010*
-.004*
9.10
10.95
13.27
18.31
21.14
24.5-
14.71
10.74
10.59
10.53
-2.99
5.73
8.50
10.60
11.87
16.45
14.08
100.0-
7.95
12.75
2.38
5.85
13.99
12.14
11.08
9.45
11.50
13.12
12.50
9.17
9.52
7.83
9.01
10.99
12.99
13.00
14.45
62.48
68.80
-63.35
1 lag phase
2 lag phases
1 lag phase
1 lag phas"e~)
1 lag phase h al§a^
, linear^ J chloro
1
r=.999
m=.673
b=-.232
300 ppb
-------
16
TABLE # 3 (con't) BOD RIVER
DATE - STA k10 L0
Aug. 31 - P8 .063 5.73
1 .056 5.97
3 -054* 14-76 1 lag phase
4
5 .073 12.77
6 .075 12.96
7 .071 14.80
8-A .059 17.89
10 .045 19.62
11 .044 15.66
Sept. 8 - P8 .016 13.04
1 .039 8.11
3 .066 10.39
4 .060 18.65
5 .060 22.81
6 .066 12.60
8-A .062 9.84
10 .026* 15.10 1 lag phase
11 .023 16.12
* Not included in calculation of average k due to their exceptionally
low correlation coefficients and lag periods in growth
k!0:
n = 50
average = .054
s.d. = .017
-------
I I ! ! I I f 1 I ! I ! i 1 f J f ! f ? f 1 f 1 I i i i * «
ro-
00'
1-3
I
ro
o
Oxygen Depletion mg/1
ro
o
o
-t
i
CO
o
I
p
'o
~T
M
o
H-
CO
M
t-<
a>
00
Oxygen Depletion mg/1
° £V-
ro -
00 -
(O
tu'
00
ro
o
K>
o
o
ro
5?
(B
8
03
is
M
O <
-------
18
Integrating over temperature and rate
/T2
d In k = / §i_ d T
Tl' RT2
\ 2. "7
In k2 - In kj_ = Ea \ T"^ d T
R TV
In
11 R \T1 T2J
In /k2\ = Ea /T2 - TL\ equation #7
Because the original assumption is that only a limited temperature
range be considered, T]_ x T2 (in K ) is essentially constant. Let
Ea = 9, which has been termed the temperature coefficient.
RTXT2
Substitution of 6 into equation #7.
In ACT / \ ^
Experimentally determined 6 values have been found to be reasonably
constant over narrow temperature ranges with the average value for
temperature coefficient over the range 5-25°C being reported ' as
0.056 "C"1 and 0.047 "C"1. The observed difference between experimental
1 5>1:L
(ke = 0.143 day'1) and classical (ke = 0.234 day"1) rates cannot
be explained based soley on fluctuation in incubation temperature. This
can be shown by substituting these values into equation #7
In f"234\ = 0.056 (20-T1°C) Equation #8
-143/
-------
19
and solving for T^
!]_ = 11°C.
A 9°C variation in temperature is necessary to explain the difference
in rates. The observed fluctuation of the Jordon Model #818 BOD
incubator was 20 +_ 1°C (measured with an NBS certified thermometer)
during the course of the Potomac Survey. Therefore it may be
concluded that the observed rate cannot be explained by temperature
fluctyation.
6. Nature and Distribution of CBOD
The distribution of the CBOD20 vs RMI and STP locations are
compiled in figures 3-8. The peak(s) CBOD area extended from the
Memorial Bridge to Gunston Cove, which corresponds to the locations
of the major STP's: Arlington; Blue Plains; Alexandria; Westgate;
Piscataway; Hunting Creek; Dogue and Pohick.
A second CBOD peak area was observed on August 24 (figure 6)
which corresponded to an algal bloom with a chlorophyll a concentration
of ^ 300ppb. The chlorophyll a_ and CBOD data for stations 8-A, 10, and 11
are compiled in Table #4. The high correlation obtained (r=.94 and
n=18) suggested this second peak demand area was largely attributable
to algal decomposition and/or respiration. The kinetics of the CBOD
process for stations 8-A, 10, and 11 were first-order exponential but
were abnormally slow (Table #2). These data points were not included
in the calculated ke of 0.143 day"-'-.
The average CBOD2Q entering the study area at Chain Bridge was
4.6 ppm while the average NOD2Q was 2.0 ppm. Figures 3 thru 8 reveal
-------
July 20, 1977
BOD2Q 0
CBOn20 X
NOD20 Q
? * I
1 I 1 i I
Miles Below Chain Bridge
1 I I * I * 1 '
T)
H
a>
-------
t i l i i I I i I * ! 1
! I I j 1
July 27, 1977
BOD20 0
CBOD20 X
NOD
2Q
18
20
22
24
26
28
30
32
34
-n
H-
oq
36
38
RMI
-------
August 3, 1977
1
(0
BOD
20
0
4-
2-
CBOD20 X
NOD2Q -
RMI
? 1 « I f t f 1 f I I I I I I I
* 1
-------
i i i i i } f
i r i i i i t f i r i
August 24, 1977
i i f ) i i i i i i f i i i
32 34 36 38
-------
August 31, 1977
BOD2o 0
CBOD2Q X
NOD20
10
38
RMI
! ft
fl 1 ?
rill fi fi || fi ft if
fi
-------
i I f j f 1 !
f i f i f i i s r ] t i ' i i i
1 t i
September 8, 1977
BOD20 0
CBOD20 X
NOD
20
n
00
22 24 26 28
38
K)
01
RMI
-------
26
TABLE # 4
Date
July 20
July 27
Aug. 3
Aug . 24
Aug. 31
Sept. 8
Station #
8 -A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
8-A
10
11
n=18
r=.942
m= . 046
b=1.907
Name
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Gunston Cove
Indian Head
Possum Point
Chlorophyll a'
ppb
86.2
81.0
90.0
123.0
129.0
112.5
103.5
76.5
85.5
306.0
312.0
168.0
187.5
195.0
148.5
85.5
100.5
120.0
CBOD20
ppm
6.2
6.2
7.2
6.4
5.1
4.6
7.8
6.4
6.2
15.4
17.3
9.0
11.1
11.9
8.7
6.1
7.3
6.9
-------
27
that CBOD is in general more significant than the NOD for the river
samples. This may be attributed to the greater masses of carbon
in the system8. The average NOD2o/BOD20 (Table #7) was 0.38, (n=58).
The algal bloom area exhibited the same trend which reflects the algae
C/N ratio of 4.6 found by elemental analysis. The few exceptions
to the dominant CBOD pattern were restricted to river locations
adjacent to the sewage plants in the reach from the 14th Street
Bridge to Broad Creek. Nitrification was largely completed above
the algal bloom area.
B. Biochemical Oxygen Demand - Nitrogenous
1. General Discussion
Nitrification is the conversion of NH3 to N03 by biological
respiration. This type of respiration is employed by seven genera
of autotrophic nitrifyers as listed in Bergey's manual12. However,
only Nitrosomonas stvp and Nitrobacter spp are regularly reported by
in situ nitrification studies13. In general, the treatment of
nitrifying river samples with inhibitors specific to Nitrosomonas
and Nitrobacter can be expected to stop all appreciable nitrification
It should be noted that heterotrophic nitrification can also occur
whereby N02 and N03 are formed by reactions that do not involve
oxidation. The contribution due to these organisms was not found to
be significant in the Potomac River, since a close correlation was
observed between the expected NOD (associated with TKN-N) and the
measured NOD which was specifically limited to autotrophic bacteria.
-------
28
2. Bacterial Growth Requirements
Nitrifying bacteria prefer temperatures of 35-40°C but can
survive well over the range of 4-45°C^-^. The rate of nitrification
increases with increasing temperature throughout the range of 5-35°C
Nitrifying bacteria are more temperature sensitive than heterotrophic
bacteria and their contribution to B.O.D. will vary more markedly
with temperature. BOD samples assayed during winter months should
incorporate a nitrification inhibitor to yield results more relevant
to river conditions. The temperature ranges observed during this
summer's Potomac survey were very narrow:
Date Temperature Range °C
July 20 31-29
July 27 28-25
Aug. 3 28-27
Aug. 24 26-27
Aug. 31 30-28
Sept. 8 28-27
14
Nitrifyers can generally tolerate a pH range of 6-10 . The "ideal"
values seems to vary with the particular environmental conditions
from which the tested bacteria were selected but in general a
slightly basic pH seems ideal O8.0). At pH levels below 7,
Dissolv
5,13,14
14
the rate of maximum growth was decreased by more than 50% . Dissolved
oxygen does not seem to affect the rate of their growth above O.Sppm.'
The average temperature and pH measured over the course of this study
were 27.0°C and 7.6 respectively.
The reactions involved in nitrification are as follows:
m + j. TL ri NitrOSOfflOnaS. 714+ , vin ~ + H n prmatinn #Q
. -r 1.^5 U^j i L,\\ "t" i\Uo novj cv-^LAdL.j.\jii ~ y
42 ^ ^
N02" + h 02 Nitrobacter? N03~ equation #10
-------
29
An average pH of 7.6 was found in the Potomac River long term BOD
samples. The pka of ammonia at 25°C is 9.26 . These factors
combined with the Henderson-Hasselbach equation:
pH = pka + log base
acid
establish that Nffy should be used in the preceeding equations and
that ammonium (NH^) represents 98% of all ammonia species present.
5. Lag Phase and Growth Characteristics
Nitrosomonas have a maximum growth rate less than that of
Nitrobacter and heterotrophic bacteria in general have a maximum
14
growth rate nearly double that of autotrophic bacteria (doubling time
of 30/hr)13. For STP effluent samples an NOD lag time of 10-15
days often occurs due to the slow growth of nitrifying bacteria and
the small population initially present. For this reason, nitrogenous
oxygen demand is often termed second stage BOD.
Nitrifiers not only have a slower growth rate but also are more
fragile than heterotrophic bacteria, resulting in more sporadic
results from an NOD experiment than from CBOD tests . The growth
of nitrifiers are inhibited by a wide variety of substances as :
halogens; thiourea and thiourea derivatives; halogenated solvents;
heavy metals; cyanide; phenol; and cresol.
A study of 52 such compounds known to inhibit nitrification revealed
that the inhibition of Nitrobacter is less severe than that of
Nitrosomonas; Nitrosomonas representing the weak link in nitrification .
Nitrification is a surface phenomenon with much of nitrification
occurring in clear, shallow rivers on the surfaces of mud (aerobic).
-------
30
plants, slime, etc . Laboratory experiments involving the incubation
of clear-shallow stream samples would not be expected to reflect
the extent of in situ nitrification. However in a turbid estuary,
such as the Potomac, the surface area of the suspended material is
expected to exceed that of the river bed, such that nitrification
would be expected to be more significant in the water column. Tests
of such water samples should estimate the extent of nitrification
actually occurring in the estuary.
4. Stoichiometry of Nitrification
The Stoichiometry of the nitrification reactions , equations #9 $ #10
dictate that the conversion of 1 gram of nitrogen from- ammonia to
nitrite utilizes 3.43 gx'ams of oxygen and the conversion of 1 gram of
nitrite-nitrogen to nitrate involves the utilization of 1.14 grams of
oxygen. However, nitrifying bacteria are autotrophic and as such
utilize a portion of the energy derived from nitrogen oxidation to
reduce 003, their primary source of carbon. The net result is a
reduction in the amount of oxygen actually consumed. Short term
(0-5 day) experiments,18'19'20 employing cultures of Nitrosomonas
and Nitrobacter have related the depletion of oxygen to the production
of nitrite and nitrate with the corresponding 0/N ratios of 3.22 and
1.11 determined. However in long term experiments, the decay of
these organisms would be expected to exert an oxygen demand approximately
equivalent to the oxygen originally generated, resulting in an overall
21
relation not significantly different from 4.57
-------
31
In Table #5, NC^g derived from long term incubation of river
samples was compared to a predicted value based upon 4.57 x TKN-N
initially assayed in the sample. A paired t-test established, at
a 95% confidence level, that no significant difference existed
between these methods of prediction with t=.7' at 57 degrees of freedom.
A plot of the predicted NOD (4.57 x TKN-N) vs that observed with
laboratory incubation is included in figure #9. The comparison of
NOD and TKN x 4.57 vs RMI is included in figures #10 and #12 - #16.
The close correlation suggests that:
1. Nitrification was essentially completed after 20 days
of laboratory incubation.
2. The inhibitor to nitrification employed, N-serve,
gave accurate NOD results.
3. The NOD observed was due to autotrophic bacteria since
the inhibitor was specific for Nitrosomonas.
Figures #3-8 include the found NOD vs River Mile Index and
indicate that nitrification occurs within a short span of the river,
between Mains Point and Fort Washington.
A second peak NOD area occurred, as with CBOD, at stations 8-A;
10 and 11 on August 3, 24, and 31. This was thought to reflect the
nitrogen contribution associated with the decay of the algae present
at these stations. A significant NOD lag time was observed in samples
obtained in the algal bloom area.
The changes in N02, N03, and NH3 concentration with RMI
for samples obtained on July 20 are included in figure #11. They
illustrate the classical relation expected during the course of
-------
32
TABLE # 5 NOD20 vs (TKN-N x 4.57)
Date Station
July 20 P-8
1
3
4
5
6
7
8-A
10
11
July 27 P-8
1
3
4
5
6
7
8-A
10
11
Aug. 3 P-8
1
3
4
5
RMI
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
NOD 20
2.2
2.3
4.4
6.2
11.0
11.1
4.0
3.6
3.0
2.6
1.4
1.5
2.6
5.3
5.6
6.8
5.5
3.8
2.4
3.6
LA
1.4
7.3
4.8
5.0
TKN
.741
.705
.821
2.05
2.495
2.20
1.358
1.074
.853
.621
.461
.380
.582
.986
1.212
1.301
.897
.727
.606
.509
.438
.358
1.477
1.262
1.298
NOD
(4. 57) (TKN)
3.4
3.2
3.8
9.4
11.4
10.1
6.2
4.9
3.9
2.8
2.1
1.7
2.7
4.5
5.5
5.9
4.1
3.3
2.8
2.3
2.00
1.6
6.7
5.8
5.9
-------
33
TABLE # 5 (con't) NOD20 vs (TKN-N x 4.57)
Date S
Aug. 3 (con't)
Aug. 24
Aug. 31
:ation
6
7
8-A
10
11
P-8
1
3
4
5
6
7
8-A
10
11
P-8
1
3
4
5
6
7
RMI
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
24.3
30.6
38.0
0.0
3.4
7.6
10.0
12.1
15.2
18.4
NOD20
(TCMP)
3.3
4.4
4.0
3.8
1.8
3.0
2.7
4.0
4.4
3.4
4.1
3.5
6.6
6.8
4.2
1.6
1.2
7.1
4.7
5.1
4.9
4.3
TKN
1.083
.877
.734
.684
.546
.484
.484
.894
1.378
1.161
1.094
1.119
1.269
1.328
.802
.472
.400
1.760
1.392
1.264
1.092
.968
NOD
(4. 57) (TKN)
4.9
4.0
3.4
3.1
2.5
2.2
2.2
4.1
6.3
5.3
5.0
5.1
5.8
6.1
3.7
2.2
1.8
8.0
6.4
5.8
5.0
4.4
-------
34
TABLE # 5 (con't) NOD2Q vs (TKN-N x 4.57)
Date
Aug. 31 (con1
Sept. 8
3 = .0965
Sd = 1.1207
S3 = .1471
df = 57.00
t = 0.6560
Station
t)8-A
10
11
P-8
1
3
4
5
6
7
8 -A
10
11
RMI
24.3
30
38
0
3
7
10
12
15
18
24
30
38
.6
.0
.0
.4
.6
.0
.1
.2
.4
.3
.6
.0
NOD 20
(TCMP)
5.2
4
5
2
2
4
8
11
-
3
3
2
3
.9
.6
.0
.2
.5
.9
.0
-
.6
.0
.5
.0
TKN
1.224
1.28
.816
.460
.406
1.056
1.43 *
1.83 *
--
.721
.451
.288
.388
NOD
(4. 57) (TKN)
5.6
5
3
2
1
4
6
8
3
2
1
1
.5
.7
.1
.9
.8
.5
.4
.3
.1
.3
.8
n = 58
r = .
m = .
b = .
876
844
774
* Not included in calculation of r or t
LA = lab accident
-------
Figure #9
35
NOD2Q (Inhibitor) vs NOD (TKNx4.57) for River Water Samples
NOD
(TKN x 4.57)
mg/1
13
12 -
11 -
10 _
9 -
7 -
6 -
5 -
4 -
3 -
2 -
1 -
n = 58
r = .876
m = .849
b = .774
-i i 1 1-i 1 r
1 2 3 4 5 6 7
-| i r
10 11 12
NOD (Inhibitor) mg/1
-------
STATION
6 7
July 20, 1977
8-A
TKN-N x 4.57
NOD2o
10
22 24 26 28 30 32 34 36 38
I f 1 f 1 f 1
I ' !
I 1 1 » 1 1
-------
Z£ 0£ 86 9Z VI ZZ OZ
I i i i i i i
81 9T
i i
PI
I
Zl OT
i i
9 17
-A 'i 1N
0
I-
Z'
£'
V
S'
8'
6'
CTI
3'I
£'T
fr'I
S'T
O
NS1
ZZ.6I '02
8-T
6'T
Z'3
£'Z
^L£
SA
TT#
-------
STATION
July 27, 1977
P-8
I I
8-A
10
I
11
Tkn-N x 4.57
NOD
20
O
n
ft
l f l I I
-------
I 1 I ! f i I 1 f ! f ! f 1 f 1 I I I 1 t I I 1 I 1 I i
111!
August 3, 1977
8-A 10
TKN-N x 4.57
O
-n
H-
s
4
CD
=tt:
t'
0-1
2 4
ID
RMI
-------
STATION
August 24, 1977
P-8
8-A
10
11
TKN-N x 4.57
NOD20 O
-n
p-
OP
246
RMI
I ( 1 : 1 - \
i i i 1 i ' i r i
-------
I I I
P-8
1 ?
f 1
3
f 1
4
f 1 f
1 fill
STATION
6 7
I I
r i
I i s
August 31, 1977
8-A 10
TKN-N x 4.57
NOD20
11
T)
H-
0)
=tt=
tn
RMI
-------
P-8
12
mg/1
11 _
10 -
9 -
8 -
7 -
6 _
5 -
4 -
3 -
1 -
STATION
6 7
I I
September 8, 1977
8-A 10
I t
TKN-N x 4.57
NOD
20
-1-
6
1
18
RMI
1 I 1
"T~
24
~T
30
11
-rt
~r
36
10 12 14 16
20 22
26 28
32 34
1 I 1 f 1 » 1 I I I 1 I I i I
-------
43
nitrification. The NOD pattern for this slack run (figure #11) is
directly associated with a decrease in NH3 and a corresponding
increase in N02~ and NC>3~.
5. Nitrification Kinetics
The kinetics of nitrification for river samples taken between
Hains Point and Ft. Washington, the peak area of nitrification
associated with the STP effluents, were found to be exclusively
first order. The average ke of 0.14 day"1 was observed with a
correlation coefficient of 0.91 for n=25 (Table #6). This k value is
consistent with the close correlation between NOD and TKN-N x 4.57,
since a ke of 0.14 day"1 predicts that 94% of the ultimate NOD will
be expressed after 20 days of incubation. The value predicted by
o
the Dynamic Estuary Model (DEM)° for the deoxygenation constant of
NOD was 0.08 day"1. The standard deviation of 0.02 for the NOD ke (Table #6)
was twice that of the CBOn rate constant and reflects the fragile and
sporadic nature of nitrification.
6. Nature and Distribution of NOD
Bracketing the region of exponential NOD are the upper stations
at Chain and Key Bridges and lower stations from Gunston Cove to
Possum Point. Occasionally these stations had poor correlation to
Thomas Plots. The upper stations correspond to a region of low
NOD2f) levels with an average of 2.0 ppm. The lower stations correspond
to a region of low NOD20 or algal blooms. The data from these stations
was plotted as D.O. depletion vs time and two additional classes
of kinetics were observed (figure 17). A two-stage or consecutive
-------
44
TABLE # 6
NOD RIVER
DATE - STA
July 20 - P8
1
3
4
5
6
7
8-A
10
11
July 27 -
Aug. 3
Aug. 24 -
k!0
-.061
-.560
.031
.040
.038
.035
.029
.001
.051
-0.178
-.016
5.19
8.03
13.47
13.07
4.71
65.45
2.46
P8
1
3
4
5
6
7
8-A
10
11
1
3
4
5
6
7
8-A
10
11
P8
1
3
4
5
6
7
8-A
10
11
--
.107
.042
.058
--
.071
--
-.000
.102
.027
.103
.083
.094
.090
.024
.030
0.033
-.052
-.025
.015
-.022
0.076
0.089
0.053
0.045
0.030
0.023
0.009
0.002
--
1.49
3.47
5.93
7.36
._
-361.09
1.93
5.16
1.53
8.00
5.23
5.20
4.60
6.21
5.13
4.08
-1.02
5.56
-1.63
4.55
4.83
3.79
4.54
4.75
-4.08
-13.38
45.92
r
-.747
-2.39
.83
.784
.966
.942
.875
.048
.871
.897
.700
.992
.991
CURVE (see figure #17)
CODE
S Low NOD
S
E
E
E
E
E
S
E
E
E
E
009
901
855
949
982
961
928
793
944
895
746
704
740
823
992
991
959
972
700
263
188
022
S
E
E
E
E
E
E
E
E
E
C
S
C
S
E
E
E
E
E
S
S
C
Low NOD
Low NOD
Low NOD
Algae 30Qppb
-------
45
TABLE # 6 (con't)
NOD RIVER
DATE - STA
Aug. 31 - P8
1
3
4
5
6
7
8-A
10
11
Sept. 8-1
3
4
5
7
8-A
10
11
k!0
.068
.077
.095
.043
.090
.073
.009
.014
.056
.077
.036
.063
.067
.054
.039
.011
1.60
7.81
5.60
5.41
4.95
5.63
15.59
9.92
-.22
5.12
12.37
13.00
79
51
73
-5.63
r
.871
.964
.989
.900
.992
.935
.229
.487
.654
.997
.714
.925
.930
.981
.734
.305
CURVE (see figure #17)
CODE
E
E
E
E
E
C
c
s
E
E
E
E
E
C
S
Algae 200ppb
Low NOD
The average was limited to Mains Point to Fort Washington stations,
because these stations represented the primary area associated with
nitrification and the kinetics were limited to "E" Kinetics.
k1Q: n = 25
y = .059
s.d. = .023
k = .14
r:
n = 25
Y = .91
r = .09
-------
Figure #17
NOD Depletion Curves
46
Oxygen
Depletion
mg/1
s-shaped
(lag + exponential)
consecutive
(2 lags + exponential curves)
time
-------
47
pattern was observed in which exponential growth occurred after a lag
phase in each of two distinct processes. This may involve the separation
of NH4+»NC>2~ and NC>2~^0?" ^^ a ^aS stage. In the majority of
the "exceptional" NOD stations an S-shaped pattern was observed with
a lag time probably occurring for the Nitrosomonas conversion of NH^
to NC^". Nitrosomonas is considered the weak link in nitrification.
All samples from the peak algal bloom period displayed a lag time
with a resultant poor correlation coefficient in Thomas Plots. This
suggests that the action of heterotrophic bacteria was necessary
to liberate the required ammonia.
A consequence of the lag-free first order NOD kinetics observed
for the majority of Potomac river samples is that the BODg contains a
significant NOD component. The average NOD5/BOD5 observed during the
study (Table #7) was 0.33 (n=56).
-------
48
TABLE # 7
NOD5/BOD5 and NOD2Q/BOD2Q
DATE - STA
July 20 - P8
1
3
4
5
6
7
8-A
10
11
July 27 - P8
1
3
4
5
6
7
8-A
10
11
NODs
0.2
0.4
1.4
2.2
4.6
4.6
0.8
1.2
0.7
1.4
1.0
1.1
3.1
2.8
4.6
1.6
1.4
1.7
TBOD5 NOD5/TBOD5
3.2 .063
3.4
6.6
4.8
9.0
9.9
5.0
5.2
4.5
5.2
2.8
4.1
5.4
5.8
8.6
4.7
4.4
3.6
.118
.212
.458
.511
.465
.160
.231
.156
.270
.357
.268
.574
.483
.535
.340
.318
.472
n = 56
y = .33
s = .18
NOD 20
2.2
2.3
4.4
6.2
11.0
11.1
4.0
3.6
3.0
2.3
1.4
1.5
2.6
5.3
5.6
6.8
5.5
6.8
2.4
3.6
TBOD2o *
7.2
8.3
12.6
12.1
18.6
20.8
11.9
9.8
9.2
9.5
5.4
5.0
7.7
9.4
10.7
14.9
14.4
10.2
7.5
8.2
IOD2o/TBOD;
.306
.278
.349
.512
.591
.534
.336
.367
.327
.242
.259
.30
.337
.564
.523
.456
.382
.666
.32
.439
n = 58
y = .38
s = .11
-------
49
TABLE # 7 (con't) NOD5/BOD5 and NOD20/BOD2o
DATE - STA NODs TBODs NODs/TBODs NOD2Q TBOD2Q NOD20/TBOD20
Aug. 3 - P8
1
3
4
5
6
7
8 -A
10
11
Aug. 24 - P8
1
3
4
5
6
7
8-A
10
11
Aug. 31 - P8
1
3
4
0.9
5.6
3.7
3.1
0.9
1.6
1.3
1.1
0.3
0.9
0.4
2.9
3.4
1.8
2.1
0.9
0.4
0.0
0.5
0.7
0.9
6.0
4.7
3.2
8.6
7.4
6.3
4.4
5.2
5.2
4.3
3.2
4.0
3.0
5.1
7.0
7.0
6.4
5.5
8.0
6.6
3.3
2.8
3.3
9.2
8.5
.281
.651
.500
.492
.204
.308
.250
.256
.094
.225
.133
.569
.486
.257
.328
.164
.050
0
.152
.250
.273
.652
.553
1.4
7.3
4.8
5.0
3.3
4.4
4.0
3.8
1.8
3.0
2.7
4.0
4.4
3.4
4.1
3.5
6.6
6.8
4.2
1.6
1.2
7.1
4.7
5.5
12.4
11.4
10.2
8.6
10.9
11.8
10.2
8.0
8.8
7.0
8.2
10.1
12.0
12.1
12.9
22.0
24.1
13.2
5.4
5.5
12.8
11.2
.254
.589
.421
.490
.384
.404
.339
.372
.225
.341
.386
.488
.436
.283
.339
.271
.300
.282
.318
.296
.218
.555
.420
-------
so
TABLE # 7 (con't] NODs/BODs and NOD20/BOD20
DATE - STA NODs TBOD5 NODs/TBODs NOD20 TBOD2Q NOD20/TBOD20
Aug. 31 -
(con't)
Sept. 8 -
5
6
7
8 -A
10
11
P8
1
3
4
5
6
7
8 -A
10
11
3.
2.
3.
4.
2.
1.
0.
0.
2.
4.
7.
--
2.
1.
1.
0.
9
8
7
5
6
7
0
1
8
6
0
-
0
8
0
5
-7
8
8
9
8
3
2
2
5
9
11
-
4
5
4
3
.6
.0
.8
.7
.9
.3
.0
.7
.3
.4
.8
--
.6
.0
.9
.6
.513
.350
.420
.464
.292
.515
0
.037
.528
.489
.593
.435
.360
.204
.139
5
4
4
5
4
5
2
2
4
8
11
-
3
3
2
3
.1
.9
.3
.2
.9
.6
.0
.2
.5
.9
.0
.6
.0
.5
.0
11
12
13
16
16
14
6
6
9
16
19
-
8
9
9
9
.8
.1
.5
.3
.8
.3
.5
.7
.5
. 3
.8
--
.1
.1
.8
.0
.432
.405
.318
.319
.292
.392
.308
.328
.474
.546
.556
.444
.330
.255
.333
-------
51
V. Oxygen Demand in the Potomac STP Effluent Samples
A. CBOD
The CBOD kinetics observed for the sewage treatment plant effluents
were first order with an average ke = 0.17 (n=19, s=0.02) and a average
correlation coefficient of 0.86 (Table #8).
B. NOD
The NOD kinetics observed for the sewage treatment plant effluents
were all characterized by a lag period which generally lasted for the
first 10 to 15 days of incubation. The NOD expressed within five days,
though relatively small compared to the NOD expressed after 10 to 12
days was significant and is included in Table #12. The average (n=30)
NODs/BODs value was 0.26 with considerable noise in the data, s=0.21.
This relationship corresponded to an average CBODs/BODs ratio of 0.74.
The observed carbonaceous kinetics of ke = 0.17 dictated a CBOD ultimate
to CBODs ratio of 1.75 and together with the observed ratio suggests:
CBOD (ultimate) = BOD5 * 1-30
The relation CBOD ultimate = BODs x 1.45 is based upon the classical
kinetics, ke=.234 associated with sewage effluents and assumes an
insignificant nitrification contribution. However, the factor 1.45
is not unsatisfactory for the Potomac STP effluents since it predicts
CBODuitimate values not significantly different from those predicted
by the 1.30 factor. An STP effluent with a BODs of 30.0 rag/1 would
yield CBODult^mate values of 39.0 mg/1 based upon the 1.3 factor and
43.5 mg/1 based upon the 1.45 factor. This is within the error
2
associated with the BOD test and provides a conservative estimate of
the carbonaceous oxygen demand.
-------
TABLE # 8
CBOD - STP
52
DATE - STA
July 20 - SI
S2
S3
S4
SB
S6
S7
S8
Aug. 24 - SI
S2
S3
S4
S5
S6
S7
S8
Aug. 31 - SI
S2
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
West gate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
kio
.105
.075
.076 *
.061
.074
.069
.050
.055
.101
.072
.092
*
.012
.064
.080
.037 *
--
.012*
.101
.101
--
--
.063
.076
LO
5.66
10.09
26.40
108.17
21.68
22.79
16.95
34.16
--
20.21
44.04
84.27
58.17
22.43
21.68
22.7
--
9.97
32.52
57.59
--
--
9.97
16.04
r
.997
.998
.844
.997
.991
.996
.983
.979
--
.998
.992
.992
.257
.998
.997
.621
--
.588
.997
.997
--
--
.976
.997
1 lag phase
2 lag phases .
2 lag phases
588} linear r=.991
m=.370 b=-.231,
-------
53
TABLE # 8 (con't)
CBOD - STP
DATE - STA
Sept. 8 - SI
A
SI
S2
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
West gate
Hunting Creek
Dogue Creek
Pohick Creek
k10
.059*
--
.069
.047
.053
.034*
.007*
k:
n=19
k^.074
s=.020
L0
29.30
--
--
94.97
28.59
24.94
20.49
89.88
k~=.017
r
.019 1 lag phase
--
--
.985
.995
.989
.799 2 lags
.469} linear r=.991
m=1.294 b=.824
r :
n=26
f=.86
s=.26
-------
54
The Thomas correlation coefficients for NOD are listed in Table #9. The
negative correlation consistently observed resulted from the lag in
NOD. The oxygen depletion plots (figures 18, 19 § 20) were restricted
to "S-shaped" and "consecutive S-shaped" patterns.
The fraction of the potential NOD, TKN-N x 4.57, expressed after
20 days is included in Table #10. The low recovery is related to
the long lag phase observed for the NOD. Since the receiving waters
have lag-free, first order kinetics, it is likely that the consistent
NOD lag phase observed in STP samples is artifical and is perhaps
due to the lack of nitrifying bacteria.
C. Loading Characteristics
The average flows and loadings based on: CBOD2Q; TKN-N x 4.57 (NOD)
and BOD5 are presented in Table #11. The ratio of NOD20 to BOD2o
for the STP effluents is compiled in Table #12 with an average value
of 0.69 (n=27; s=0.11). The effluent loadings were therefore
predominantly NOD, and as pointed out previously, the river samples
were dominated by the CBOD. The predominant nitrogen form, in the
STP effluents, (nearly to the exclusion of all other oxidation states)
was ammonium (Table #13). This suggested that a portion of the
discharged ammonium was being lost from the system, since nitrification
would be expected to be very efficient for ammonia. A mechanism
for this loss may be sorption of ammonia onto clays and organic
22
colloids in sediments and loss to the bottom by sedimentation. On
the bottom denitrification would be expected to predominate
-------
TABLE # 9 (con't)
NOD - STP
55
DATE - STA
July 20 - SI
Aug. 24 -
Aug. 31 - SI
DA
SI
S2
S3
S4
S5
S6
S7
S8
SI
S2
S3
S4
S5
S6
S7
SB
SI
S2
S3
S4
S5
S6
S7
S8
Name
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
Piscataway
Arlington
Blue Plains
Alexandria
Westgate
Hunting Creek
Dogue Creek
Pohick Creek
kio
-.005
- . 0464
-.089
-.024
-.034
-.064
-.014
-.063
-.025
-.089
-.098
-.098
-.076
-.050
-.082
-.066
-.004
-.063
-.051
-.012
.008
-.011
LO
-77.76
-5.68
-1.85
-30.13
-5.240
-3.35
-25.8
-2.59
-10.70
-.89
-.606
-.739
-1.43
-6.61
-.989
-2.09
-176.6
-3.98
-3.91
-4.46
109.17
-81.8
r
-.098
-.758
-.743
-.428
-.627
-.811
-.220
-.912
-.437
-.927
-.825
-.863
-.986
-.895
-.797
-.894
_ _ _
-.083
-.730
-.547
-.1058
.117
-.388
Curve
Type (see fig.20)
1 lag stage
1 lag stage
2 lag stages
2 lag stages
1 lag stage
2 lag stages
2 lag stages
1 lag stage
2 lag stages
1 lag stage
2 lag stages
-------
56
H
TABLE #_9_ (con't) NOD - STP
rti
Curve
DATE - STA Name k10 L0 r Type (see fig.20)
Sept. 8 - SI Piscataway -.021 -24.59 -.526 ""
S2 Arlington
S3 Blue Plains
S4 Alexandria -.044 -14.30 -.899 2 lag stages
S5 Westgate -.026 -13.44 -.406
S6 Hunting Creek -.027 -17.4 -.591 2 lag stages «
S7 Dogue Creek -.074 -2.38 -.689
*
S8 Pohick Creek -.057 -6.89 -.897 2 lag stages
-------
f 1 f I { 1 I I f ! f
f 1 f
f ! f i f ] f
i 1
Oxygen Depletion mg/1
o
ro
cr\ -
t-3
s-
00 -
ro
00
O
vo
o
4s-
o
VJ1
O
o\
o
-1
CQ
o Co
(0 (V
ro-
cr\-
oo-
o -
ro
ro
o
Oxygen Depletion mg/1
00
(0
CO VoO
H I-1
§
J?
0)
CO
^
M O
vo a
0)
CO
-------
Oxygen Depletion mg/1
Oxygen Depletion mg/1
o
o
oo
o.
o\
00
ro
o
o
ro
o
VJl
o
00
o
o
da
(D
IX)
o
oo
I
s
s?
n>
cf
H-
B
1 I I
f I I i I I
-------
59
Figure #20
Oxygen
?"*pletion
STP Oxygen Depletion Curves
CBOD
NOD (consecutive)
2 lag phases
NOD (exponential)
1 lag phase
time
-------
60
TABLE* 10 Summary Sheet of % fNOD^n/NOD^ir\mate) for STP's
Station
Sl-Piscataway
S2-Arlington
S3-Blue Plains
S4-Alexandria
S5-Westgate
S6 -Hunting Creek
S7-Dogue Creek
S8-Pohick Creek
7/20
.747
.549
.873
.961
.24
.469
.214
.417
8/24
.85
.56
.78
.82
.61
.55
.41
.62
8/31
.52
.57
.68
.32
.53
9/8
.92
1.06
.40
.32
.42
.66
ave. ,
y
.84 ±
.54 ±
.74 ±
.88 ±
.42 ±
.45 ±
.34 ±
.56 ±
std.
dev.
s
.09
.02
.16
.17
.19
.12
.10
.11
NOD2Q = NOD determined with the inhibitor
* NOn . - TK"M-M y 4 57
NUUultimate ~ 1KlN N x 4>;3/
-------
61
TABLE # 11
STP Loadings of CBOD2Q, NOD Ultimate, and BODs
DATE - NAME
July 20-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
aH
Dogue Creek STP
Pohick Creek STP
«n
fuly 27-Piscataway STP
*rf
Arlington STP
**
Blue Plains STP
Alexandria STP
" Westgate STP
Hunting Creek STP
Mb*
Dogue Creek STP
Pohick Creek STP
oig. 3-Piscataway STP
M
Arlington STP
i*%
Blue Plains STP
Alexandria STP
" Westgate STP
Hunting Creek STP
wr
Dogue Creek STP
»
Pohick Creek STP
Flow
(MGD)
12.48
21.00
280.00
19.40
11.63
3.90
2.28
14.26
16.00
19.90
251.00
19.73
11.51
3.75
2.28
13.79
7.50
20.20
261.00
19.09
11.15
4.17
2.16
14.18
20-day TKNx4.57=
CBOD Loading NOD
(mg/1) (Ib/day) (mg/1)
4.8 499.9 24.05
9.1 1,594.8 85.14
27.6 64,491.4 81.78
99.0 16,027.7 98.61
19.2 1,863.4 95.73
20.4 663.9 110.64
15.0 285.4 157.30
31.2 3,712.8 139.50
39.15
61.67
66.10
81.98
77.55
84.57
73.49
97.86
19.63
73.20
65.43
98.56
83.01
92.42
90.38
110.42
Loading
(Ib/day)
2,504.7
14,920.6
191,090.7
15,964.6
9,291.0
3,600.9
2,992.9
16,600.8
5,227.4
10,241.5
138,455.3
13,498.0
7,448.9
2,646.6
1,398.3
11,261.7
1,228.6
12,339.5
142,512.1
15,701.5
7,724.0
3,216.2
1,629.1
13,066.5
BOD 5
Loading
(Ib/day)
749.8
2,102.9
53,274.9
11,462.0
1,630.5
507.7
285.4
2,499.0
881.2
1,096.0
40,216.2
4,346.7
864.5
187.8
79.9
1,726.2
262.9
606.8
58,807.2
7,073.2
558.3
229.7
54.1
994.0
-------
TABLE * 11 (con't)
DATE - NAME
Aug. 24-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Cr-ek STP
Pohick Creek STP
Aug. 31-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
Sept. 8-Piscataway STP
Arlington STP
Blue Plains STP
Alexandria STP
Westgate STP
Hunting Creek STP
Dogue Creek STP
Pohick Creek STP
* 18-dav BOD
62
STP Loadings of CBOD2o> NOD Ultimate, and BODs
Flow
(MGD)
10.99
19.30
282.00
19.24
10.43
4.04
2.09
13.70
12.13
20.80
297.00
20.18
10.59
4.09
2.15
13.91
10.95
20.80
313.00
19.44
10.44
4.00
2.63
14.24
Loading
20 -day
CBOD'
Cmg/1)
0
17.4
39.6
75.6
23.4
20.0
19.5
16.2
--
7.2
28.2
49.8
15.6*
14.4*
9.0
14.4
12.0
15.6*
132.0*
84.6
25.4
21.0
18.0
27.9
(Ib/day)
Loading
(Ib/day)
0
2,802.5
93,192.0
12,138.4
2,036.7
674.3
340.1
1,852.1
1,249.7
69,892.7
8,386.4
1,378.6
491.5
161.5
1,671.5
1,096.6
2,707.8
344,781.9
13,724.6
2,212.9
701.0
595.1
3,315.5
TKNx4.57=
NOD
(mg/1)
22.52
97.31
76.71
99.99
90.44
94.64
95.41
48.46
20.84
55.20
67.64
85.92
77.51
87.74
79.34
100.90
33.36
37.07
77.44
82.58
102.15
107.92
103.80
115.74
= BOD (mg/1) x Flow
Loading
(Ib/day)
2,065.3
15,672.6
180,520.9
16,054.2
7,871.7
3,190.7
1,664.1
5,540.3
2,109.5
9,581.4
167,645.3
14,469.1
6,849.8
2,994.7
1,423.5
11,712.4
3,048.4
6,434.6
202,275.9
13,364.5
8,899.7
3,602.4
2,278.2
13,754.0
(MGD) x 2000
BOD5
Loading
(Ib/day)
27.5
2,415.9
57,890.9
8,959.1
1,357.8
505.7
230.2
1,714.9
0
208.3
69,892.7
6,971.8
1,537.7
512.0
495.2
2,577.0
1,069.1
2,707.8
344,781.9
11,193.6
1,672.7
560.8
322.6
1,853.8
239.66
-------
63
TABLE # 12 Proportion of Total STP Demand Expressed as NOD
DATE - STA
July 20 - SI
Aug. 24 -
Aug. 31 -
'A
SI
S2
S3
S4
S5
S6
S7
S8
SI
S2
S3
S4
S5
S6
S7
S8
SI
S2
S3
S4
S5
S6
S7
S8
NOD 5
3.0
6.0
1.8
14.4
3.6
2.4
7.2
3.6
0
1.2
0.6
2.4
1.8
3.6
0.6
1.8
-
0
6.0
1.8
2.4
0.6
22.8
12.4
BOD5 NOD5/BOD5
7.2 .42
12.0
22.8
70.8
16.8
15.6
15.0
21.0
0
15.0
24.6
55.8
15.6
15.0
13.2
15.0
-
1.2
28.2
41.4
17.4
15.0
27.6
22.2
.50
.079
.20
.21
.15
.48
.17
-
.080
.024
.043
.12
.24
.045
.12
-
0
.21
.044
.14
.040
.83
.56
NOD 20
18.0
46.7
71.4
94.8
28.8
51.9
33.6
58.2
19.2
54.6
60.0
82.2
55.8
52.2
39.0
30.0
31.2
38.4
58.8
-
-
27.6
55.8
BOD2Q I1
22.8
55.8
99.0
193.8
48.0
72.3
48.6
89.4
19.2
72.0
99.6
157.8
79.2
72.2
58.5
46.2
38.4
66.6
108.6
-
-
36.6
70.2
roD20/Bi
.789
.837
.721
.489
.600
.718
.691
.651
1
.758
.602
.521
.704
.723
.667
.649
.812
.576
.541
.754
.795
-------
64
TABLE #12 (con't) Proportion of Total STP Demand Expressed as NOD
DATE
Sept.
- STA
8 - SI
S2
S3
S4
S5
S6
S7
S8
NOD5
6.3
10.2
42.0
11.4
7.2
4.8
6.3
6.6
BOD5
11.7
15.6
132.0
69.0
19.2
16.8
14.7
15.6
NOD5/BOD5
.54
.65
.32
.17
.38
.29
.43
.42
n=30
x=.26
s=.21
NOD 20
42.0
-
-
87.6
41.2
34.8
44.0
76.5
BOD2Q r
54.0
-
-
172.2
66.6
55.8
62.4
104.4
TOD 2 Q/ BO
.778
.509
.619
.624
.705
.733
n=27
x=.69
s=.ll
-------
TABLE # 15 N02-N Concentration and the Resulting NOD Error 6S
""DATE/STA
July 20
P-8
P-4
1
, 1-A
**"* 2
- 3
4
5
*«. 5A
»> 6
*"* 7
- 8
«w
8A
9
10
v~ 10B
^ 11
***=*
12
13
Vfetn*
14
w 15
»» ISA
*" 16
*" SI
S2
N03-N
Ong/D
N.D.
N.D.
N.D.
N.D.
N.D.
.174
.160
.162
.360
.535
.892
1.243
1.060
.893
.834
.618
.382
.164
.080
.144
.073
.046
N.D.
5.755
2.189
N02-N
(mg/D
N.D.
N.D.
N.D.
N.D.
N.D.
.107
.155
.222
.558
.606
.328
.126
.078
.055
.059
.063
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
.315
.241
1.14x
N02-N
N.D.
N.D.
N.D.
N.D.
N.D.
.1
.2
.2
.6
.7
.4
.1
.1
.1
.1
.1
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
.4
.3
NH3-N
Cmg/D
.087
N.D.
N.D.
N.D.
N.D.
.234
1.094
1.240
1.02
.800
.291
.186
.134
.071
.095
.092
.026
N.D.
N.D.
.128
.060
.094
.040
3.09
18.4
TKN-N
(mg/1)
.741
.621
.705
.632
.632
.821
2.052
2.495
2.429
2.200
1.358
1.179
1.074
.842
.853
.726
.621
.600
.453
.474
.863
.442
.621
5.263
18.631
4.57x
TKN-N
3.4
2.8
3.2
2.9
2.9
3.8
9.4
11.4
11.1
10.1
6.2
5.4
4.9
3.8
3.9
3.3
2.8
2.7
2.1
2.2
3.9
2.0
2.8
24.1
85.1
Error
N.D.
N.D.
N.D.
N.D.
N.D.
2.6
2.1
1.8
5.4
6.9
6.4
1.8
2.0
2.6
2.6
3.0
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
1.6
.4
STA
P-8
P-4
1
1-A
2
3
4
5
5A
6
7
8
8A
9
10
10B
11
12
13
14
15
ISA
16
SI
S2
RMI
0.0
1.9
3.4
4.9
5.9
7.6
10.0
12.1
13.6
15.2
18.4
22.3
24.3
26.9
30.6
34.0
38.0
42.5
45.8
52.4
58.6
62.8
67.4
STP
STP
-------
66
TABLE # 13 (con't) N02-N Concentration and the Resulting NOD Error
'E/STA
.y 20
S3
S4
S5
S6
S7
S8
N03-N
Cmg/1)
N.D.
N.D.
N.D.
1.557
.734
.048
N.D.
< .04
N02-N
Cmg/1)
N.D.
N.D.
N.D.
.213
.236
.044
N.D.
< .04
1.14x
N02-N
N.D.
N.D.
N.D.
.2
.3
.1
NH3-N
Cmg/1)
16.4
17.0
36.6
23.1
29.4
22.6
N.D.
< .02
TKN-N
Cmg/1)
17.894
21.578
20.941
24.210
34.420
30.525
4.57x
TKN-N
81.8
98.6
95.7
110.6
157.3
139.5
Error
N.D.
N.D.
N.D.
.2
.2
.1
STA
S3
S4
S5
S6
S7
S8
RMI
STP
STP
STP
t
STP ,
STP
STP '"
m
Vn
-------
67
References
1. "Standard Methods for the Examination of Water and Wastewater,"
14th ed., APHA, 1975.
2. Ballinger, D. G. and Lishka, R. J., "Reliability and Precision of
BOD and COD Determinations." J.W.P.C.F., p. 470-474, (May 1962).
3. Wang, L. K. and Wang, M. H., "Computer Aided Analysis of Environmental
Data Part II: Biochemical Oxygen Demand Model," 22nd Annual Proceedings
Institute of Envir. Science 1976.
4. Benedict, A. H. "Temperature Effects on BOD Stoichiometry,"
J.W.P.C.F., 48, p. 864-5, 1976.
5. Effects of Polluting Discharges on the Thames Estuary, p. 202-225,
Reports of the Thames Survey Committee and of the Water Pollution
Research Laboratory, Crown Copyright, 1964.
6. Thomas, H. A., "Grophical Determination of B.O.D. Curve Constants,"
Water and Sewage Works, p. 123-124, (March 1950).
7. Moore, W. E. and Thomas, H. A., "Simplified Methods for Analysis
of B.O.D. Data," Sewage and Industrial Works, 22, p. 1343-1355, 1950.
8. Clark, L. J. and Jaworski, N. A., "Nutrient Transport and Dissolved
Oxygen Budget Studies in the Potomac Estuary," Technical Report 37,
AFO Region III, Environmental Protection Agency, 1972.
9. Daniels, F. and Alberty, R. A., Physical Chemistry, 4 ed., John
Wiley and Sons, Inc., 1975.
10. Streeter, H. W. and Pheips, E. B., Public Health Bull., Wash..,
No. 146, 1925.
11. Sawyer, C. N. and McCarty, P. L., Chemistry for Sanitary Engineers,
2nd ed., McGraw-Hill, 1967.
12. Breed, R. S., Murry E. G. D., and Hitchens, A. P., Sergey's
Manual of Determinative Bacteriology, 6th ed., The Williams and
Wilkens.
13. Srinath, E. G., Raymond, L. C., Loehr, M. and Prakasam, T.B.S.,
"Nitrifying Organism Concentration and Activity." J. of Env.
Engineering, p. 449-463, 1976.
14. Mattern, E. K., Jr., "Growth Kinetics of Nitrifying Microorganisms,"
CE 756A6 prepared for Office of Water Research and Technology.
15. Segel, I. H. Biochemical Calculations, John Wiley § Sons, Inc.,
New York, 1968.
16. Finstein, M. S. et al, "Distribution of Autotrophic Nitrifying
Bacteria in a Polluted Stream;" The State Univ., New Brunswick,
N. J. Water Resources, Res. Inst. W7406834, Feb. 74.
-------
68
. ' " References
17. Hockenbury, M. R. , and Grady, C. R. Jr. "Inhibition of Nitrification
Effects of Selected Organic Compounds," JWPCF, p. 768-777, (May 1977).
18. Wezernak, C. T. and Gannon J. J., "Evaluation of Nitrification
in Streams," J. Sanitary Engineering Div., Proc. of .American
Soc. of Civil Engineers, p. 883-895, (Oct. 1968).
19. Wezernak, C. T. and Gannon, J. J., "Oxygen-Nitrogen Relationships
in Autotrophic Nitrification," Applied Microbiology, 15, p. 1211-1215, t
(Sept. 1967).
20. Montgomery, H. A. C. and Borne, B. J., "The Inhibition of
Nitrification in the BOD Test," J. Proc. Inst. Sew. Purif., '
p. 357-368, 1966.
21. Young, J. C., "Chemical Methods for Nitrification Control," 24th t
Industrial Waste Conference, Part II. Purdue University,
pp. 1090-1102, 1967.
22. Allen, H. E. and Kramer, J. R., Nutrients in Natural Waters, *"
Wiley-Interscience Publication, New York, 1972. i
23. Van Kessel, J. F. "Factors Affecting the Denitrification Rate **
in Two Water-Sediment Systems,"Water Research, 11, pp. 259-267,
CJuly 1976).
24. Goring, C. A., "Control of Nitrification by 2-Chloro-6-(Trichloro- **
methyl) Pyridine Soil Science, 93, p. 211-218, (Jan. 1962).
25. Mullison, W. R. and Norris, M. G., "A Review of Toxicological, m>
Residual and Environmental Effects of Nitrapyrin and Its w
Metabolite, 6-Chloropicolinic Acid," Down to Earth, 32, p. 22-27, ""
(Summer 1976). m
26. Redemann, C. T., Meikle, R. W. and Widofsky, J. G.," The Loss of -
2-Chloro-6(Trichloromethyl) Pyridine from Soil," J. Agriculture
and Food Chemistry, 12, p. 207-209, (May-June 1964). "*
27. Young, J. C., "Chemical Methods for Nitrification Control," JWPCF,
45, 4, p. 637-646, (April 1973). ~
28. Laskowski, D. A., O'Melia E. C., Griffith, J. D. et al, "Effect of *
2-Chloro-6(Trichloromethyl) Pyridine and Its Hydrolysis Product
6-Chloropicolinic Acid on Soil Microorganisms," J. of Env. **
Quality, 4, p. 412-417, (July-Sept. 1975). «.
29. Bundy, L. G., "Control of Nitrogen Transformations," Ph.D. m
Dissertation, Iowa State University, 1973.
-------
69
Appendix
A. N-Serve/NOD Determinations
The inhibitor incorporated was formula 2533 Nitrification
Inhibitor, a product of the Hach Chemical Company. The product
consists of 2-chloro-6(trichloromethyl) pyridine known as TCMP or
N-Serve. This compound is plated on a simple inorganic salt which
serves as a carrier and is soluble in water. The Dow Chemical Company,
Midland, Michigan, markets this chemical under the name N-Serve as a
23,24,25,26
fertilizer additive. Studies using N-Serve suggest that it acts as a
"biostat" at moderate concentrations to delay nitrification and aids
the retention of ammonia or urea fertilizers on crops by retarding the
conversion to the more highly leachable N03~. Ideally TCMP is slowly
biodegraded to 6-chloropicolinic acid which leaves the fields in
their original state, with no further inhibition to nitrification.
This allows long term (20-30 day) NOD assays without significant
21,27 28
inhibitor contribution to the carbonaceous demand. Extensive studies
were performed on the toxicity of this material, because of concern
for the environment. These have revealed it to be very selective
21,27
and effective at stopping nitrification at 10 ppm.
Although the mechanism of its action is still unclear, it is
restricted to Nitrosomonas. This selectivity is an advantage in that
it stops the process of nitrification at ammonia with little or no
29
effect on urea hydrolysis, assuring an adequate nitrogen source for
the heterotrophic bacteria contributing to the CBOD. The disadvantage
of this selectivity is that Nitrobacter are not inhibited and NC>2~ will
be oxidized to N03~. This limitation generally represents a small error
-------
70
since NC>2~ is generally much smaller than TKN in river water and
the demand associated with the N02 initially present is . or one-
T" ^ /
quarter that associated with the TKN initially in the sample.
The Potomac intensive survey did not include the separate
determination of NC^ and NO,, but incorporated cadmium reduction
technique whereby the sum concentration of N02 plue NOj was determined. ,
The initial run, however, was assayed for N02 separately to determine
the significance of the potential error associated with TCMP. This '
*
data is compiled in Table #13 with a maximum potential error of 5 to 7%
*
associated with the NOD determination of 3 out of a total of 23 river
t
stations and 9 waste treatment effluents. This error was not considered
ft!
significant enough to justify the added time and cost involved in the *
analysis of N02 throughout the course of this study. «*
Mm
B. Alternative Methods
«K
Several other alternate approaches to determining NOD were
w&>*
considered. In situ tests, where a segment of water is followed
and assayed for D.O. and states of nitrogen would give actual "river ^
rates" for NOD and CBOD. However; the flows of a large, complex, tidal m
estuary are not adequately defined. Even if the segment of water *
could be followed it is altered by diffusion and by the input of **
effluents, resulting in a faulty estimate of the NOD rate.
Laboratory studies involving the incubation of samples with
M**
analysis of sub-samples at timed intervals for all nitrogen states, ^
coupled with the determination of NOD based upon the stoichiometric *»
relation between oxygen utilization and nitrogen oxidation is a <
second method for NOD determinations.
-------
71
A second approach to laboratory studies involves only D.O. analyses,
not the extensive laboratory committment associated with frequent
N-series determination. One such method involves killing all of the
bacteria present by pasteurization, chlorination, or acidification and
reseeding with populations containing few nitrifyers. However, these
methods involve the disadvantages associated with extensive sample
modification. A second D.O. method involves killing or inhibiting
the nitrifyers by addition of: methylene blue; thiourea; allylthiourea
ATU; and TCMP. Methylene blue interferes with Winkler D.O. determinations
as does thiourea. Further, only Temp has been found effective for
long term experiments, because the others were either degraded thus
contributing to the CBOD or Nitrosomonas quickly acclimated to their
21
effect and nitrification began.
-------
72
TABLE #14
C. Study Data
Potomac River Long-Term BOD Survey Data-Summer 1977
Date: 7/20/77
Days of Incubation
STA #
P-8
P-4
1
1-A
2
3
4
5
T*
C*
N*
T
T
C
N
T
T
T
C
N
T
C
N
T
C
N
5
3.2
3.0
0.2
3.6
3.4
3.0
0.4
3.7
4.0
6.6
5.2
1.4
4.8
2.6
2.2
9.0
4.4
4.6
8
4.2
4.0
.2
4.9
4.0
0.9
7.7
5.2
2.5
9.7
4.4
5.3
12.8
5.5
7.3
11
5.6
4.3
1.3
6.1
4.6
1.5
8.3
5.2
3.1
11.0
5.1
5.9
14.1
6.5
7.6
15
6.8
4.6
2.2
7.4
5.2
2.2
10.8
7.6
3.2
11.7
5.5
6.2
17.1
7.0
10.1
18
7.0
4.8
2.2
8.0
5.8
2.2
11.2
8.0
3.2
12.0
.58
6.2
17.5
7.4
10.1
20
7.2
5.0
2.2
8.3
6.0
2.3
12.6
8.2
4.4
12.1
5.9
6.2
18.6
7.6
11.0
5-A T
6
7
T
C
N
T
C
N
8
9
5
4
5
4
0
.1
.9
. 3
.6
.0
.2
.8
11.4
5.0
6.4
8.0
5.5
2.5
11
5
6
9
6
3
.8
.0
.8
.8
.0
.8
17
8
8
11
7
3
.0
.6
.4
.1
. 3
.8
19
9
9
11
7
3
.3
.4
.9
.5
.7
.8
20.8
9.7
11.1
11.9
7.9
4.0
5-A T
C
N
4.6
5.2
4.0
1.2
7.3
5.0
2.3
8.1
5.7
2.4
9.0
6.0
3.0
9.2
6.2
3.0
9.8
6.2
3.6
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
73
TABLE # 14 (con't)
Date: 7/20/77
10-B T
3.9
Days of Incubation
STA #
9 T
10 T*
C*
N*
5
4.9
4.5
3.8
0.7
8
6.2
4.7
1.5
11
7.8
5.4
2.4
15
8.2
5.6
2.6
18
8.9
5.9
3.0
20
9.2
6.2
3.0
11
12
13
14
15
15-A
16
S-l
S-2
S-3
S-4
S-5
T
C
N
T
T
T
T
T
T
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
5
3
1
4
4
2
13
4
7
7
4
3
12
6
6
22
21
1
70
56
14
16
13
3
.2
.8
.4
.6
.5
.5
.2
.0
.8
.2
.2
.0
.0
.0
.0
.8
.0
.8
.8
.4
.4
.8
.2
.6
6
4
1
18
4
13
13
7
6
28
19
9
88
73
15
18
14
3
.1
.7
.4
.0
.6
.4
.8
.4
.4
.6
.0
.6
.0
.0
.0
.0
.4
.6
7.
5.
1.
20.
4.
15.
16.
8.
7.
55.
18.
37.
102.
83.
18.
25.
18.
7.
1
7
4
4
8
6
0
3
8
4
0
4
3
5
8
2
0
2
8.
6.
1.
22.
4.
18.
33.
8.
24.
66.
17.
49.
117.
94.
23.
26.
19.
7.
2
3
9
8
8
0
0
7
3
4
0
4
6
0
6
2
0
2
9.3
7.0
2.3
22.8
4.8
18.0
54.7
9.1
45.6
89.1
26.7
62.4
153.6
94.0
59.6
39.0
19.2
19.8
9.5
7.2
2.3
22.8
4.8
18.0
55.8
9.1
46.7
99.0
27.6
71.4
193.8
99.0
94.8
48.0
19.2
28.8
*T - BOD Qng/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE # 14 (con't) 74
Date: 7/20/77
Davs of Incubation
STA
S-6
S-7
S-8
#
T*
C*
N*
T
C
N
T
C
N
5
15.6
13.2
2.4
15.0
7.8
7.2
21.0
17.4
3.6
8
25.2
15.6
9.6
17.2
10.0
7.2
23.4
19.8
4.2
11
48.0
18.0
30.0
18.2
11.0
7.2
35.0
26.0
9.0
15
58.2
20.4
37.8
23.0
14.0
9.0
57.6
27.0
30.6
18
68.4
20.4
48.0
40.8
14.4
26.4
61.2
29.4
31.8
20
72.3
20.4
51.9
48.6
15.0
33.6
89.4
31.2
58.2
Date: 7/27'/77
STA #
P-8 T
C
N
2
.3
--
5
1.5
--
8
1.1
1.1
0
11
2.2
2.2
0
15
4.5
3.2
1.3
18
5.1
3.8
1.3
20
5.4
4.0
1.4
P-4 T .7 2.2
1 T 1.0 2.8 3.5 3.7 4.2 5.0 5.0
C 1.0 1.8 2.5 2.7 3.2 3.5 3.5
N 0.0 1.0 1.0 1.0 1.0 1.5 1.5
1-A T 1.0 2.4
2 T 1.2 2.2
T
C
N
T
C
N
T
C
N
2.1
1.6
0.5
2.4
1.0
1.4
2.1
1.5
0.6
4.1
3.0
1.1
5.4
2.3
3.1
5.8
3.0
2.8
5.6
3.8
1.8
6.8
3.2
3.6
6.8
3.8
3.0
6.6
4.4
2.2
7.8
3.5
4.3
7.7
--
--
7.3
4.8
2.5
8.8
3.8
5.0
8.9
4.7
4.2
7.7
5.1
2.6
9.4
4.1
5.3
9.8
4.9
4.9
7.7
5.1
2.6
9.4
4.1
5.3
10.7
5.1
5.6
5-A T 3.3 7.5
6 T 3.9 8.6 10.5 12.2 13.6 14.6 14.9
C 1.7 4.0 5.5 6.5 7.2 8.0 8.9
N 2.2 4.6 5.0 5.7 6.4 6.6 6.8
*T - BOD Cmg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE #14 (con't)
75
Date: 1121 111
Days of Incubation
STA #
7 T*
C*
N*
8 T
8-A T
C
N
9 T
10 T
C
N
10-B T
11 T
C
N
12 T
13 T
14 T
15 T
15-A T
16 T
S-l T
S-2 T
S-3 T
S-4 T
S-5 T
*T -
*C -
2
3.6
2.1
1.5
2.6
0.8
0.4
0.4
1.6
1.5
1.5
0.0
1.5
1.2
.6
.6
1.0
0.7
0.8
1.2
0.0
1.1
1.8
3.6
9.6
12.0
3.3
BOD (mg/1)
CBOn fmtJ/r
5
.51
--
5.6
4.7
3.1
1.6
4.2
4.4
3.0
1.4
3.7
3.6
1.9
1.7
2.7
2.2
1.9
3.4
1.2
2.6
6.6
6.6
19.2
26.4
9.0
)
8
5.7
3.0
2.7
7.6
3.8
3.8
5.0
3.6
1.4
4.0
2.3
1.7
10.8
11.2
22.8
32.4
15.6
11
7.5
4.2
3.3
8.7
4.9
3.8
6.0
4.6
1.4
5.6
3.2
2.4
16.2
11.2
25.8
32.4
15.6
15
9.6
5.6
4.0
9.0
5.2
3.8
6.1
4.7
1.4
7.2
3.8
3.4
27.0
12.0
45.6
32.4
15.6
18
11.8
6.3
5.5
9.8
6.0
3.8
6.4
5.0
1.4
8.0
4.4
3.6
28.2
13.2
57.6
32.4
17.4
20
14.4
8.9
5.5
10.2
6.4
3.8
7.5
5.1
2.4
8.2
4.6
3.6
28.8
13.2
72.0
32.4
18.6
*N - NOD
-------
76
TABLE #14 (con't)
Date: 7/27/77
STA #
S-6 T
S-7 T
S-8 T
2
5.4
2.4
7.8
5
6.0
4.2
15.0
Days of
8
12.0
12.0
21.6
Incubation
11
12.0
12.0
21.6
15
13.2
12.6
22.2
18
18.0
14.4
26.4
20
22.8
16.8
28.8
Date: 8/03/77
STA #
P-8 T
P-4 T
2
1.3
1.4
5
1.7
2.4
8
1.7
11
1.7
15
1.7
18
2.2
20
2.4
1
1-A
2
3
4
5
5-A
6
7
T*
C*
N*
T
T
T
C
N
T
C
N
T
C
N
T
T
C
N
T
C
N
2.
1.
0.
2.
2.
3.
0.
2.
4.
1.
2.
4.
1.
2.
3.
2.
2.
0.
2.
1.
0.
2
3
9
6
9
2
5
7
1
9
2
2
5
7
8
6
0
6
3
5
8
3.2
2.3
0.9
4.2
4.0
8.6
3.0
5.6
7.4
3.7
3.7 '
6.3
3.2
3.1
6.4
4.4
3.5
0.9
5.2
3.6
1.6
4.4
3.3
1.1
9.4
3.8
5.6
8.5
4.8
3.7
7.5
4.1
3.4
6.2
4.6
1.6
8.0
5.0
3.0
4.6
3.5
1.1
10.4
4.5
5.9
9.4
5.7
3.7
8.3
4.9
3.4
6.9
5.0
1.9
9.0
5.5
3.5
4
3
1
11
4
7
10
5
4
10
5
4
7
5
2
9
5
4
.9
.6
.3
.9
.8
.1
.4
.8
.6
.0
.2
.8
.9
.3
.6
.9
.9
.0
5
3
1
12
5
7
10
6
4
10
5
4
8
5
2
10
6
4
.3
.9
.4
.4
.1
.3
.9
.1
.8
.0
.2
.8
.1
.3
.8
.8
.2
.4
5.5
4.1
1.4
12.4
5.1
7.3
11.4
6.6
4.8
10.2
5.2
5.0
8.6
5.3
3.3
10.9
6.5
4.4
T - BOD (mg/1)
C - CBOD (mg/1)
N - NOD (mg/1)
-------
TABLE #14 (con't)
77
Date: 8/03/77
Days of Incubation
STA
8
8-A
9
10
10-B
11
12
13
14
15
15-A
16
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
#
T
T*
C*
N*
T
T
C
N
T
T
C
N
T
T
T
T
T
T
T
T
T
T
T
T
T
T
2
2.9
3.0
2.2
0.8
3.2
2.0
1.6
0.4
1.7
1.8
1.7
0.1
1.6
0.5
1.2
1.3
1.0
1.4
4.2
3.6
18.6
31.8
6.0
0.6
3.0
8.4
5
5.3
5.2
3.9
1.3
5.4
4.3
3.2
1.1
3.8
3.2
2.9
0.3
2.9
1.3
1.3
1.9
0.8
1.6
4.2
3.6
27.0
44.4
6.0
6.6
3.0
8.4
8 11 15 18 20
7.4 8.8 10.6 11.1 11.8
5.4 6.3 6.8 7.1 7.8
2.0 2.5 3.8 4.0 4.0
7.0 7.8 9.1 9.7 10.2
4.5 5.3 5.6 6.0 6.4
2.5 2.5 3.5 3.7 3.8
4.8 5.9 6.6 7.2 8.0
4.0 4.7 5.3 5.4 6.2
0.8 1.2 1.3 1.8 1.8
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE #14 (con't)
78
Date: 8/24/77
STA #
P-8T*
C*
N*
P-4 T
1 T
C
N
1-A T
2 T
3 T
C
N
4 T
C
N
5 T
C
N
5-A T
6 T
C
N
7 T
C
N
8 T
8-A T
C
N
9 T
2
2.0
1.6
0.4
1.3
1.8
1.6
0.2
1.7
1.5
2.6
1.4
1.2
3.6
2.0
1.6
3.3
2.6
0.7
3.6
3.4
2.6
0.8
3.1
2.3
0.8
1.5
2.3
2.3
0
2.6
Days of Incubation
5
4.0
3.1
0.9
2.9
3.0
2.6
0.4
2.7
2.5
5.1
2.2
2.9
7.0
3.6
3.4
7.0
5.2
1.8
7.4
6.4
4.3
2.1
5.5
4.6
0.9
5.0
8.0
7.6
0.4
8
4.8
3.6
1.2
4.1
3.3
0.8
6.5
2.9
3.6
8.0
4.2
3.8
8.8
6.0
2.8
8.1
5.6
2.5
9.2
6.6
2.6
12.8
10.2
2.6
10
5.8
4.4
1.4
4.8
3.8
1.0
7.0
3.4
3.6
8.7
4.8
3.9
9.6
6.8
2.8
9.1
6.3
2.8
9.6
7.0
2.6
16.2
11.4
4.8
15
7.0
5.0
2.0
6.3
4.0
2.3
7.6
3.6
4.0
9.2
5.3
3.9
10.8
7.9
2.9
10.6
7.3
3.3
11.4
8.2
3.2
19.2
13.3
5.9
18
8.0
5.4
2.6
6.6
4.2
2.4
8.1
4.1
4.0
9.9
5.6
4.3
11.4
8.3
3.1
11.6
7.9
3.7
12.4
9.0
3.4
21.4
15.1
6.3
20
8.8
5.8
3.0
7.0
4.3
2.7
8.2
4.2
4.0
10.1
5.7
4.4
12.0
8.6
3.4
12.1
8.0
4.1
12.9
9.4
3.5
22.0
15.4
6.6
6.4
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
TABLE # 14 (con't)
79
Date: 8/24/77
STA #
10 T*
C*
N*
10-B T
11 T
C
N
12 T
13 T
14 T
15 T
15-A T
16 T
S-l T
C
N
S-2 T
C
N
S-3 T
C
N
S-4 T
C
N
S-5 T
C
N
S-6 T
C
N
2
3.0
3.0
0
1.8
1.2
1.2
0
1.8
0.9
0.5
0.8
0.8
1.1
0
0
0
8.1
8.1
0
13.8
13.8
0
33.8
33.6
0.2
2.0
2.0
0
7.8
6.0
1.8
5
6.6
6.6
0
3.0
3.3
2.8
0.5
3.0
1.6
1.4
1.0
1.2
1.3
0
0
0
15.0
13.8
1.2
24.6
24.0
0.6
55.8
53.4
2.4
15.6
13.8
1.8
15.0
11.4
3.6
Days of Incubation
8 10 15
13.6 17.3 20.9
12.2 14.1 15.7
1.4 3.2 5.2
4.7
3.8
0.9
4.2
0
4.2
19.6
16.0
3.6
35.4
29.4
6.0
71.4
61.2
10.2
18.0
13.8
4.2
27.6
15.0
12.6
6.5
5.6
0.9
13.2
0
13.2
26.6
17.0
9.6
47.2
34.0
13.2
80.2
70.0
10.2
22.2
13.8
8.4
33.8
17.0
16.8
10.2
7.7
2.5
18.6
0
18.6
66.0
17.4
48.6
88.8
39.6
49.2
106.2
72.6
33.6
45.6
22.2
23.4
57.0
19.2
37.8
18
23.1
16.8
6.3
11.8
8.6
3.2
19.2
0
19.2
72.0
17.4
54.6
94.8
39.6
55.2
138.6
74.4
64.2
63.0
22.8
40.2
64.4
20.0
44.4
20
24.1
17.3
6.8
13.2
9.0
4.2
19.2
0
19.2
72.0
17.4
54.6
99.6
39.6
60.0
157.8
75.6
82.2
79.2
23.4
55.8
72.2
20.0
52.2
*T - BOD (mg/1)
*C - CBOD (mg/1)
*M - NOD (mg/1)
-------
TABLE #14 (con't)
80
STA #
P-8 T
C
N
2
1.7
1.0
0.7
5
2.8
2.1
0.7
8
3.4
2.6
0.8
12
4.6
3.2
1.4
15
4.8
3.4
1.4
18
5.1
3.7
1.4
20
5.4
3.8
1.6
Date
STA
S-7
S-8
Date
STA
P-8
P-4
1
1-A
2
3
4
5
5-A
6
:
#
T*
C*
N*
T
C
N
:
#
T
C
N
T
T
C
N
T
T
T
C
N
T
C
N
T
C
N
T
T
C
N
8/24/77
2
7.6
7.0
0.6
2.6
2.0
0.6
8/31/77
2
1.7
1.0
0.7
2.1
1.2
1.2
0
2.7
1.9
2.4
0.5
1.9
4.7
1.9
2.8
3.8
1.6
2.2
3.8
3.8
3.0
0.8
5
13.2
12.6
0.6
15.0
13.2
1.8
Days of Incubation
8 10 15
22.6 29.0 44.4
16.0 18.2 18.3
6.6 10.8 26.1
20.4
13.2
7.2
26.8
16.0
10.8
46.2
16.2
30.0
3.0
3.3
2.4
0.9
3.8
2.9
3.8
2.9
0.9
4.6
3.7
0.9
4.9
4.0
0.9
6.7
8.0
5.2
2.8
9.4
6.3
3.1
10.4
6.9
3.5
11.1
7.2
3.9
18
58
19
39.0
46.
16,
30.0
4.9
4.0
0.9
11.4
7.2
4.2
20
58,
19,
39.0
46.
16.
30.0
5.5
4.3
1.2
T
C
N
T
C
N
T
C
N
2.4
0.5
1.9
4.7
1.9
2.8
3.8
1.6
2.2
9.2
3.2
6.0
8.5
3.8
4.7
7.6
3.7
3.9
10.5
4.3
6.2
9.6
4.9
4.7
8.8
4.6
4.2
11.4
5.1
6.3
10.3
--
--
10.1
5.7
4.4
11.8
5.2
6.6
10.5
6.0
4.5
10.8
5.9
4.9
12.2
5.5
6.7
10.8
6.3
4.5
11.7
6.8
4.9
12.8
5.7
7.1
11.2
6.5
4.7
11.8
6.7
5.1
12.1
7.2
4.9
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
81
TABLE #14 (con't)
Date: 8/31/77
STA # 2 58 12 15 18 20
7 T* 4.0 8.8 10.7 12.1 12.7 13.0 13.5
C* 2.5 5.1 6.8 7.8 8.4 8.7 9.2
N* 1.5 3.7 3.9 4.3 4.3 4.3 4.3
8 T 3.7
8-A T 4.0 9.7 11.7 13.6 14.9 15.5 16.3
C 2.8 5.2 7.2 9.0 10.3 10.7 11.1
N 1.2 4.5 4.5 4.6 4.6 4.8 5.2
9 T 3.5
10 T 3.3 8.9 11.2 13.7 15.0 16.0 16.8
C 2.9 6.3 8.3 10.0 10.- 11.4 11.9
N 0.4 2.6 2.9 3.7 4.3 4.6 4.9
10-B T 3.2
11 T 3.3 6.3 7.5 9.9 11.7 13.3 14.3
C 2.5 4.6 5.8 7.1 8.0 8.5 8.7
N 0.8 1.7 1.7 2.8 3.7 4.8 5.6
12 T 2.0
13 T 1.4
14 T 0.7
15 T 0.9
15-A T 0.8
16 T 1.3
S-l T 0.6 1.2 3.0 30.6 32.2 36.6 38.4
C 0.6 1.2 3.0 4.2 5.8 6.0 7.2
N 0 0 0 26.4 26.4 30.6 31.
S-2 T 19.0 28.2 36.8 39.6 58.8 66.6 66.6
C 13.0 22.2 26.0 27.0 28.2 28.2 28.2
N 6.0 6.0 10.8 12.6 30.6 38.4 38.4
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
Days of Incubation
5
8.8
5.1
3.7
9.4
9.7
5.2
4.5
9.1
8.9
6.3
2.6
7.9
6.3
4.6
1.7
4.2
2.8
1.7
1.6
1.8
2.6
1.2
1.2
0
28.2
22.2
6.0
8
10.7
6.8
3.9
11.7
7.2
4.5
11.2
8.3
2.9
7.5
5.8
1.7
3.0
3.0
0
36.8
26.0
10.8
12
12.1
7.8
4.3
13.6
9.0
4.6
13.7
10.0
3.7
9.9
7.1
2.8
30.6
4.2
26.4
39.6
27.0
12.6
15
12.7
8.4
4.3
14.9
10.3
4.6
15.0
10.-
4.3
11.7
8.0
3.7
32.2
5.8
26.4
58.8
28.2
30.6
-------
82
TABLE #14 (con'tO
Date: 8/31/77
Days of Incubation
STA
S-3
S-4
S-5
S-6
S-7
S-8
#
T*
C*
N*
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
2
19.0
13.0
6.0
24.1
22.8
1.8
12.6,
10.2
2.4
1.2
0.6
0.6
4.8
3.0
1.8
4.8
4.8
0
5
28.2
22.2
6.0
41.4
39.6
1.8
17.4
15.0
2.4
15.0
14.4
0.6
27.6
4.8
22.8
22.2
9.8
12.4
8
36.8
26.0
10.8
67.0
46.6
20.4
18.8
15.6
2.4
15.0
14.4
0.6
28.8
6.0
22.8
32.2
11.2
21.0
12
39.6
27.0
12.6
67.2
48.0
19.2
31.6
15.6
16.0
15.0
14.4
0.6
31.2
7.8
23.4
34.9
13.5
21.4
15
58.8
28.2
30.6
91.2
49.8
41.4
45.0
15.6
29.4
19.2
14.4
4.8
36.6
9.0
27.6
60.0
14.0
46.0
18
66.6
28.2
38.4
107.6
49.8
57.8
52.8
15.6
37.2
19.2
14.4
4.8
36.6
9.0
27.6
69.6
14.4
55.2
20
66.6
28.2
38.4
108.6
49.8
58.8
55.8
__
--
19.2
--
36.6
9.0
27.6
70.2
14.4
55.8
Date: 9/08/77
STA #
P-8 T
C
N
3
1.4
1.4
0
5
2.0
2.0
0
7
3.0
2.6
0.4
10
4.0
'3.3
0.7
15
5.3
3.7
1.6
17
6.4
4.4
2.0
20
6.5
4.5
2.0
P-4 T 2.0 2.6
1 T 2.2 2.7 3.5 5.0 5.8 6.5 6.7
C 2.0 2.6 3.3 3.6 4.2 4.4 4.5
N 0.2 0.1 0.2 1.4 1.6 2.1 2.2
1-A T 1.2 1.8
2 T 1.6 2.4
3 T 3.9 5.3 7.0 8.0 8.7 9.1 9.5
C 1.8 2.5 3.2 3.7 4.2 4.6 5.0
N 2.1 2.8 3.8 4.3 4.5 4.5 4.5
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD (mg/1)
-------
83
TABLE #14 (con't)
Date: 9/08/77
Days of Incubation
STA # 3 5 7 10 15 17 20
4 T* 5.5 9.4 13.5 14.6 15.4 16.1 16.3
C* 3.7 4.8 5.8 6.2 6.8 7.1 7.4
N* 1.8 4.6 7.7 8.4 8.6 9.0 8.9
5 T 6.5 11.8 16.5 17.8 19.0 19.6 19.8
C 3.1 4.8 5.9 6.8 8.0 8.4 8.8
N 3.4 7.0 10.6 11.0 11.0 11.0 11.0
5-A T 7.0 11.2
6 T 4.9 6.6 8.2 9.4 10.3 11.4 11.6
7 T 3.8 4.6 5.5 6.2 7.0 7.9 8.1
C 1.9 2.6 3.4 3.8 3.8 4.3 4.5
N 1.9 2.0 2.1 2.4 3.2 3.6 3.6
8 T 3.5 4.7
8-A T 3.6 5.0 6.2 6.9 8.0 8.8 9.1
C 2.5 3.2 4.3 4.6 4.9 5.7 6.1
N 1.1 1.8 1.9 2.3 3.1 3.1 3.0
9 T 3.1 4.6
10 T 1.8 4.9 5.8 7.2 8.6 9.6 9.8
C 1.0 2.9 4.8 6.0 6.7 7.2 7.3
N 0.8 1.0 1.0 1.2 1.9 2.4 2.5
10-B T 3.2 4.9
11
12
13
14
15
15-A
T
C
N
T
T
T
T
T
2.
1.
0.
2.
2.
1.
1.
0.
3
8
5
2
6
3
2
6
3
3
0
3
3
1
1
1
.6 4.7 7.2
.1 3.6 4.8
.5 1.1 2.4
.1
.4
.6
.8
.2
8.8 9.6 9.9
5.8 6.6 6.9
3.0 3.0 3.0
T - BOD (mg/1)
C - CBOD (mg/1)
N - NOD (mg/1)
-------
84
TABLE #14 (con't)
Date: 9/08/77
Davs of Incubation
STA
16
S-l
S-2
S-3
S-4
S-5
S-6
S-7
S-8
#
T
T*
C*
N*
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
T
C
N
3
1.3
1.0
1.0
0
9.6
5.4
4.2
102.0
102.0
0
31.0
31.0
0
8.2
8.2
0
7.0
7.0
0
5.1
4.5
0.6
4.2
4.2
0.0
5
1.7
11.7
5.4
6.3
15.6
5.4
10.2
132.0
90.0
42.0
69.0
57.6
11.4
19.2
12.0
7.2
16.8
12.0
4.8
14.7
8.4
6.3
15.6
9.0
6.6
7
17.1
6.0
11.1
15.6
5.4
10.2
132.0
90.0
42.0
79.6
67.2
12.4
22.2
15.0
7.2
24.0
15.0
9.0
16.2
8.4
7.8
17.4
9.6
7.8
10
26.6
9.9
16.7
41.4
6.0
35.4
183.0
111.0
72.0
98.6
76.4
22.2
25.2
18.0
7.2
43.2
17.4
25.8
37.8
8.4
29.4
40.2
13.2
27.0
15
26.6
9.9
16.7
69.0
--
--
220.0
--
--
131.0
80.0
51.0
33.6
22.2
11.4
47.8
21.4
26.4
51.0
12.6
38.4
65.4
18.7
46.7
17
53.4
11.1
42.3
72.0
--
--
264.
--
--
171.6
83.3
88.3
63.6
23.4
40.4
55.8
21.4
34.3
59.4
16.2
43.2
101.4
22.8
78.6
20
54.0
12.0
42.0
72.6
--
--
270.
--
--
172.2
84.6
87.6
66.6
25.4
41.2
55.8
21.0
34.8
62.4
18.0
44.0
104.4
27.9
76.5
*T - BOD (mg/1)
*C - CBOD (mg/1)
*N - NOD 9mg/l)
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA 903/9-79-003
:, RECIPIENTS ACCESSION NO.
1
4. TiTLE AND SUBTITLE
CARBONACEOUS AND NITROGENOUS DEMAND STUDIES
OF THE POTOMAC ESTUARY
5. REPORT DATE
Summer 1977
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
J. L. Slayton
and E. R. Trovato
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AIMO ADDRESS
I Annapolis Field Office, Region III
"-"' U.S. Environmental Protection Agency
Annapolis Science Center
""j Annapolis, Maryland 214.01
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
|12. SPONSORING AGENCY NAME AND ADDRESS
Same
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/903/00
,15. SUPPLEMENTARY NOTES
(16. ABSTRACT
I
The biochemical oxygen demand of Potomac River and STP effluent samples was
determined during the summer of 1977. The fraction associated with N.O.D.
was measured using an inhibitor to nitrification and the oxygen depletion
v/as monitored during long term incubation. The average deoxygenation constants
for the river sample C.B.O.D. and N.O.D. were 0.14 day"1 (kg). The N.O.D. was
found to be a significant component of the B.O.D.c for STP effluent and river
samples. The peak C.B.O.D. was associated with an algal bloom of Oscillatcria.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Biochemical Oxygen Demand
Nitrification
Nitrification Inhibitor
Respiration
Lag Tine
Depletion Curves
Deoxygenation
Kinetics
18. DISTRIBUTION STATEMENT
RELEASE TO FJBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
90
20. SECURITY CLASS (This page}
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (C-73)
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