EPA-670/4-74-001
February 1974
Environmental Monitoring Series
                            LITERATURE SURVEY
             OF INSTRUMENTAL MEASUREMENTS
             OF BIOCHEMICAL OXYGEN DEMAND
        FOR  CONTROL  APPLICATION 1960-1973
                             National Environmental Research Center
                               Office of Research and Development
                              U.S. Environmental Protection Agency
                                     Cincinnati, Ohio 45268

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                               EPA-670/4-74-001
                               February 1974
   LITERATURE SURVEY OF INSTRUMENTAL MEASUREMENTS

GP BIOCHEMICAL OXYGEN DEMAND FOR CONTROL APPLICATION

                      1960-1973
                         by

                 Robert J. O'Herron
      Methods Development and Quality Assurance
                 Research. Laboratory
             Program Element.No. 1HA327
       NATIONAL ENVIRONMENTAL RESEARCH CENTER
         OFFICE OF RESEARCH AND DEVELOPMENT
        U.S. ENVIRONMENTAL PROTECTION AGENCY
               CINCINNATI, OHIO 45268

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                  REVIEW NOTICE
The National Environmental Research Center --
Cincinnati has reviewed this report and approved
its publication.  Approval does not signify that
the contents necessarily reflect the views and
policies of the U. S. Environmental Protection
Agency, nor does mention of trade names or
commercial products constitute endorsement or
recommendation for use.
                      11

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                             FOREWORD
Man and his environment must be protected from the adverse effects
of pesticides', radiation, noise and other forms of pollution, and
the unwise management of solid waste.  Efforts to protect the
environment require a focus that recognizes the interplay between
the components of our physical environment--air, water, and land.
The National Environmental Research Centers provide this multi-
disciplinary focus through programs engaged in
      •   studies on the effects of environmental
          contaminants on man and the biosphere, and
      •   a search for ways to prevent contamination
          and to recycle valuable resources.
This report is part of a continued effort by the Instrumentation
Development Branch, Methods Development and Quality Assurance
Research Laboratory, NERC, Cincinnati, to evaluate instruments
and provide information to both users and suppliers.  It is also
intended that instrumentation be upgraded and that a choice of
the most suitable instrument can be made for a particular appli-
cation.
                                  A. W. Breidenbach, Ph.D.
                                  Director
                                  National Environmental
                                  Research Center, Cincinnati
                                111

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                             ABSTRACT
Development of a rapid, instrumental method for determining waste
loading in terms of biochemical oxygen demand  (BOD) would further
the efforts of controlling the unit processes of sewage treatment.
This report attempted to determine the "state of the art" of
instrumental biochemical oxygen demand methods through a survey
of related literature that included material published between
1960 and 1973.  The slow rate of microbial reactions made the
task of an instrumental approach to BOD difficult.  Microorganism
variability in numbers, kind, and acclimation caused a lack of
reproducibility.  Although the present "state of the art" does not
permit instrumental measurement of BOD for process control, an
alternative solution is suggested for secondary treatment plants.
Further research is needed to supplant the BOD test with this
method.  A process needs to be determined (e.g., biofiltration
and recirculation) to reduce the BOD of a secondary effluent sam-
ple to a sufficiently low value.  Differential measurements (ATOC,
ATOD, or ACOD) of the secondary effluent and the processed sample
produces a good estimate of the ultimate BOD.  Successful efforts
in this research would produce greater operating efficiency and
reduction in pollution discharge to receiving streams by the waste
treatment plants.
                                IV

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                            CONTENTS
                                                         Page
Abstract                                                  iv
Sections
I      Conclusions                                         1
II     Recommendations                                     2
III    Introduction                                        4
IV     Background                                          5
V      BOD Test                                            6
VI     Instrumental BOD                                    8
VII    Related Organic Pollution Measurement              10
VIII   Correlations Between BOD, COD, TOG, and TOD        13
IX     Differential Measurements                          15
X      Differential Measurements for Process Control      17
XI     Summary                                            21
XII    References                                         22

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                             SECTION I
                            CONCLUSIONS
A most urgent need in the waste treatment field is that of an on-
line biochemical oxygen demand (BOD) instrument suitable to control
the treatment process.  The slow rate of microbial reactions makes
the task of an instrumental approach to BOD difficult.  The BOD
test is losing its status as a standard method; lack of reproduci-
bility because of microorganism variability in numbers, kind, and
acclimation are the reasons that BOD test results are questioned.
Therefore, a new standard, amenable to instrumental measurement,
is critically needed to supplant the BOD test for the measurement
of waste water loading.  In addition, the standard should be
independent of microbiological activities and their inherent un-
certainties, although it must show the results of biological
action because, presently, secondary treatment plants are almost
exclusively biological.

Differential measurements, such as differential chemical oxygen
demand (ACOD), in conjunction with further treatment of sampled
effluents of treatment plants, will show the effects of bio-
logical action.  The differential indications are a result of
organic wastes being removed by the degradation and assimilation
of microorganisms in the treatment process.  More research effort
is needed on the differential measurement approach so that the
BOD test can be supplanted as the standard of waste load, and
the information of the BOD test can be obtained more directly,
rapidly, and reproducibly.

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                            SECTION II
                          RECOMMENDATIONS
The approach contemplated for this literature survey was to relate
ACOD measurements across a treatment- plant to methods of process
                                  19 20
control.  Although papers by Gaudy  '   and others indicated that
this approach was not unique, the practice does not appear to be
widespread, possibly because further refinement is necessary.  The
ACOD does give a measurement related to the organic matter removed
by microorganisms in the treatment plant, but it does not give any
estimate of the total organic matter in the waste to begin with.
The efficiency of waste removal is a variable to be determined
itself; therefore, more information is needed.  More research in
this area could lead to ways to further remove BOD from a sampled
effluent.  If the rate and extent of BOD removal is acceptable, a
very good estimate of the ultimate BOD can be made by adding the
ACOD measured across the process to that measured across the treat-
ment plant.  This differential approach may also be applied to
total organic carbon (TOC) and total oxygen demand (TOD).  In fact,
the TOC would be the measurement of choice because all of the carbon
of a sample is converted to carbon dioxide without interferences.
Incomplete combustion occurs for some nitrogen and sulfur compounds
in the instrumental measurement of TOD and COD.  The effect, however,
of the incomplete combustion is reduced because the measurement of
difference is being made.  Therefore, it is recommended that various
biofiltration media be tested and that ATOC, ATOD, ACOD, or all
three measurements be made and analyzed for correlation to the BOD
dilution test.  The intent is to provide a sample process amenable
to inclusion in a control approach for waste treatment plants.

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Automation of these differential measurements would involve various
sampling devices and their control, analog to digital converters,
storage registers, and other digital logic techniques.  Servo-
mechanism techniques, or direct digital control would be adaptable
for controlling elements of the individual processes.  Process
control ability can be demonstrated, initially, in a pilot treat-
ment plant.

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                            SECTION III
                           INTRODUCTION
The intent of this literature survey, which includes material
published between 1960 and 1973, is to determine the "state of
the art" of instrumental biochemical oxygen demand (BOD) methods.
The ultimate goal is an instrument capable of controlling the
waste treatment process.  Such an instrument must detect waste
loads and indicate the effectiveness of the waste treatment
process in removing the waste.

Sources of information for this survey have included textbooks
concerning waste treatment, U.S. Environmental Protection Agency
(EPA) publications and training manuals, journals in the environ-
mental and waste treatment field, and bibliographic references.
                                                       28
Of particular usefulness was a related abstract search.    The
Water Resources Abstract publication of the U.S. Department of
the Interior was also very useful.  Background information was
obtained on the microbial, mathematical, and chemical aspects of
BOD as well as on instrumental approaches to its measurement.  Some
pertinent background information is not specifically referred to
elsewhere in the text.13>21>31>34>37>40>44  The NERC _ Cincinnati
Library was most helpful in obtaining copies of the related papers.

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                            SECTION IV
                            BACKGROUND
The development of an effective and practical control scheme for
treating municipal sewage is hindered by the inability to measure
            2 4 24 25
BOD on-line.   '*    Although the BOD test has many disad-
vantages, it is the conventional standard of waste load measure-
ment.  '  '    Development of a rapid, instrumental method for
determining waste loading in terms of BOD or its equivalent would
further the efforts of controlling the unit processes of sewage
treatment.  This control would result in greater plant operating
efficiency.  The resultant reduction in pollution discharge to
receiving streams would enhance their quality significantly.  A
direct, rapid, reproducible measurement of waste loading, then,
is required for the often-stated goal of EPA and the waste treat-
ment field—obtaining an on-line BOD sensor.

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                             SECTION V
                             BOD TEST
BOD is usually defined as the amount of oxygen that bacteria
require while stabilizing decomposable organic matter under aero-
bic conditions.    Dissolved oxygen (DO) is the energy source of
these microorganisms when they act upon the organic waste.  In
Standard Methods for the Examination of Water and Wastewater,
it states that BOD determination is an empirical test used to
estimate the relative oxygen requirements of wastewaters, effluents,
and polluted waters and that its most frequent use is in measuring
waste loadings of treatment plants and in evaluating the efficiency
(BOD removal) of such treatment systems.  Since complete stabili-
zation of a given waste is not feasible, a 5-day standard is used
to obtain a practical estimate of the BOD.  Mathematical rela-
                                  38
tionships based upon a first-order   chemical reaction are used
in determining the ultimate BOD.  Dilution commonly provides the
excess oxygen required for heavy oxygen demanding wastes.  An
acclimated seed from a receiving stream is generally employed to
furnish microorganisms for the test.

The BOD test is losing its status as a standard because of the
difficulty encountered in controlling the variables involved:
time, seeding, dilution, temperature, pH, and toxic substances.
In addition, the first-order assumption is presently recognized as
                      1 18
an oversimplification. '    The variability and acclimation of
microorganisms used in seeding are given as the primary cause for
lack of accuracy and reproducibility of interlaboratory BOD tests
on known, single source samples.  Process control using the BOD
measurement is completely ruled out because of the extensive time

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required to complete the test.   Many sources, however, have
indicated the urgent need for an on-line instrumental measurement
of BOD. ' '  '    Perhaps, this controversy over the BOD is put
in its proper perspective by A. F. Gaudy, whose recommendation
                                   19 20
will be discussed more fully later.  '

     "It is necessary to make a distinction between the
     concept and the test (BOD  test).  While we can defend
     and recommend the concept, we shall not defend the
     test for all its present applications, but will rec-
     ommend a more satisfactory measurement for assessing
     efficiency of treatment by the activated sludge
     process."

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                            SECTION VI
                         INSTRUMENTAL BOD
An automated version of the BOD test can be obtained by employing
respirometers.  Numerous versions are described in the literature
                                           •z c 17 jj •zq 42 A\
by authors in the United States and abroad. »''*'  '    The
fundamental concept is adding either air or pure oxygen to micro-
organisms in a reaction chamber to replenish the oxygen consumed.
One version generates oxygen, upon the sensed requirement, by
                      Q 47 48 49 50
means of electrolysis. '  '  '  '    The oxygen consumption is
generally measured manometrically through the difference in pres-
sure or by means of a DO sensor.  A caustic solution, usually
potassium hydroxide, is placed in the air circulation stream to
absorb carbon dioxide.  Various transducer devices are usually
employed to record the potentiometric output on a strip chart.

Originally, respirometers were manually operated by highly trained
technicians capable of interpreting the derived results analyti-
cally.  The operation has been simplified over the years, and the
outputs have been related to BOD directly.

Respirometric methods are an improvement upon the dilution test
in the sense that generally the oxygen uptake is obtained directly
from the undiluted sample; however, time, seeding, temperature,
pH, and toxic substances remain as variables that will affect the
results as they do in the standard BOD dilution test.  Recently,
the time factor has been assailed by relating the short-term
oxygen uptake to the BOD test.    An improved approach is to
relate the impact of a waste sample 'upon the endogenous respi-
                                           45
ration rate of a suitable activated sludge:    the slope change

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encountered in oxygen consumption is correlated to BOD loads.
However, short-term BOD tests, utilizing respirometers, are based
upon a relationship, to the dilution test; i.e., they are being
based upon a test that is already of questionable value.   As in
the dilution test, microorganism variability render the results
suspect.  The respirometer utilizing these short-term techniques
does, however, serve a need for determining, rapidly, the treat-
ability or toxic nature of a waste.

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                            SECTION VII
              RELATED ORGANIC POLLUTION MEASUREMENTS
Other measurements of pollution load are chemical oxygen demand
(COD), total organic carbon (TOG), and total oxygen demand (TOD).
The COD test, although determined more rapidly than BOD, still
requires 2 or more hours to obtain meaningful results.  TOC and
TOD are instrumental measurements requiring .5 minutes or less for
results.  Automated wet chemical procedures have been perfected
for the measurement of COD.  '  '    The primary disadvantage of
all these measurements is that the biological nature of the waste
treatment plant loads are not characterized.

The COD test is a measure of those organic materials oxidizable by
dichromate (a strong chemical oxidant) in acid solutions at high
temperature.   Some organic compounds  (e.g., acetic acid) require
a catalyst to be oxidized.  Ammonia is not oxidized by dichromate
at all.  This is important because acetic acid and ammonia are
oxidized biologically.  Other organic compounds  (e.g., cellulose)
are oxidized in the COD test although they do not present an im-
mediate biochemical load to a receiving water.  An undersirable
aspect of the test is the requirement to handle hazardous chemi-
cals.  When applicable, however, the COD test is preferred to the
BOD because it is more rapid and reproducible.  Most organics are
oxidized to 95 to 100 percent of theoretical amount in the COD
test.    A comparison of recent rapid methods and past methods of
determining COD with the method of present choice in Standard
Methods shows the latter to be, by far, the most accurate.

The TOC measurement is obtained instrumentally by an operator
                                10

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first measuring the total carbon and then substracting a separate
                                    15 32
measurement of the inorganic carbon.  '    Oxygen gas is passed
continually through a combustion chamber containing a cobalt oxide
catalyst.  A micro sample is injected into the chamber, which is
maintained at 950°C.  The sample is vaporized, and all the carbona-
ceous material is oxidized.  The oxygen carrier gas transports the
carbon dioxide and steam from the chamber.  An infrared analyzer
measures the carbon dioxide present; the amount present, which is
in the form of a peak on a strip-chart recorder, is proportional
to the total carbon of the injected sample.  Output calibrations
are performed with samples of known carbon content.  A low tem-
perature combustion chamber is operated in parallel at 150°C, a
temperature below that that oxidizes organic matter.  An identical
micro sample is injected in this chamber over quartz chips coated
with phosphoric acid.  Inorganic carbon is oxidized to carbon
dioxide.  An oxygen carrier gas, again, conducts the carbon dioxide
to the infrared analyzer for measurement.  This value substracted
from the total carbon previously determined results in a value for
the TOC.

TOC is considered one of the fundamental measurements of pollu-
tion.    When performed properly, TOC determinations can be made
reliably, rapidly, and reproducibly.  Some disadvantages are the
initial instrument cost and the requirements of operator experi-
ence and technique to obtain reproducible results.

Another instrumental measurement is TOD,  '   the quantitative
measure of oxygen required to combust organic matter of a sample
at high temperature.  A nitrogen carrier gas with a fixed amount of
oxygen (usually 200 ppm) flows continuously through a combustion
                                11

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chamber that is maintained at 900°C and contains a platinum cata-
lyst.  The oxygen in the carrier stream is continuously measured
in a silver-lead fuel cell detector.  A continuous output on a
strip chart recorder results from this equilibrium condition.
An aqueous sample with impurities injected into the combustion
chamber will disturb this equilibrium.  The impurities are oxidized
by partially depleting the oxygen on the platinum surface.  The
oxygen in the carrier gas replenishes the oxygen on the platinum
surface.  This momentary demand on the oxygen in the carrier gas
is detected by the silver-lead fuel cell, and a negative going
peak (or trough) is recorded.  The measurement consists of com-
paring the peak heights with calibration of known sample contents.

Complete combustion of carbon and hydrogen takes place during the
measurement of TOD.  Nitrogen compounds are oxidation-state
dependent where molecular nitrogen  (the carrier gas) is unaffected.
Sulfur compounds are only partially oxidized.  DO contributes to
the oxidation process and thus reduces the measured demand equiv-
alent to the milligrans of DO per liter of sample.  A very close
correlation between TOD and COD has been demonstrated on several
types of effluent.
                                12

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                           SECTION VIII
            CORRELATIONS BETWEEN BOD, COD, TOC, AND TOD
Utilizing correlations between BOD and COD has been discussed in
the literature.  '    Some sources  '   qualify their use only
to fixed effluents such as, the industrial effluent from an un-
changing process.  The consensus is that for treatment of mixed
industrial and municipal wastes the BOD load varies over a wide
range of values.  The COD also ranges over a considerable span,
but these variations in BOD and COD are not in the same ratio
with each other.  Municipal waste treatment loads vary from week
to week, day to day, and even from hour to hour.  Individual
measurements of BOD, COD, TOC, and TOD can tell a lot about the
characteristics of a waste, but no attempt should be made to
replace BOD measurements with COD, TOC, or TOD.  Ford1  listed
factors to consider when attempting to use correlations between
the various measurements.

     "In attempting to correlate BOD or COD of an indus-
     trial waste with total organic carbon concentration
     one should recognize those factors which may dis-
     credit the correlation.  These limitations include:
     1) a portion of the COD of many industrial wastes
     is attributed to the dichromate oxidation of ferrous
     iron, nitrogen, sulfites, sulfides, and other oxygen
     consuming inorganics;  2) the BOD and COD tests do
     not include many organic compounds which are par-
     tially or totally resistant to biochemical or
     dichromate oxidation (however, all of the organic
     carbon in these compounds is recovered in the TOC
                                13

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analysis); and 3) the BOD test is susceptible to
variables which include seed acclimation,  dilution,
temperature, pH, and toxic substances."
                           14

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                            SECTION IX
                     DIFFERENTIAL MEASUREMENTS
     19 20
Gaudy  '   has strongly recommended replacing the BOD test with.
the ACOD measurements across an activated sludge process.  Others
have discussed similar use of the COD in the literature, '  '  '
but widespread acceptance has not been indicated.  The ACOD tech-
nique may be practiced in the field without a great deal of
publicity.  Nonetheless, Gaudy defined ACOD as "the amount of COD
removed at any time, i.e., the difference between the COD present
at the time of measurement and the COD initially present."  The
organic matter removed from a waste treatment plant is, then, the
difference between the effluent COD and the influent COD.
         ACOD   =  COD. - COD                            (1)
             r        i      e
where
         ACOD   =  metabolizable organic wastes removed
                   by microorganisms used in the process
          COD.  =  plant influent COD
          COD   =  plant effluent COD
             G
Gaudy stated that the day-to-day operation of the waste treatment
process can be assessed with a determined efficiency of COD re-
moval :
                                     ACOD
         efficiency of COD removal =      •

Another operational parameter is that of the COD ,  which is
                                                €
continually compared with the base line COD  established in
                                           C
treatability studies performed before the design stage.  In
                                15

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addition to the operational parameters, Gaudy recommended periodi-
cal sampling of the influent waste in a batch laboratory reactor.
COD tests are performed on this sample until changes in COD no
longer occur.  The ACOD of this sample gives a direct assessment
of the actual purification achieved when compared with that of
the ACOD across the treatment plant.
     0
Busch  indicated that the change in TOC measurements due to bac-
terial action  (similar to ACOD) is a prime parameter in water
pollution control work.  Also, process control capability was
indicated by "a mass culture aeration procedure for a rapid (1 to
4 hours) determination of biodegradable carbon content."  Busch
expressed this differential as total bacterially available carbon
(T, AC).   Busch  advocated using ATOC measurement along with short-
term (24 hour) BOD measurements to obtain the total biological
oxygen  (T OD).  Busch contended that the increase in bacterial
mass must also be accounted for in the use of oxygen consumption.
This results in some simple-to-complex combination measurements of
varying accuracies and time intervals to account for the materials
balance concept.
                                16

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                             SECTION X
           DIFFERENTIAL MEASUREMENTS FOR PROCESS CONTROL
This literature survey has not revealed a direct, rapid, and
reproducible instrument or method of determining BOD that is
suitable for process control.  The literature has instances of
respirometers successfully monitoring sewage treatment influent/
                22
effluent wastes.    Short-term oxygen demands are related to 5-day
BOD's.   The suitability of indirect estimates of BOD by respiro-
meters for process control is questionable.  As in the dilution
test, results depend on microbial reactions, which are not re-
producible in a measurement sense.

Since the status of the BOD test as a standard is waning, an
alternative test should be pursued.  The BOD test has had its
widest application in determining waste loadings and efficiencies
in waste treatment plants.  By 1977, municipal waste treatment
plants are required to use secondary treatment, and differential
measurements such as ACOD, ATOC (i.e., T, AC), and ATOD all can
be applied across these secondary waste treatment plants to
obtain useful information.  Refinements and further research,
however, are needed before differential measurements can be used
for process control.

Before differential measurements can be applied to process con-
trol, a better estimate of the total biologically degradable
organic waste must be made, i.e., each measurement must include
an estimate of this total metabolizable material so that process
modifications can be made intelligently.  If the waste removed
and a good estimate can be made of the maximum waste that can be
                                17

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removed are both known, then the process efficiency can also be
determined.  It is herein theorized that a sufficiently accurate
estimate of the total metabolizable waste is obtained if a small
sample is processed after secondary treatment so that complete
removal of BOD is approached.  A. differential measurement across
this processed sample, when added to the differential across the
secondary treatment plant (i.e., from influent to primary) will
give this estimate.  Optimally, simple biological filtration of a
sample, settling, recirculation, and subsequent passage through
a 0.45y filter will approach the complete removal of BOD.  The
development of this process, utilizing various filter media,
would be the subject of further research in this area.  Monitoring
the recirculated sample for several of the instrumentally measur-
able basic parameters  (DO, pH, ORP, temperature, turbidity, and
ammonia, if available) would also be of interest.  One of these
parameters could be an indicator of the completion of the process.
If the biofiltration approach is unsuccessful, biological suspen-
sion by aeration might be pursued.   Initially, however,
biofiltration would appear to be the simpler approach.  Again,
the ultimate goal is instrumental control of the waste treatment
process.

Processing a secondary effluent sample to achieve an acceptable
degree of BOD removal would make possible determining the waste
discharge load to the receiving stream in terms of the differ-
ential measurement.  For example, in terms of COD:
                                18

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         COD  - COD  = A COD .                             (3)
            e      p       d                             v J
where
         COD  = plant effluent COD
            G
         COD  = sample processed to approach zero BOD
        ACOD, = metabolizable organic waste in the plant
                effluent
Then the total organic matter of an influent waste that is decom-
posable by microorganisms is
         Total decomposable waste = COD  + COD,          (4)

The efficiency of the plant's waste removal operation is
                              COD.  - COD
         Plant efficiency =   ^ -    - X 100          (5)
                                 1
                             ACOD
                             ACODr + ACODd

Data obtained from the standard BOD and COD tests can be collected
at various secondary treatment facilities to verify these relation-
ships.  In summary, equations (1), (3), (4), and (5) will enable
the daily determination of:
     1.  waste treatment plant load in terms of ACOD
     2.  waste load discharged to the stream
     3.  the total oxygen demanding load of the influent to the
         plant
     4.  the efficiency of the treatment plant to remove metabo-
         lizable organic waste.
                                19

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The use of COD values for equations (3), (4), and (5) is for
illustrative purposes only; TOG, TOD, or instrumental COD can
be used equally well, and their use may very well be better.
In fact, if funding permitted, it would be well to purchase
these instruments and compare all three methods.  The chemical
ACOD method is directly applicable to small waste treatment
plants that cannot afford expensive instrumentation.  The ulti-
mate goal, however, is to automate the measurement for control
purposes, and instrumental TOC, TOD, or COD may be more amenable
to this.  The sample-handling of TOD is already capable of con-
tinuous operation.
                                20

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                            SECTION XI
                              SUMMARY
Prospects for process control of waste treatment plants appear
favorable if differential measurement capabilities can be devel-
oped further.  If rapid, reproducible removal of BOD to an
acceptable value can be accomplished, differential measurements
(ATOC, ATOD, or ACOD) can give the information of the ultimate
BOD in less than 1 day.  Instrumental TOC, TOD, and COD can
already be determined in less than 5 minutes.  Detention times
for secondary waste treatment would add 6 to 8 hours.  The addi-
tional processing method and detention time would be the subjects
of further research.-  The method of choice would be biological
filtration in which various filtration media, and biological
activation techniques would be pursued.
                                21

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                             SECTION  XII

                             REFERENCES

 1.   American  Public  Health  Association,  "Standard Methods  for  the
     Examination  of Water  and Wastewater,"  13th  Edition,  New  York,
     1971.

 2.   American  Public  Works Association,  "Feasibility  of Computer
     Control of Wastewater' Treatment," Project #17090 DOY,  Water
     Pollution Control  Research  Series,  EPA,  1970.

 3.   Arthur, R. M., "An Automated BOD Respirometer,"  Proceedings
     19th Industrial  Waste Conference, Purdue University, 628-637,
     1964.

 4.   Berkovitch,  I.,  "Instruments and Control Systems," Pollution
     Control Report,  p.  27,  April 1972.

 5.   Bridie, A. L. A. M.,  "Determination of Biochemical Oxygen
     Demand With  Continuous  Recording of Oxygen  Uptake,"  Water
     Research, Pergamon Press, 3, 2,  157-165, 1969.

 6.   Busch, A. W., Grady,  L., Rao,  T. S., and Swilley, E. L. , "Short-
     Term Total Oxygen  Demand Test,"  JWPCF, 34,  4,  354-362, 1962.

 7.   Busch, A. W., "Energy,  Total Carbon, and Oxygen  Demand," Pro-
     ceedings  20th Industrial Waste Conference,  Purdue University,
     May 1965.

 8.   Busch, A. W., "Carbon Analysis as a Concept and  Procedure  in
     Water Pollution  Technology," The Analyzer,  Beckman Instruments,
     p.  3-7, February 1967.

 9.   Clark, J. W., "Electrolysis Biochemical  Oxygen Demand,"  South-
     west Water Works Journal, 46,  5, 26, 1964.

10.   Clifford, D. A., "Automatic Measurement  of  Total Oxygen  Demand,"
     Proceedings  23rd Industrial Waste Conference,  Purdue University,
     May 1968.

11.   Davis, E. M., "BOD vs COD vs TOC vs TOD," Water  and  Wastes
     Engineering,  8,  2, 32-34, 38,  1971.
                                 22

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12.   Eckenfelder, W.  W.,  Jr., Industrial Water Pollution Control,"
     McGraw-Hill Book Company,  New York, 1966.

13.   Eye, J.  D., and Ritchie, C.  C.,  "Measuring BOD With a Membrane
     Electrode System,"  JWPCF,  38, 1430-1440, 1966.

14.   Fair, G. M., Geyer,  J.  C., and Okun, D.  A., "Water Supply and
     Waste Water Disposal," Volume 2, Wiley,  New York, 1968.

15.   Ford, D. L., "Application of the Total Carbon Analyzer for
     Industrial  Wastewater Evaluation," Proceedings 23rd Industrial
     Waste Conference, Purdue University, 989-999, 1968.

16.   Foulds,  J.  M., and  Lunsford, J.  V., "An Analysis of the  COD
     Method," Water and  Sewage  Works, March 1968.

17.   Gannon,  J.  J., Pelton,  J.  R., and Westfield, J., "Respirometer
     Assembly for BOD Measurement of River Waters and Biologically
     Treated  Effluents,"  International Journal Air and Water
     Pollution,  Pergamon  Press, 9, 27-40, 1965.

18.   Gates, W. E., and Ghosh, S., "Biokinetic Evaluation of BOD
     Concepts and Data,"  Journal  Sanitary Engineering Division,
     Proceedings ASCE, 97, SA3, 287-309, 1971.

19.   Gaudy, A. F., Jr.,  and Gaudy, E. T. , "Biological Concepts for
     Design and  Operation of the  Activated Sludge Process," Project
     #17090 FQJ, Water Pollution  Control Research Series, EPA, 1971.

20.   Gaudy, A. F., and Gaudy, E.  T.,  "ACOD Gets Nod Over BOD  Test,"
     Industrial  Water Engineering, 9, 5, 30-34, 1972.

21.   Genetelli,  E. J., Nemerow, N. L., and Barbaro, R. D., "Instru-
     ment for Determining the Treatability of Industrial Waste,"
     Proceedings 26th Industrial  Waste Conference, Purdue University,
     1971.

22.   Genthe,  W.  K., Arthur,  R.  M., and Srinivasaraghavan, R.,  "Go
     On-Line; It's Vital  for Automation," Water and Wastes Engineer-
     ing, 9,  7,  42-44, 1972.
                                 23

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23.  Goldstein, A.  L.,  Katz, W.  E., Meller, F.  H. ,  and Murdoch, D.  M.,
     "Total Oxygen Demand - A New Automatic Instrumental Method for
     Measuring Pollution and Loading on Oxidation Processes," pre-
     sented American Chemical Society, Division Water, Air and Waste,
     September 1968.

24.  Guarino, C. F., Gilman, H.  D., Nelson, M.  D.,  and Koch, C. M.,
     "Toward Computer Control of Wastewater Treatment," presented
     44th Annual Conference Water Pollution Control Federation,
     October 1971.

25.  Guarino, C. F., "The Use of Computers in Philadelphia's Water
     Pollution Control  Activities," Water Research, Pergamon Press,
     6, 597-600, 1972.

26.  Haines, G. D., and Anselm,  C. D., "Improved Automated Chemical
     Oxygen Demand Measurements," Advances in Automated Analysis,
     Technicon International Congress 1969, Mediad Inc., 1970.

27.  Hiser, L. L.,  and  Busch, A. W., "An 8-Hour Biological Oxygen
     Demand Test Using  Mass Culture Aeration and COD," JWPCF, 36,
     4, 505-516, 1964.

28.  Holoman, V. L., "Methods for Determining Biochemical Oxygen
     Demand," Analytical Methodology Information Center (AMIC),
     Battelle, Columbus, 1972.

29.  Ickes, J. H.,  Gray, E. A.,  Zaleiko, N. S., and Adelman, M. H.,
     "Operating Experience with  a COD Instrument in Industrial
     Wastes," Technicon Symposia, 1, 1967.

30.  Ingols, R. S., "Short-Term  BOD," Water and Sewage Works, 115,
     258-260, 1968.

31.  Isaacs, W. P., and Gaudy, A. F., Jr., "Comparison of BOD
     Exertion in a Simulated Stream and in Standard BOD Bottles,"
     Proceedings 22nd Industrial Waste Conference,  Purdue
     University, 165-182, 1967.

32.  Jones, R. H., and Dageforde, A. F., "Application of a High
     Sensitivity Total  Organic Carbon Analyzer," Analysis Instru-
     mentation, 6, 43-51, 1969.
                                 24

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33.   Mullis, M. K.,  and Schroeder, E. D.,  "A Rapid Biochemical
     Oxygen Demand Test Suitable for Operational Control," JWPCF,
     43, 2, 209-215, 1971.

34.   ReVelle, C. S., Lynn, W. R.,  and Rivera, M. A., "Bio-Oxidation
     Kinetics and a Second-Order Equation  Describing the BOD Re-
     action," JWPCF, 37, 1679-1692, 1965.

35.   Rowe, D. R., and Canter, L. W., "Correlation of BOD and COD for
     Synthetic and Domestic Waste Influent," Public Works, October
     1968.

36.   Sawyer, C. N.,  "Chemistry for Sanitary Engineers," McGraw-Hill,
     New York, 1960.

37.   Schroeder, E.  D., "Importance of the  BOD Plateau," Water
     Research, Pergamon .Press, 2,  803-809, 1968.

38.   Sletten, 0., "Determining BOD Curve Parameters," Water and
     Sewage Works,  January 1966.

39.   Snaddon, X. V.  M., and Jenkins, S. H., "Biological Oxidation in
     a Self Operating Respirometer," Advances in Water Pollution
     Research, Proceedings 2nd International Conference, Pergamon
     Press, 2, 289-323, 1964.

40.   Stumm, W., and Morgan, J. J., "Aquatic Chemistry," Wiley-
     Interscience,  New York, 1970.

41.   Symons, J. M.,  McKinney, R. E., and Hassis, H. H., "A Procedure
     for Determination of the Biological Treatability of Industrial
     Wastes," JWPCF, 32, 8, 841-852, 1960.

42.   Tool, H. R., "Manometric Measurement  of the Biochemical Oxygen
     Demand," Water and Sewage Works, 114, 211-218, 1967.

43.   Umbreit, W. W., Burris, R. H., and Stanffer, J. F., "Manometric
     Techniques," 4th Edition, Burgess, Minneapolis, 1964,

44.   Velz, C. J., "Applied Stream Sanitation," Wiley-Interscience,
     New York, 1970.
                                  25

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45.  Vernimmen, A. P., Henken, E. R., and Lamb, J.  C.,  III, "A Short-
     Term Biochemical Oxygen Demand Test," JWPCF, 39,  6,  1006-1020,
     1967.

46.  Welt, T. W., and Reiter, W. M., "Constant COD  Vigil-Keeps Lid on
     Process Upsets," Chemical Processing, October  1965.

47.  Young, J. C., Garner, W., and Clark, J. W., "An Improved
     Apparatus for Biochemical Oxygen Demand," Analytical Chemistry,
     37, 784, 1965.

48.  Young, J. C., and Clark, J. W., "Growth of Mixed  Bacterial
     Populations at 20°C and 35°C," Water and Sewage Works, 112,
     251-255, 1965.

49.  Young, J. C., and Clark, J. W., "High Temperature BODs by
     Electrolysis," Water and Sewage Works, 112, 341-345, 1965.

50.  Young, J. C., and Clark, J. W., "Second Order  Equation for BOD,"
     Journal Sanitary Engineering Division, Proceedings ASCE, 91,
     SA1, 43-57, 1965.
                                 26

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                                   TECHNICAL REPORT DATA
                            (Please read Intimations on the reverse before completing)
 1 REPORT NO.
  EPA-670/4-74-001
                              2.
                                                            3. RECIPIENT'S ACCESSIOI*NO.
 4. TITLE AND SUBTITLE
  Literature Survey of Instrumental  Measurements of
  Biochemical Oxygen Demand  for  Control Application
  1960-1973
                5. REPORT DATE
                 February  1974;  Issuing Date
               6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
  Robert J.  O'Herron
                                                            8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORG "VNIZATION NAME AND ADDRESS
 Methods  Development § Quality Assurance Research Labo-
 ratory,  National Environmental  Research Center
 Office of Research & Development
 U.S.  Environmental Protection Agency
 Cincinnati. Ohio  45268	
                10. PROGRAM ELEMENT NO.
                 1HA327; ROAP  01AAD;  TASK 02
                11. CONTRACT/GRANT NO.
 12. SPONSORING AGENCY NAME AND ADDRESS
  Same  as above
                                                            13. TYPE OF REPORT AND PERIOD COVERED
                                                            14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
  Development of a rapid,  instrumental method for determining  waste loading in terms
  of biochemical oxygen demand  (BOD)  would further the  efforts of controlling the unit
  processes of sewage treatment.   This report attempted to determine the "state of the
  art"  of instrumental biochemical oxygen demand methods through  a survey of related
  literature that included material published between 1960 and 1973.   The slow rate of
  microbial reactions made the  task of an instrumental approach to BOD difficult. Micro-
  organism variability in numbers, kind,  and acclimation caused a lack of reproducibility
  Although the present "state of  the  art" does not permit instrumental measurement of
  BOD for process control, an alternative solution is suggested for secondary treatment
  plants.   Further research is  needed to  supplant the BOD test with this method.   A
  process needs to be determined  (e.g., biofiltration and recirculation) to reduce the
  BOD of a secondary effluent sample  to a sufficiently low value.   Differential measure-
  ments  (ATOC, ATOD, ACOD) of the  secondary effluent and the processed sample produces
  a  good estimate of the ultimate  BOD.  Successful efforts in  this research would
  produce greater operating efficiency and reduction in pollution discharge to receiving
  streams by the waste treatment plants.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
  b.IDENTIFIERS/OPEN ENDED TERMS  C. COSATI Field/Group
*Biochemical  oxygen demand (BOD), Activated
sludge process,  *Waste treatment, Industrial
wastes,  *Process control
   *Secondary  treatment,
   *BOD instruments,
   *Chemical oxygen demand
   (COD), *Total  oxygen
   demand (TOD),  *Total
   organic carbon (TOC),
   BOD removal
       13B
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