WATER POLLUTION CONTROL RESEARCH SERIES
17010DXD08/70
   PHOSPHOROUS REMOVAL
           BY AN
  ACTIVATED SLUDGE PLANT
U.S. ENVIRONMENTAL PROTECTION AGENCY

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          WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of pollution
in our Nation's waters.  They provide a central source of
information on the research, development and demonstration
activities in the Environmental Protection Agency, through
inhouse research and grants and contracts with Federal,
State, and local agencies, research institutions, and
industrial organizations.

Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Chief, Publications Branch
(Water), Research Information Division, R&M, Environmental
Protection Agency, Washington, B.C. 20460.

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       PHOSPHORUS REMOVAL BY AN ACTIVATED SLUDGE PLANT
                               by
        Sewerage Commission of the City of Milwaukee
                 Milwaukee, Wisconsin  53201
                              for  the
                ENVIRONMENTAL PROTECTION AGENCY
                       Program #17010 DXD
                      Grant #WPD  188-01-67
                                  188-02-68
                                  188-03-69
                           August,  1970
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, B.C. 20402 - Price $1.00

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            EPA Review Notice
This report has been reviewed by the
EPA, and approved for publication.
Approval does not signify that the con-
tents necessarily reflect the views and
policies of the Environmental Protection
Agency, nor does mention of trade names or
comnercial products constitute endorsement
or recommendation for use.
                     ii

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                              ABSTRACT


The Milwaukee plants removed an average of Q0% of the influent total
phosphorus (TP).  Milwaukee offered an opportunity for plant scale
demonstration and study of the activated sludge process parameters
effects on TP removal.

The high TP removals were due to sufficient solids production from
the amounts of TP, BOD and suspended solids in Milwaukee sewage.
Phosphorus balances demonstrated an average of 95.7$ of the phospho-
rus removed was recovered in the waste sludge withdrawn as Milorganite.

An equation was developed for predicting % TP removal from East Plant
(EP) 1968 data.  Applied to 1969 and 1970 data when TP removals
exceeded 80#, the significant parameters were food to microorganisms
(F/M), MLSS, and TP to microorganisms (TP/M).  The significance of
ML-DO, air application rate and detention time could not be shown.

Plant scale studies revealed that F/M, MLSS and TP/M mainly affected
soluble orthophosphate (SOP) removal.  The removal of SOP was
associated with MLSS biological activity by oxygen uptake rate
measurements in tank studies.  A ML-DO^ 2.0 mg/L past the tank turn-
point was effective for SOP removal.  Insolubilization of SOP by
sewage soluble  cations appeared to be insignificant in the process.
It  appears that brewery waste water  aids  soluble phosphorus removal
at  the Milwaukee  plants.

The cyclic removal  of TP  in  an activated  sludge plant was shown by
the analyses of hourly influent and  effluent  samples  for BOD, TP  and
SOP during a year's study.   These  cycles  corresponded to the hourly
changes  in sewage composition and  flows and  clarifier sludge blanket
build-up.  At times TP removal efficiency was greatly reduced by  the
loss of  solids  from overloaded clarifiers at  peak  flows.

Continuous addition of ferrous sulfate waste  pickle  liquor  to EP-ML
at  a 15 mg/L-Fe rate  provided hourly effluent soluble phosphorus
residuals of 0.05 mg/L-P.   X-ray diffraction  studies  of freeze dried
sludges  showed  iron present  as vivianite.

This report  was submitted in fulfillment  of  Grant  No. WPD 188-01-67,
188-02-68, and 188-03-69, Program  No.  17010  DXD, between the Federal
Water  Quality  Administration (now Environmental Protection Agency) and
the Sewerage Commission of  the City  of Milwaukee,  Wisconsin.

Key Words:   Phosphorus removal,  activated sludge  process, process
             parameters, wastewater treatment, biological treatment.
                                 111

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                           CONTENTS

Section

           Abstract                                               iii
                                                                    v
           Contents

           List of Figures                                        vii

           List of Tables                                          lx

           List of Appendices                                      xl

 I         Conclusions
                                                                    3
 II        Recommendations

 III       Introduction                                             5

 IV        Literature Survey

 V         Procedures

           A.  Milwaukee Waste Water Treatment Facilities           11
               at  Jones Island

           B.  Sampling and Analytical Techniques                   13

 VI        Research Phases, Results &  Discussion

           A.  Correlation of Activated Sludge Process             15
               Parameters  to Phosphorus Removal  on a
               Plant Scale

           B.  Demonstration of Cyclic Removal of Phosphorus       19
                from Sewage by an Activated Sludge Plant

            C.  Plant Study of the Effect of Clarifier Blanket      23
               Depths on Clarifier Effluent Residual SOP

           D.  Plant Loading Study (F/M and TP/M)                  26

           E.  Effect of Brewery Waste Load                        30

           F.  Plant Scale Phosphorus  Balances                      36

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                             CONTENTS

Section

            G. Relationship Between the Removal of Total BOD         38
               and Removal of TSP in an Activated Sludge
               Plant (BODR/TSP/R)

            H. Study of Soluble Phosphorus Uptake in East Plant      41
               Aeration Tanks (General)

            I. Effect of MLSS-02 Uptake Rates and Air Appli-         42
               cation Rates on Soluble Phosphorus Uptake in an
               Aeration Tank

            J. Evaluation of MLSS Activity by Glucose Dehydro-       52
               genase Assay

            K. X-Ray Diffraction Studies  of Sewage Suspended         56
               Solids and Waste Sludge Solids

            L. Cationic  Removal of Phosphorus  from Sewage            57

            M. Effect of Iron Addition to an Aeration Tank on       60
               Soluble Phosphorus  Removal

            N. Plant  Scale Iron Addition Study                      66

   VII      Acknowledgements                                        77

   VIII     References                                               79

   IX       Nomenclature and Glossary                               83

   X        Appendices                                               85
                                   vi

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                           FIGURES

                                                              PAGE
1.   JONES ISLAND SEWAGE TREATMENT PLANT                        12

2.   SEWAGE AND EFFLUENT AVERAGE HOURLY COMPOSITION             20
     13/3/67 to 6/15/68

3.   SOP RELEASE AND DIFFUSION FROM SLUDGE BLANKET              24
     VERSUS TIME

U.  EFFECT OF PLANT LOADINGS ON PLANT EFFLUENT                  28
    SOP LEVELS

5.   EFFECT OF BREWERIES SHUTDOWN ON RS COMPOSITION             33

6.   FREQUENCY DISTRIBUTION BODR/TSPR WEEKDAY DATA              39

7.   FREQUENCY DISTRIBUTION BODR/TSPR WEEKEND DATA              40

8.   AERATION TANKS DO PROFILES  (9-30-1969,  8:00 A.M.)         43

9.    AERATION TANKS DO PROFILES  (10-6-1969,  12:30 P.M.)        45

10.    EFFECT OF AIR APPLICATION RATE ON ML-DO LEVEL             47

11.    EFFECT OF AIR APPLICATION RATE ON MLSS-02 UPTAKE RATE     48

12.   EFFECT OF AIR APPLICATION RATE ON ML-TSP LEVEL             49

13.   EFFECT OF AIR APPLICATION RATE ON ML-SOLUBLE BOD LEVEL     50

lU.   EFFECT OF IRON ADDITION ON EAST PLANT RESIDUAL SOP         68

15.   COMPARISON OF EAST AND WEST PLANT SDI'S                    69

16.   ACCUMULATION OF  IRON  IN EP-RS                              71

17.   RETURN SLUDGE ASH CONTENT  (DRY BASIS)                      72

18.   RETURN SLUDGE NITROGEN CONTENT (DRY BASIS)                 73

19.   TECHNICON AUTOANALYZER SCHEMATIC                           87
                              VII

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                              TABUS

Table                                                           pafte

  1.  Effect of Clarifier Sludge Blanket Depths on               22
      East Plant Effluent Quality

  2.  Comparison of SOP Concentration (mg/L-P) of Aeration       25
      Tank No. 10 Outlet ML, Clarifier No. 5 ML - Feed,
      Clarifier No. 5 Effluent in Relation to Clarifier
      Blanket Depth

  3.  Averages of Daily Data by Periods                          27

  U.  Summary Period Averages                                    31

  5.  Comparison of Period Averages                              32

  6.  Relation of Phosphorus Removed to Solids Synthesis         35

  7.  Calculated Weekly Phosphorus Recoveries                    37

  8.  Average BODR/TSPR Ratios                                   38

  9.  Air Application Rates                                      42

  10.  Effect of Air Application Rates                            44

  11.  Daily Process Parameter Data                               46

  12.  MLSS-02 Uptake Rate After Six Hours Aeration               51

  13.  Dehydrogenase Assay Variability                            53

  lU.  Dehydrogenase Assay Data                                   53

  15.  Variability  of ML - Dehydrogenase Activity and MLVSS       54
      at Different Sample Locations

  16.  Comparison of Coefficients  of Variation (C.V.)             54

  17.  Average  Cation Concentrations (mg/L)  for July, 19&9        58

  18.  Effect  of Iron Dosage on  ML - TSP Level                   61

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                               TABLES

Table


  19.  Run 6 Observation Data
                                                                62
20.  Reduction of Soluble Iron Concentration in an              63
     Aeration Tank

21.  Average Iron Recoveries                                    64-

22.  Soluble Iron and TSP Release by MLSS                       65

23.  Effluent SOP (mg/L-P)                                      67

21*.  Average Return Sludge Composition                          75

25.  Aerobic Digestion of Sludge                                92

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                             APPENDICES


Appendix                   Title

   A    Phosphorus Determination with Technicon Autoanalyzer     85

   B    Procedure used for MLSS and RSSS Determination           88

   C    BOD Determination                                        89

   D    Discussion of Material Found Floating on the Surface     91
        of the EP Aeration Tanks and the Aerobic Digestion
        of Waste Sludge

   E    Average Daily Screened Sewage Characteristics and        94
        Plant Operation Data

   F    Total Phosphorus Removal at the Jones Island Plants      95
        Based on Plant Flows
                                   xi

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                           SECTION   I


                           CONCLUSIONS


A three-year plant scale study on the phosphorus removal by an acti-
vated sludge plant conducted at Jones Island Plant, Milwaukee, Wis-
consin, resulted in the following observations:

1.  The Milwaukee plants on the average removed 80# of the TP from
sewage.  The effluent TP concentrations coincided with the hourly
changes in sewage composition and flow, and at times with the hourly
build-up of clarifier sludge blankets.  The effluent TP concentrations
increased as the sewage flow, BOD and TP concentrations increased.
Low effluent TP concentrations were usually observed with low sewage
flow, BOD and TP concentrations.

2.  The relationship of total BOD removal to total soluble phosphorus
removal was found to vary according to the day of the week; on the
average, the ratios were 88:1 for weekdays, 62:1 for Saturdays, and
Vf:l for Sundays.

3.  Weekly plant scale phosphorus balances during  a 37 week study
showed that an average of 95.1% of the sewage phosphorus removed by
both plants could be accounted for in the Milorganite produced.
This indicated that the removal of waste sludge  (as Milorganite)
was the vehicle for withdrawal of phosphorus from  the waste treat-
ment system.

1*.  Overloaded clarifiers at peak flows resulted in lower  TP  removals
due to spewing of solids over the weirs. However,  the  detention  of
solids for  2 to 3 hours at  different sludge blanket depths had very
little influence on the clarifier effluent  SOP concentration.

5.  A  substantial release of  SOP  was observed  when the RS  was mixed
with the  screened sewage.   The  concentration of SOP in the resulting
ML was  2  to 3 times greater than  that expected from the calculated
amount  in a corresponding mixture.

6.  The  removal of TSP by  MLSS appears to be related to MLSS
metabolic activity  as  was  shown by  MLSS-02  uptake  rate measurements
along  the aeration tank.

 7.   A loading  study with the  two plants showed that an average F/M
 and TP/M loadings  of 0.291 and .011, respectively, resulted in slightly
 higher average SOP  removals compared to the higher average loadings of
 0.511* and 0.019»  respectively.

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 8.   There  was  a marked  drop in the  soluble phosphorus removal during
 the shutdown of the  Milwaukee breweries  in 1969,  compared with the
 high soluble phosphorus removals before  and  after the shutdown.  The
 rapid recovery of soluble phosphorus removal by both plants indicates
 the brewery waste water aids soluble phosphorus removal.

 9.   Aeration tank studies in the East Plant  indicated that an air
 application rate of 0.86 cu. ft. /gal. of influent or larger and a
 ML-DO of 2.0 ag/L beyond the tank turnpoint  was adequate and effective
 in reducing soluble BOD to 10 ag/L  and TSP to  0.5 mg/L-P at MLSS
 concentrations of 2530  to 2910 mg/L.  A  ML-DO  of  1.0 ag/L beyond the
 tank turnpoint did not  result in as much SOP removal as was observed
 with a ML-DO of 2.0 mg/L.

10.  The quantity of insoluble phosphorus (58£  for 1969) in Milwaukee
 sewage is unusually high compared to  normally  reported values for
 municipal waste waters.  No significant  differences were found in
 influent and plant effluent soluble iron, aluminum, calcium and mag-
 nesium concentrations.   This indicated that  very little insolubli-
 zation of phosphorus by these cations occur  in the  activated  sludge
 process.  It appears that the cationic fixation of  phosphorus
 probably occurs in the  sewage prior to its  reaching the plant.

11.  Limited X-ray diffraction studies on freeze dried WS  samples
 revealed that  iome of the iron in the WS was in the form of a crystal-
 like iron orthophosphate, vivianite Pe3
12.  Limited phosphorus removal studies with the addition of waste
 pickle liquor to the mixed liquor indicated that enhanced SOP
 removals can be achieved by iron addition.  The waste pickle liquor
 appeared to have no effect on the ML biota.

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                             SECTION II

                          RECOMMENDATIONS
          The results of this three year study have shovn that  the
City of Milwaukee Severage Commission's East Plant can consistently
average 80$ total phosphorus removal from sewage.   A short term study
of continuous iron addition, as ferrous sulfate waste pickle liquor,
to the East Plant has demonstrated the feasibility of a long term
plant study.  The preliminary data indicated that  it could be possible
to consistently produce a plant effluent with a TSP residual of
approximately 0.5 mg/L-P or less.  It could also be possible to improve
the plant total phosphorus removal efficiency from an average of &0%  to
an average of 90$.

          A one year study to determine the long term effects of con-
tinuous iron addition on the 115 mgd East Plant and to compare  its
performance to the 85 mgd West Plant which will receive no additional
iron is proposed.  The effects of continuous iron addition upon mixed
liquor flora, mixed liquor settleability, waste sludge conditioning
requirements and plant physical facilities would be evaluated along
with effluent phosphorus and iron concentrations.

          This would require the continuous feeding of ferrous  iron
(as waste pickle liquor) to the mixed liquor feed channel of the
115 »gd East Plant.  Twenty four hour composite samples of East and
West Plant effluent would be analyzed to determine the ability of
ferrous iron to increase phosphorus removal.  Microscopic examination
of mixed liquor samples would be utilized to determine if iron
affected the mixed liquor culture.

          Extension of the test period  over one year would establish
the feasibility of iron addition as a method for enhanced sewage
phosphorus removal.  If iron addition proves to be feasible it could
provide an economic method of phosphorus removal for existing acti-
vated sludge plants, and provide effluents with consistently low
phosphorus residuals.

          The completed work has shown  that excellent removal of
phosphorus from sewage can be obtained  in an activated sludge plant.
However, due to the size of the operation (115 mgd) and limitations
in the method of waste sludge removal  (fertilizer production) it was
extremely difficult to control and/or change the process parameters
on a day to day basis.  It  is therefore suggested that consideration
b« given to modifying the East Plant. The modifications would be the
isolation  of two  aeration tanks  and one clarifier  and a  separated
mixed  liquor feed.  This would provide  a 12 mgd plant operated on  its
own  return sludge,  in which all  process parameters  could be  controlled
and  varied as  required to establish the mechanisms  of phosphorus
fixation  in the  activated sludge process.

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                          SECTION III

                         INTRODUCTION
          It has long teen recognized that phosphates are one of the
major factors contributing to the progressive fertilization of streams
and lakes which result in frequent and highly objectionable algae
blooms.

          Although over 90% of the biologically oxidizable organic
matter and suspended solids are removed in the conventional  activated
sludge process, the reduction of dissolved mineral nutrients is gener-
ally very low.  Most municipal plants employing the activated sludge
treatment process, report phosphorus removals from sewage of 20 to 30%.
There are a few exceptions, such as the Milwaukee  (l), San Antonio
(2), and Baltimore (3) plants where phosphorus removals as high as &Q%
to 96% have been reported.

          No significant conclusions have been reached as to the
reason for such wide variation in the effectiveness of the convention-
al activated sludge process to remove total phosphorus from sewage.
One group of investigators, Menar and Jenkins  (U), hypothesized that
based on a normal BOD  of about 200 mg/L and total phosphorus of
10 mg/L-P in sewage, the biological removal of phosphorus in the form
of waste activated sludge should be 20 to  30%  and any additional re-
moval observed is the  result of  the insolublization of phosphate by
the soluble cations  (mainly calcium and iron)  present either in the
hard carriage waters or coining from steel  industries or  both.  The
second group  (Levin  and Shapiro  (5),  and Vacker,  et. al.  (6)) hold
the theory that the  activated sludge   microorganisms under  optimum
operating conditions  can  store phosphorus  far in  excess  of  their
metabolic requirements (100 BOD: IP)  and have called this exces«
uptake "luxury uptake".

          The Milwaukee Jones Island plants  have  been  consistently
 showing  good total phosphorus removals (usually over 80%).   The  two
plants  (East  and West) are  operated in parallel and each plant treats
 a part of the total  flow.   In 1967,  the Federal Water Pollution Con-
 trol  Administration  initiated a three year research and demonstration
 project  with the Sewerage Commission of the City  of Milwaukee.   The
 objective of the study was  to  demonstrate and optimize the effects
 of the activated sludge process  parameters on a plant scale for the
 removal  of  total phosphorus from sewage.

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                            SECTION IV

                         LITERATURE SURVEY
           Sewage phosphorus removals "by the activated sludge process
have been reported by a number of investigators,  Owens (7)  2 to  U6$,
Stone (8), 6U to ?1#, for three Chicago waste water treatment plants
Hurwitz (9) reports removals of 76.7$, 36.6$, and 53.9$.Some of  the
short term plant scale investigations made by the Federal Water
Pollution Administration as summarized by Witherow (3) have indicated
total phosphorus removals of 51 to 15% in the Northside plant of
Amarillo and the Village Creek plant in Fort Worth. The Rilling plant
in San Antonio and the Back River plant in Baltimore have been report-
ed to consistently remove an average of 80$ and 90$ of the  total
phosphorus respectively.

           Phosphorus has also been successfully removed from waste
waters by using chemicals such as lime, alum, ferric chloride,  ferric
sulfate, ferrous sulfate, and sodium  aluminate.   These chemicals have
been used to precipitate phosphorus in tertiary treatment by  Owens (7),
Lea, et. al. (10), Rohlich  (ll), Malhotra, et. al. (12) and Nesbitt
(13).  Chemicals have also been used to insolublize phosphorus  in the
biological treatment units by their addition to the aeration  units,
Tenney and Stumm (lU), Barth and Ettinger  (15), Eberhardt and Nesbitt
(16), or by their addition prior to the primary sedimentation units,
Rudolf (17), Neil (l8), Schmid and McKinney  (19).

           A review of the  current literature  suggests that two schools
of thought are being used to explain the wide  variation in the phospho-
rus removals observed at different plants  in the United States.  Sawyer
(20), Sekikawa, et. al.  (21), Hall and Engelbrecht  (22), Menar and
Jenkins  (U), support the theory that the biologically incorporated
phosphorus in the activated sludge solids  is between  2 to  3% phosphorus
on the volatile mass basis  and any additional  removal is cationic.
Menar and  Jenkins  (H) indicate that biological phosphorus  removal is not
affected by the sludge  growth rate or  by  standard  process  operating
parameters and that the phosphorus removal is  directly proportional to
the net  sludge growth.   This means that the phosphorus removed biologi-
cally in a conventional  activated sludge  sewage  treatment  plant would
be  in the  range of approximately  100 parts of BOD  removed  to 1 part of
soluble  phosphorus removed.  Based on  an  average BOD  removal of  200 mg/L
and influent total phosphorus  content  of  10 mg/L-P, about  20 to  30$ of
the  influent phosphorus  would be  removed  biologically.

           The  second theory was  presented in papers  by  Levin and
Shapiro  (5), Borchardt  and Azad  (23),  and Connell  and Vacker (2); they
indicated that  activated sludge  solids under certain  conditions  were
 capable  of removing  more phosphorus  than  they require for  cell  growth.

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The "biological uptake of excess phosphorus was called "luxury uptake".
They reported that luxury uptake vas enhanced by high ML-DO concen-
trations, and the phosphorus incorporated by this mechanism was re-
leased from the solids by anaercaic or acidic conditions.   They report-
ed that luxury uptake leads to sludges containing as high as 1% phos-
phorus on the VSS basis.

           Most investigations, Sawyer (20), Hall and Engelbrecht (22),
Levin and Shapiro (5), were laboratory experiments to study the acti-
vated sludge process parameters effect on the removal of SOP from
sewage.  Connell and Vacker (2), Witherow (3), have reported the process
parameter effects based on full scale plant studies which showed good
phosphorus removals.  Sawyer (20) found that an addition of glucose to
increase the sewage BOD by 1*00 mg/L reduced the sewage phosphorus from
2.68 mg/L-P to 0.00 mg/L-P. Sekikawa, et. al. (21), Hall and Engel-
brecht (22), and Levin and Shapiro (5), also observed higher phosphorus
removals when the initial BOD concentration of the substrate was in-
creased.  Witherow (3) reported that the phosphorus removal in the
aeration tank was affected by the BOD load applied to the tank and he
observed good phosphorus removals with the influent BOD in the range
of 118 to 202 mg/L.  Menar and Jenkins (U) found that the phosphorus
content of the activated sludge volatile solids did not vary signifi-
cantly over a wide range of substrate removal rates and the weighted
average per cent phosphorus on the VSS basis was 2.62%.

           The effect of high initial phosphorus content of the sub-
strate on phosphorus removal has been reported by Witherow (3).  He
observed good phosphorus removals when the influent phosphorus was in
the range of U.2 to 10.5 mg/L-P.  Higher phosphorus levels in the in-
fluent resulted in decreased % phosphorus removals in the activated
sludge process.

           The effect of detention time on phosphorus removal has
been reported by Srinath (2U), Alarcon (25), Hall and Engelbrecht (22),
Levin and Shapiro (5), Srinathfs (2U) data showed that the phosphorus
and BOD removal rates appear to coincide, approximately 10% removal
after one hour and then gradually increasing to 90$ after five addition-
al hours of aeration.  Levin and Shapiro (5) observed over 7055
soluble phosphorus removals in an aeration time of 3 hours.  Witherow
(3) recommends a modal detention of > 2.5 hours in the aeration tank
for good phosphorus removal.  Sekikawa et. al. (21) and Alarcon (25)
found that after all the  BOD had been consumed, further aeration of
ML caused the release of phosphorus from the sludge solids due to cell
oxidation (i.e., endogenous respiration).

           There are divided opinions on the role of MLSS concent-
ration in the removal of phosphorus in the aeration tanks.  Hall and
Englebrecht (22) and Sekikawa, et. al. (21) found MLSS concentrations
had very little effect on the rate or the extent of soluble uptake.

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Srinath, et. al. (2U) reported that maximum phosphorus uptake was
produced "by 20 to 30 percent return sludge.  Feng (26) observed low
MLSS (500 mg/L) to effect the best phosphorus removals when the aer-
ation rates were high (18 cu.ft./gallon of ML).   Connell and Vacker
(2) obtained maximum phosphorus removal at an average daily BOD loading
rate of about 50 Ibs. of BOD/100 Ibs. of aeration solids.  Witherow (3)
observed good phosphorus removals with MLSS >1200 mg/L and loading
rates ranging from 0.26 to 0.35 Ibs. of BOD/lb.  of MLSS/day.

           Levin and Shapiro (5) found that ML pH had a pronounced
influence on phosphorus removal, a pH range of 7 to 8 was most effec-
tive while pH values >8 and <6 resulted in phosphorus release from the
sludge solids.

           Rudolf (17) in 19^7 reported a release of soluble phospho-
rus during anaerobic sludge digestion.  In 196l,Alarcon (25) demon-
strated that the soluble phosphorus content of ML decreased during
aeration and increased when aeration was stopped.  Campbell (27)
reported that return sludges kept under anaerobic conditions at room
temperature for four hours released phosphorus from the sludge solids
into the liquid.  Levin and Shapiro (5), Connell and Vacker (2),
Han and Englebrecht (22), and Witherow (3) indicate that a ML-DO
level of approximately 2 mg/L was necessary for the optimum uptake
of soluble phosphorus.  Hall and Engelbrecht (22) and Connell and
Vacker (2) found that the release of phosphorus from the solids
back into the liquid (such as in the final clarifier) was not signi-
ficant if a high dissolved oxygen level had been sustained during
the second half of the aeration period.

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                        SECTION  V
                        PROCEDURES
      MILWAUKEE WASTE WATER TREATMENT FACILITIES AT JONES ISLAND
          The wastewater treatment system of the Sewerage Commission
of the City of Milwaukee on Jones Island consists of the East and
West Plant.  The capacity of the activated sludge plants is  115 mgd,
and 85 mgd respectively.  The physical layout of these plants is
shown in Figure 1.  The Milwaukee plants serve a total drainage area
of UlO square miles having a connected population of approximately
1,000,000.  Combined sewers serve approximately 6.6% of the total
area and the remainder of the area has a separate sewer system.

          The volume of wastewater from this highly industrial area
consists of approximately 225? industrial and 78$ domestic wastewater
(28).  The daily average characteristics of screened sewage and some
daily average operation data for 1967» 1968 and 19^9 are given in
appendix E.  The wastewater flows through mechanically cleaned "bar
screens (l inch openings) and then flows through a battery of eight
grit chambers (8 x 8 x 90 feet long each) at a velocity of approxi-
mately one foot per second.  Fine screenings are removed by passage
of the degritted sewage through eight rotary drum screens having
3/32 inch slots.  Approximately 60 wet tons of screenings and grit
are removed and incinerated daily in a 5 stage multiple hearth
furnace.  The screened sewage flow is then divided between the two
activated sludge plants (East and West).

          After screening the sewage flows into aeration tanks where
air is supplied through plate diffusers arranged in a ridge and furrow
type pattern.  Design detention time is 6 hours.  Final sedimentation
in peripheral feed clarifiers is accomplished during a 2 hour design
time for detention.  The waste sludge is disposed of by processing
it into Milorganite fertilizer.  Further details of the Jones Island
plants can be found in reference 28.
                               11

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                    HIGH • LOW iFvfl.
                    V tCWIGt  IWHONt?

                           If
HARBOR
ENTRANCE
KINNICKINNIC


   RIVER
                                                                                                         EWERAGE COMMISSION
                                                                                                         CITY OF  MILWAUKEE
                                                                                                            GENFRAL PLAN
                                                                                                       JONES ISLAND SEWAGE
                                                                                                         TREATMENT PLANT
                                                      FIGURE  I

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                  SAMPLING AND ANALYTICAL TECHNIQUES
           Sewage sampling - Initially, screened sewage samples were
single grab samples which were used for the hourly study.   Aliquots
proportional to flow from these hourly samples were used to make the
2^-hour composite sample.

           On 6-13-68, a Phipps - Bird sewage sampler was  put into
operation to provide hourly sewage composites (30 - 200 ml. portions/
hour).  Aliquots proportional to flow from these hourly composites
were used to make the 2k hour composite.  This sampling procedure
markedly reduced the fluctuations in the sewage phosphorus and BOD
concentrations exhibited by the hourly grab samples.

           Effluent sampling - Plant effluent samples were hourly
grab samples.  The 2k hour composites were prepared the same way as
for sewage.  Hourly grab samples of the plant effluent showed very
little fluctuation in BOD and phosphorus concentrations from hour to
hour compared to screened sewage hourly grab samples.

           Others - All other samples used in short term studies
were seven liter grab samples.

           Analytical methods - Listed below are brief descriptions
of the analytical methods and instrumentations used in this study.
Some of the analytical methods used are described in the appendix
and the instruments manufacturer operation manuals are listed in the
references.  Angel Reeves glass fiber filter pads (2.U cm., 93^AH)
were used to provide the filtrates for the analyses of "soluble
components".

           Determination of phosphorus - Technicon Autoanalyzer as
described in Appendix A was used.  The Autoanalyzer was used only
for SOP analyses because the Technicon acid digestion system, auto-
matic sampler for liquids with colloidal suspended solids and the
automatic filtration system were found to be inadequate.

           Dissolved oxygen measurements - were made by a variety
of instruments.  The ML-DO was continuously monitored at the outlets
of six EP aeration tanks by means of "galvanic cell" probes.  Spot
ML-DO measurements were made by a YSI Model 5^18 probe and Model 51
meter.  The YSI Model 5^20 probe and Model 5^ meter were used to
determine the DO levels for the BOD determination.  The MLSS-02
uptake rates were determined with a YSI Model 53 Biological Oxygen
Monitor.  The procedure used was as described in the suppliers manual
(29) using 1 to  2 and 1 to 5 dilutions on each ML sample.
                                13

-------
           East Plant effluent turbidity - vas continuously monitored
by a Hach CR surface turbidimeter Model 1889.  Spot turbidity measure-
ments were made with a Hach Laboratory Turbidimeter Model 2100.  The
turbidimeters were operated and calibrated as described in manufactur-
er's "Instruction Manuals" (30) and (31).

           The MLSS and RSSS concentrations - were ascertained by a
procedure in use in the Milwaukee Sewerage Commission's Laboratory
(Appendix B).

           The total and total soluble cations concentrations  (Fe,
Al, Ca and Mg) - were determined on "ternary acid digestates" of the
sample by means of an Atomic Absorption instrument (instrumentation
Laboratory, Inc. Model No. 153).  The instrument operation and cali-
bration were as described in the manufacturer's "Procedure Manual"
(32).

           Biochemical oxygen demand (BOD) - the "Azide Modification
of the lodometric method" for the BOD analyses as given in Standard
Methods 12th edition (33) was compared with a modified procedure
using a YSI Model 5^20 probe and Model 5*+ meter to determine DO levels.
The modified procedure is described in appendix (C).  A comparative
study of these methods showed good agreement.

           A study to determine a factor for converting U day  and
6 day BOD's to 5 day BOD's (l.lU and 0.93) showed good agreement
with those reported by B. L. Goodman & J. W. Foster  (31*) of 1.13 &
0.91 respectively for sewage.
                                14

-------
                            SECTION VI

              RESEARCH PHASES, RESULTS AMD DISCUSSIONS
    CORRELATION OF ACTIVATED SLUDGE PROCESS PARAMETERS TO  PHOSPHORUS
    REMOVAL ON A PLANT SCALE.
           In this study, all pertinent data from the Milwaukee
Sewerage Commission East Plant located on Jones Island for the 1968
year and for the 1969 year thru September 30 was transferred to IBM
computer cards.  The month of January, 1970 was used for the comparison
study of 1968 loge equation.

           The data from these cards was then used to establish the
variables included in this analysis.  It was initially assumed that the
percent of total phosphorus removed by the activated sludge process is
a linear function of a set of process parameters (note : effluent
soluble orthophosphate was considered as a variable not as a process
parameter).  The predictive equation of phosphate removal can then be
expressed as :
           Y = ai + a2x2

           a-^ = intercept of the regression line

           a^ = regression coefficient for ith parameters ,
                      i = 2, 3, ... 8

where      Y = % removal of total phosphate

           Xp = food to  microorganism ratio (F/M)

                F = Ibs. of BOD/ day
                M = Ibs. of volatile suspended solids (MLVSS)

           x~ = detention time (hours) in aeration tank

           x^ = cu. ft. of air/ gallon of sewage

           Xc - mixed liquor suspended solids (mg/liter) (MLSS)

           x/r = dissolved oxygen in the effluent of aeration
                      tank (mg/liter)

           X.T = total phosphate in the influent in Ibs/day (TP)
                           microorganisms (M)   (MLVSS)

           xg = soluble orthophosphate in the effluent (mg/liter)
                                 15

-------
           Another set of statistical evaluations vas made on the
basis of the assumption that the distribution of parameters influenc-
ing percent removal of total phosphate (x2, x^, ... xg) is exponential,
such that the logarithm of the dependent variable (percent removal of
total phosphate) varies linearly with the logarithm of the independent
variables.  The regression equation for this assumption can be ex-
pressed as
           Y = aixp  X3  ' * * X8


           The data was analyzed in the following groups with several
trials in each group.

           1968 Data - Natural Form (362 cards)
           1969 Data - Natural Form (273 cards) 1/1/69 - 9/30/69
           1968 + 1969 Data - Natural Form (601 cards)
           1969 excluding brewery strike period -
                Natural Form (217 cards)
           1968 Data - Logarithmic Form (3U2 cards)
           1968 Data - Logarithmic Form (231* cards)
           1969 E&ta - Logarithmic Form (259 cards)
           1968 + 1969 Data - Logarithmic Form (601 cards)
           1969 excluding brewery strike period -
                Logarithmic Form (217 cards)

           During 1969, a brewery strike from June 9 to July 15
 caused significant  differences to occur at the sewage treatment plant
 Thus,  the 1969 data was analyzed including and excluding the strike
 period to determine the effect of large volumes of brewery wastes
 on the Milwaukee treatment plant.

           Method of analysis - A multiple regression analysis was
 performed with the  data from 1968 and 1969 in both the natural form
 and in the logrithmic form  (log to the base e) and is explained
 completely in a separate report ( 35 ) •

           Results  - Several equations were developed for each set
 of data both in natural form and in logarithmic form.  Generally the
 significant  variables were:

           Xg F/M ratio

           Xg Detention Time

           xc Mixed Liquor  Suspended Solids

           x.' TP/M  ratio
                                  16

-------
            As  an example,  the best  equation  developed for the 1968
 data was the following-  Equation Number  1

            Loge Y a 3.55118 - 0.02855  Loge x2 +  0.05819 Loge x

                   - 0.10076 Loge x~


            This equation used data  from  those days  (23^) in 1968
 when the effect of overloaded clarifiers was not evident.  This was
 determined by  using the  following criteria:

            1.   Effluent  BOD < 20 mg/1
            2.   Effluent  SS < 20  mg/1
            3.   Clarifier Blanket <  lU'
            k.   (Total P - Soluble P) in the effluent < O.U mg/l-P

If any 3 of the above U criteria were satisfied,  the data for the
respective date in 1968 was accepted and analyzed in the multiple
regression analysis.

           The above equation was then tested against the 1969  data
from January 1 to September 30,  minus the June 9  to July 15 brewery-
strike period, plus  January 1,  1970.  The same criteria for over-
loaded clarifiers was used.  A total of 256 days  during the  above
period was compared.

           Comparison is best shown as follows by relating the
measured % phosphorus removal to that removal calculated in the
above equation  (l).
           On 193  days, the calculated $ removal was within 10$ of the
           measured  % removal.

           On 115 days, the calculated % removal was within 5# of the
           measured  % removal.

           On 102 days, the calculated % removal was within U$ of the
           measured  % removal.

           On 86 days, the calculated % removal was within 3>% of the
           measured  % removal.

           On 65 days, the calculated % removal was within 2% of the
           measured  % removal.

           On those  days  (196 out of 256) when the measured % removal
           was  > 80$, the calculated % removal was within 10% except
           for  3 days.
                                   17

-------
          A conclusion can be drawn from this analysis.  When the
removal of phosphorus exceeds B0% in the Jones Island plant, the
significant parameters are Food/Microorganism ratio, mixed liquor
suspended solids and Total Phosphorus/Microorganism ratio as
related in Equation (l).
                               18

-------
DEMONSTRATION OF CYCLIC REMOVAL OF PHOSPHORUS FROM SEWAGE BY AN
ACTIVATED SLUDGE PLANT.


           In the literature prior to 1966, the majority of the studies
reported on phosphorus removal from sewage by the activated sludge^
process were small scale laboratory experiments under ideal conditions.
A few plant scale investigations were reported but were limited to the
study of SOP levels in the effluent from the aeration tanks and not in
the effluent from the secondary clarifier.  Very little information
from long term studies was available on an activated sludge plant's
capability to remove total and soluble phosphorus from sewage on a hour-
ly basis.  At the outset of this investigation, the influent and the
effluent of a 115 mgd activated sludge plant were monitored on an hour-
ly basis, 7 days a week.  This initial approach was taken to study the
effects of plant operation practices, sewage flow and composition on
the hourly removal of sewage phosphorus by an activated sludge plant.
This study was carrried over a period from 12-3-67 to 12-19-68.

           Screened sewage and East Plant effluent grab samples were
taken  every hour and stored under  refrigeration.  These samples were
analyzed the next  day  for BOD, TP  and SOP.   The  data from the hourly
grab samples of screened sewage exhibited extreme fluctuations, where-
as  the data  from the effluent hourly grab samples showed very little
 fluctuation.   Data for each hour  for each day of the week was aver-
 aged because the  data showed  that  sewage  total phosphorus  removal
was influenced by the  sewage  composition  and volume of flow, and by
 operation of the  clarifiers which varied  from day  to  day.   For
 example, on Sunday and Saturday sewage  volume of flow, BOD and
 phosphorus concentration were consistently lower than those for
 Monday thru Friday.  The data for Monday  thru Friday was considered
 separately because insufficient capacity  in the dewatering facilities
 on those days controlled the MLSS level and the clarifier blanket
 depths.  Because of this, it was usually not possible to maintain a
 given MLSS level in the aeration tanks from day to day during this
 study.

            The averaged hourly data for the screened sewage and for
 the East Plant effluent are presented in Figure 2.  The East Plant
 effluent data was adjusted by 9 hours to compensate for the plant
 flow thru time.  After this adjustment, the effluent data correspond-
 ed fairly close to the influent data.

            Figure 2 exhibits the  cyclic nature  of phosphorus re-
 moval by the East Plant.  It also demonstrates  that three cycles
 occur during each week in the East Plant.   These cycles are related
 to three sets of  circumstances which occur  weekly and may vary from
 week to week.
                               19

-------
               4OO

               360

               320

               280

             -1240

             j 200

               160
             O
             O 120
             m
                so

                 :
                 o
	 LEGEND
	SEWAGE
   	EFFLUENT
	FLOW
/  X
/    x
                                                                     /   X
                                                                    /    X
140

 H

120

110
    O
100  O

90

80  £
    O
70  J^

60

51
I
•

                                       X  /
                                                                                                            A
                                                                                                                             V    /
                                                                                                                             ~^—r~
                 N
               TUESDAYS
                                                                           WEDNESDAY
                                                                            N
                                                                         THURSDAY
                                                                                                                         M                 M
                                                                                                               FRIDAYS          SATURDAYS
                FIGURE  2 SEWAGE a EFFLUENT  AVERAGE   HOURLY  COMPOSITION  12/3/67 TO 6/15/68 (EFFLUENT  ADJUSTED FOR 9  HOUR  DETENTION)

-------
           The first cycle was labeled the "Sunday Cycle".   It
started at approximately U PM (see Figure 2) on Saturday (actual
effluent time would "be 1 to 2 AM Sunday) and continued until 6 AM
Monday (actual effluent time, 3 to k PM Monday.). The reduced sewage
flow and BOD concentrations occurring during this cycle resulted in
increased detention time and air application rate which in turn in-
creased the ML-DO.  The most striking characteristic of the Sunday
Cycle was the consistency of the low levels of TP, SOP and BOD in the
East Plant effluent from hour to hour, which averaged below 1.0 mg/L-P,
0.5 mg/L-P and 10 mg/L respectively.  This period appeared to have the
most favorable conditions for the activated sludge process to remove
phosphorus from sewage.

           The second cycle was called the "Daily Cycle".  It differed
from the first in that the effluent TP, SOP and BOD levels fluctuated
over a 2k hour period in the same manner as' the sewage flow and
nutrient (phosphates) concentrations.  This cycle started with peak
flow and BOD levels at 2 to 3 PM on any day and gradually decreasing
to the lowest values at about 3 AM.  The daily cycle occurred Monday
thru Friday as shown in Figure 2.

           The third cycle was the  "Weekly Cycle".  The main charac-
teristics of this cycle were the increase in the amount of insoluble
phosphorus and BOD in the plant effluent starting from Monday which
kept on increasing as the week progressed.  This cycle was found to
be  dependent on the mixed liquor settleability and the capacity of
the  dewatering facilities for removing  the waste sludge.  Most of the
time  dewatering facilities were unable  to remove the waste sludge as
fast  as it was produced.  As  a result,  the  unremoved waste sludge
accumulated  in the  clarifiers causing higher sludge blankets  during
hours  of  peak flow  on  certain days.  The  amount  of waste sludge
accumulated  in the  system generally increased  from Monday  to  Saturday,
resulting in high sludge blankets  during the peak flow hours.  The
final result was  that  the  overloaded clarifiers  sometimes  discharged
MLSS over the weir  during peak  flow hours and  caused  an  increase  in
the effluent BOD  and insoluble phosphorus concentration  as  shown  in
Figure 2.

           The effect of clarifier sludge blanket depths  on the  TP,
SOP and SS concentrations  of the  East Plant effluent  are  summarized
in  Table  1 on the next page.
                                21

-------
                             TABLE 1
   EFFECT OF CLARIFIER SLUDGE BLANKET DEPTHS ON EP EFFLUENT QUALITY
Maximum Clarifier Daily Averages from Hourly Number
Blanket Depth Effluent Sample Data of Days
Reached in 24 Hours 12/3/67 to 9/15/68 Observed

Feet
0 to U
5 to 8
9 to 13.5
TP
mg/L-P
1.11
1.04
2.10
SOP
mg/L-P
0.70
0.64
0.88
Insoluble -P*
mg/L-P
0.41
0.40
1.22
• ss
mg/L
16
14
45


107
75
102
«  Insoluble P = TP - SOP

           The above data shovs that the effluent SOP levels on the
average did not change greatly with increasing sludge blanket depths,
                                 22

-------
PLANT STUDY OF THE EFFECT OF CLARIFIER BLANKET DEPTHS ON CLARIFIER
EFFLUENT SOP RESIDUAL

           It is well known that SOP is released by sludge solids when
they are detained in the final clarifiers for extended periods  of time.
Thus, the release of SOP from the clarifier sludge solids could in-
crease the clarifier effluent SOP concentration.  If this occurred,the
effects of the process parameters in removing SOP by MLSS during
aeration would be obscured.

           The effect of sludge detention time on the release of SOP
from sludge solids was first studied in the laboratory.  A typical
laboratory experiment consisted of using a ML sample which had been
taken from an aeration tank after six hours of aeration ( .and contained
0.3 mg/L - P of SOP).  This ML sample was then divided into five
portions which were placed into five one liter graduate cylinders  and
allowed to settle at room temperature (72°F).  Then at hourly intervals
(from one cylinder each hour) the supernatant was carefully removed in
200 ml aliquots (four in all).  The supernatant fractions and the
sludge fraction were then analyzed for SOP.  The SOP release and dif-
fusion data are presented in Figure 3.  This experiment showed that the
amount of SOP released from the sludge solids increased with increased
sludge detention time as expected.  However, as shown in figure 3,  the
majority of the released SOP remained in the quiescent sludge blanket
fraction and only a  small amount of released SOP diffused into the
supernatant with time.  This means that the clarifier effluent can
contain some SOP released by the sludge  solids detained in the
clarifier by the process of diffusion.  But, more  important are
clarifier operations during periods of high blanket  and peak flows.
The  data indicates  that  it  is possible that if  the inflow ML causes
turbulent conditions during periods of high blankets the clarifier
effluent could  contain  SOP  released by the solids  detained in the
clarifiers.

            Plant  studies to determine if clarifier sludge SOP release
had  a  significant  influence on  the clarifier  effluent  SOP residual
were also made.   During  a  ten day period the  ML effluent  from an
aeration tank  (EP Tank  #10), the ML influent  to clarifier #5 and the
final  effluent  from a clarifier (EP Clarifier #5)  were  sampled  5
times  a day.  The  SOP content was determined  on each sample.

            The  data in  Table  2  showed that during this  study period
there  was  very  little diffusion of  SOP from the clarifier sludge
blankets  to the clarifier  effluent.
                               23

-------
                                     SOP    MG/L -  P
V)
f~

O
o
m

CD
m
H



m

co

co
       - m
       H X
       O O
o
c
^)
m

CM

co
o
T)
r
m

co
m

>

o

o
d  m en
CO

o
       00°   5
       -< m
       CD ro
o
   SLUDGE

  BLANKET
FRACTION  4
                                           SUPERNATA
FRACTION  3
                                                 r-o
                                                 cnO
r   LIQUID-

 FRACTION  2
                                                       C/)
FRACTION
m Q

-------
                             TABLE 2
             COMPARISON OF SOP CONCENTRATION (MG/L-P)
        OF AERATION TANK-10 OUTLET ML, CLARIFIER #5 ML-FEED,
  CLARIFIER #5 EFFLUENT IN RELATION TO CLARIFIER BLANKET DEPTH

                                      SAMPLING TIME

12-23
1968


12-2U



12-26



12-27



12-30



12-31



1-3
1969


1-1*



1-6



1-7




Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
Outlet
Feed
Effluent
Blanket Depth
7:30 AM
O.U1*
-
0.05
6
0.07
0.03
0.22
6
0.19
0.21
0.28
U
0.12
0.3U
0.37
6
0.67
0.77
0.76
1
O.U2
0.66
0.63
1
1.1*
1.1*
1.1*
1
1.0
0.92
1.5
1
3.1
3.2
2.9
1
3.7
1*.0
3.7
1
9:30 AM

_
0.03
6
0.19
0.06
0.13
6
0.20
0.19
0.27
U
0.06
0.19
0.2k
6
0.61
0.57
0.61*
1
0.13
O.lU
0.37
1
1.3
1.3
1.1*
1
0.27
0.2l*
0.70
1
3.0
3.0
3.0
1
2.9
2.7
2.7
2
11:30 AM
0.05
0.02
0.03
7
O.Ol*
O.Ol*
0.07
6
0.26
0.22
0.29
1*
0.06
0.08
0.13
6
0.1*2
0.1*1
O.U6
1
0.15
0.13
0.19
1
1.1
1.1
1.0
1
0.12
0.06
0.16
1
3.0
2.9
2.9
1
2.0
1.8
1.7
2
1:30 PM
0.06
0.03
o.ou
8
O.Ol*
0.02
—
6
0.35
0.36
0.3**
1*
0.05
0.05
0.07
k
0.32
0.27
0.31
1
0.07
0.11
-
1
0.88
0.71*
1.0
1
o.oi*
0.06
0.09
1
2.7
2.7
2.6
1
1.6
1.2
1.3
3
3:00 PM
0.05
0.01
_
8
_
_
_
6
0.36
0.31
_
U
O.Ol*
0.06
_
1*
0.39
0.35
_
1
_
_
—
1
0.83
0.71*
_
1
o.ou
0.07
_
1
2.7
2.6
^
1
1.6
1.3
_
k
Blanket nepth - Feet
                               25

-------
                  PLANT LOADING STUDY (F/M AND TP/M)


          The first year's data indicated that the plant loading
parameters, food to microorganism ratio (F/M) and total phosphorus
to microorganism ratio (TP/M), appeared to be related to the removal
of phosphorus by the activated sludge process.  The effects of the
F/M and TP/M loadings were studied simultaneously in both the acti-
vated sludge plants.  The following loadings were chosen for this
study:

          Plant               Loading Ratios      Remarks

                             F/M         TP/M

          East (EP)         0.300       0.012     Optimal Loading

          West (WP)         0.600       0.02U     High Loading

Under these loadings the EP was expected to yield good phosphorus
removals as compared to the WP.  It was further planned to reverse
the above loadings between the two plants to see if the reverse
results could be observed.  The desired F/M and TP/M loadings were
obtained by modifying the operations of both plants.

          The pertinent data summarized in Table 3 are averages of
the daily data for the periods indicated.  In general, the data
indicated that the high loadings (with average values of 0.511* F/M
and 0.019 TP/M in the WP for period II) reduced the WP-SOP removal
efficiency.  The effect of the plant loadings on the daily EP and
WP effluent SOP concentrations are shown in Figure U.

          The initial plan was to then reverse the plant loadings
to see if the EP - SOP removal efficiency would be reduced.  A
viscous floating material appeared on the surface of the EP aeration
tanks in period II but none was observed in the WP.  The amount of
this viscous material continued to increase in the EP until it was
felt that this material and the continuation of the loading study
would jeopardize the EP treatment efficiency.  Regular defoaming
agents were ineffective in breaking this foam.  Vacuum skimming
of the EP aeration tanks and clarifier feed channels reduced the
amount of this foam and aided in overcoming this problem.  Thus,
the plant loadings were not reversed and this study was suspended.
The sewage flow distribution and other process parameters were then
changed in both plants and were gradually restored to their normal
values in period III.  Further details on this foam problem are
given in appendix (D).
                               26

-------
                                                        TABLE 3
                                          AVERAGES OP DAILY DATA BY PERIODS.
K>
         Period
         Plant
         % Sewage Distribution
         % Return Sludge
I - Prior to Study
        Period
    2/1 to 2/16-
    Dnr
East
58
25
         Air - Million cu.ft./day 133
Vest
1*2
25
           107
II -
East
50
35
Loading Study
Period
2/17 to 3/10-
Dry Flow
West
50
25
III -
East
25
After the Study
Period
3/11 to 3/18-
Dry flov
West
U6
25
IV -
3/19
East
51*
25
Period of
Excessive
Rainfall
to 3/31-Rain
West
U6
25
         133
          107
                                                                            133
                                                     107
                                                    118    107
SEWAGE
SOP
TSP
TP
BOD
SS
FLOW
EFFLUENT
SOP
TSP
TP
BOD
SS
MG/L-P
MG/L-P
MG/L-P
MG/L
MG/L
MGD

MG/L-P
MG/L-P
MG/L-P
MG/L
MG/L
2.5
M
9.8
258
218
100.1

1.5
1.9
2.2
15.8
18


69.1

1.7
2.2
2.1*
15.8
19
2.7
I*. 2
9.7
260
253
88.1

1.1
1.1*
1.9
17.0
23


86.1

1.8
2.1
2.9
21.0
26
2.5
k.Q
9.9
306
258
93.0

0.59
0.91*
1.3
19.6
21


77.0

1.6
2.2
2.6
22.2
26
2.0
3.2
8.5
21*7
232
102.2

0.28
0.1*1*
0.82
18.8
18


86.1

0.77
0.97
1.5
20.5
28
         PROCESS PARAMETERS
         F/M
         T?/M
         MLSS          MG/L
         DO            MG/L
         DETENTION     HRS
         AIR CU.FT./GAL

         % REMOVAL
         SOP
         TSP
         TP
O.U36
0.0167
2l*6l
U.3
7.3
1.3H
0.372
0.0ll»2
2513

7.5
1.57
0.291
0.0109
2953
3.1
7.9
1.53
0.511*
0.0188
2273

6.2
1.26
0.366
0.0319
2989
3.9
7.7
l.UU
0.1*72
0.0152
2657

6.9
i.Uo
0.320
0.0109
3051*
3.1
7.1
1.18
0.335
0.0118
3291*

6.2
1.26
 1*0.0
 59.6
 77.6
32.0
53.2
75.5
59.3
66.7
80.1*
33.3
50.0
70.1
76.1*
76.5
86.9
28.0
1*5.0
73.7
86.0   61.5
86.3   69.7
90.1*   82.U

-------
I '
 ,,
                                                         STUDY  PERIOD
 AFTER  THE
STUDY PERIOD
3/11/69 TO 3/18/69
PERIOD OF CONTINUOUS
     RAINFALL
  3/19/69 TO 3/31/69
PRIOR TO STUDY  PERIOD
                                                     2/17/69 TO  3/10/69
                        2/1/69 TO 2/16/69
                                                                                                      LEGEND
                                                                                                      - EAST PLANT
                                                                                                        WEST PLANT
                                                                                                        SEWAGE
                                                                                                  So
                                                                                                  3/23
                               So
                               3/30
                  FIGURE  4   EFFECT  OF  PLANT  LOADINGS  ON   PLANT  EFFLUENT  SOP   LEVEL

-------
          Reduced TP/M and F/M loadings observed in period IV vere
caused "by surface runoff due to continuous rainfall in this period
(1.02 inches in 13 days) which affected influent composition and flow
volumes.  The reduced loadings frequently happen because of infil-
tration, since approximately 6.6% of the Commission's service
area is served by combined sewers.  Throughout this three year study,
improved SOP removals in both plants were usually observed during
such periods of continuous rainfall similar to the data shown in
period IV.
                                   29

-------
                     EFFECT OF BREWERY WASTE LOAD
          The effect of the industrial wastewater from the brewery in-
dustries in Milwaukee on the activated sludge plants operations were
studied in 1969 when they were shut down due to a strike lasting from
June 9 to July 15.  The loss of the brewery industrial wastewater and
the changes in sewage treatment plant operations made to offset the
effects of this loss offered an excellent opportunity for another plant
scale loading study (F/M and TP/M) in the East and West plants.

          One of the significant effects of this industrial waste loss
was a substantial reduction in the average sewage BOD when compared to
the periods prior to and after the shutdown period as shown in Table U.
The data indicated that the Milwaukee breweries average BOD contri-
bution comprised approximately 22% of the normal total BOD load.  The
BOD removal efficiencies for both plants *rere not affected; however,
they continued to exhibit greater than 90% BOD removals.

           It was  also  observed in a previous breweries  shutdown in
1953 that  the  sewage BOD was  substantially lower.  During this previous
period  of  low BOD the  Milorganite nitrogen content decreased to an
average of 5.31J&  from  a normal value  of  6.0%.  During the 1969 shut-
down, the  plant operations  were modified to  reduce nitrification by
decreasing the MLSS level,  decreasing the detention  time and decreas-
ing the air applied in both plants.   These plant operational changes
were successful during the  19^9 brewery  shutdown, as evidenced by the
small decrease in the  average Milorganite nitrogen content, 5.75$ N
vs normal  of 6,0% N.

           During  the 1969 strike period  however, the TP removal effi-
ciencies for both plants dropped from a  monthly average of B5% to 63%.
This decrease  in  TP removal efficiency was due to a  significant
reduction in the  SOP removal  efficiency  from a monthly  average of B0%
to an  average  of  12.55? and  0.2% in the East  and West plants respect-
ively  as shown in Table U.  The decreased SOP removal was apparently
influenced by  an  increase in  F/M, an  increase in TP/M and a decrease
in the MLSS levels, these are shown in Tables U and  5.  After  the
breweries resumed their normal production and the sewage treatment
plant  returned to their normal operating parameters, the SOP removal
efficiency for both plants  improved tremendously.

           During  this  long  period of  continuously poor  removal of
soluble phosphorus  from sewage, one could expect to  observe the RSSS
phosphorus content  to  decrease.   In Figure  5 are plotted  the nitrogen
and phosphorus contents of RS based on VSS  (from the weekly composites
for EP and WP return sludges).  The data in Figure  5 shows  that the
RSVSS  phosphorus  did not  decrease  during this period of poor soluble
phosphorus removal.  Therefore, it may be  assumed that  a  portion  of
                                 30

-------
                                              TABLE U

                                      SUMMARY PERIOD AVERAGES
Period
April, 1969      May, 1969       Breweries Shutdown      August, 1969
                                 June 9th - July 15th
Plant
% Sewage
% Return
SEWAGE
SOP
TSP
TP
BOD
SS
FLOW
EFFLUENT
SOP
TSP
TP
BOD
SS

Distribution
Sludge

MG/L-P
MG/L-P
MG/L-P
MG/L
MG/L
MOD

MG/L-P
MG/L-P
MG/L-P
MG/L
MG/L
East
56
21*

2,1
3.3
7.8
230
210
109. 1*

0.31
0.51*
0.70
9.9
11
West
1*1*
26






85.0

0.32
0.5l*
0.96
13.2
18
East
60
23

2.0
3.1
7.7
238
238
112.1

0.27
0.1*8
0.79
17.5
19
West
1*0
27






7»». 9

0.26
0.1*7
0.90
15.2
31
East
58
22

2.1
3.6
7.1
182
196
110.9

1.9
2.1
2.1*
10.5
12.6
West
1*2
26






79

2.
2.
2.
12.
16.







.9

1
3
7
0
5
East
59
2»*

2.3
2.8
7.3
221
218
115.6

0.50
0.60
0.93
9.U
15
West
1*1
26






81

0.
0.
1.
12.
28








.5

1*1
53
2
9

PROCESS PARAMETER
F/M
TP/M
MLSS         MG/L
DO           MG/L
DETENTION    HOURS
AIR CU.FT./GAL

% REMOVAL
SOP
TSP
TP
0.352
0.012
2880
3.2
6.7
1.08
0.366
0.012
2970

6.3
1.21*
0.381*
0.012
2700
1.7
6.5
1.10
0.350
0.011
2770

6.9
1.32
0.1*76
0.019
1850
3.6
6.2
0.99
0.529
0.021
1870

5.3
1.10
0.1*35
O.Oll*
2390
U.9
6.1
1.09
0.389
0.013
2590

6.2
1.25
86
8U
91
8U
83
87
87
85
90
87
85
12.5
 1*0
 65
0.2
35
62
79
80
87
81
82
81*

-------
                             TABLE  5


                COMPARISON OF PERIOD AVERAGES;

            LOADING STUDY VS. BREWERIES SHUTDOWN
Period
1969
Plant
% Sewage Distribution
% Return Sludge
SEWAGE
SOP MG/L-P
TSP MG/L-P
TP MG/L-P
BOD MG/L
SS MG/L
FLOW MGD
Loading
Study
Feb. 17th - Mar. 10th
East
50
35

2.7
U.2
9.7
260
253
88.1
West
50
25






86.1
                                                 Breweries  Shutdown
                                                 June 9th - July 15th
EFFLUENT
SOP
TSP
TP
BOD
SS
MG/L-P
MG/L-P
MG/L-P
MG/L
MG/L
1.1
l.U
1.9
17.0
23
PROCESS PARAMETER
  F/M                 0.291
  TP/M                0.011
  MLSS      MG/L      2950
  DO        MG/L      3.1
DETENTION HRS.        7.9
AIR CU.FT./GAL        1.53

% REMOVAL
  SOP                  59
  TSP                  67
  TP                   80
                                    1.8
                                    2.1
                                    2.9
                                   21.0
                                   26
0.511*
0.019
2270

6.2
1.26
 33
 50
 70
                                                 East
                                                 58
                                                 22
                                                  2.1
                                                  3.6
                                                  7.1
                                                  182
                                                  196
                                                110.9
               1.9
               2.1
               2.1*
              10.5
              12.6
12.5
UO
65
                        West
                        U2
                        26
                           79.9
               2.1
               2.3
               2.7
              12.0
              16.5
O.U76
0.019
1850
3.6
6.2
0.99
0.529
0.021
1870

5.3
1.10
 0.2
35
62
                               32

-------
• i
i j
                                                   SHUTDOWN
IN   OPERATION
OPERATION
            % NITROGEN  BASED  ON  RSVSS
            % PHOSPHORUS  BASED ON RSVSS
       3.0
       2.0
            4/13  4/20 4/27 5/45/M  5/18  5/25  6/1   6/8  6/15 6/22 6/29  7/6   7/13 7/20 7/27 8/3  8/10 8/17
       FIGURE 5 EFFECT OF  BREWERIES  SHUTDOWN  ON  R S  COMPOSITION
                                  (WEEKLY  COMPOSITES)

-------
the sewage insoluble phosphorus vas made available for assimilation
by the microorganisms either in the initial aeration period vith MLSS
or in the subsequent recycling vith the RS.

          In the Milwaukee vaste treatment plants the solids synthe-
sized from the sewage BOD, suspended solids, and phosphorus are
continuously removed from the system as Milorganite.  During the
breweries shutdown Milorganite production dropped significantly as
shown in Table 6.  Weekly balances are presented because it was
difficult to calculate a reliable estimate for solids detention or
withdrawal from the two plants on a day to day basis.  The weekly
pounds applied of sewage BOD and VSS also declined for the same
period as shown in Table 6.  The Milorganite phosphorus content did
not appear to change significantly before, during, or after the
shutdown as shown in Table 6.  Phosphorus balance data showed that,
on a weekly basis, the phosphorus removed from sewage was recovered
in the waste solids withdrawn from the system as Milorganite.  It
appears that the reduction in phosphorus removal observed during
the breweries shutdown was due to insufficient synthesis of solids
for the quantity of phosphorus present in the sewage.  In the
Milwaukee plants the amount (and/or efficiency) of phosphorus
removed from sewage appears to be influenced more by the amount of
solids produced in the activated sludge process than by the
activated sludge process parameters studied.  In addition, it
appears that the brewery waste water aids soluble phosphorus re-
moval at the Milwaukee plants.
                               34

-------
                       TABLE 6 RELATION  OF  PHOSPHORUS  REMOVED TO  SOLIDS  SYNTHESIS
                                            (1969  WEEKLY   DATA)
SOLIDS PRODUCED (DRY BASIS)*
WEEK

3-30
U-6
U-13
1*-20
U-27
5-U
5-11
5-18
5-25
6-1
6-8 '
6-15
6-22
6-29
7-6
7-n
7-20
7-27
8-3
8-10
8-17
8-2U
OF
to
11
ti
it
it
ii
it
it
it
it
—TT
it
11
it
ii
it
—IT
II
It
II
II
ti

l*-5
lt-12
1*-19
l*-26
5-3
5-10
5-17
5-21*
5-31
6-7
6-lU
6-21
6-28
7-5
7-12
7-19
7-26
8-2
8-9
8-16
8-23
8-30
TONS
WEEK
1376
1682
1650
183U
1655
1537
13W
1656
161*0
lll*8»*
15U7***
1309
1076
8Ul
1026
1171
lU7
11*1*6
1509
1678
151*5
151*9
%
P
TONS

PHOSPHORUS
2.
2.
2.
2.
2.
2.
2.
2.
2.
?.
2.
2.
2.
2.
2.
?.
2.
2.
2.
2.
2.
2.
25
26
27
18
23
30
3»4
28
30
35
57
59
38
19
30
30
17
33
U3
5H
53
63
31.
38.
37.
1*0.
36.
35.
31.
37.
37.
27-
39.
33.
25.
18.
23.
26.
31.
33.
36.
U2.
39.
UO.
0
1
5
0
9
1*
5
8
7
0
8
9
6
)*
6
9
5*
7
7
6
1
7
TONS APPLIED/WEEK
(BOTH
PLANTS)
PHOSPHORUS BOD
M*. 8
1*7.0
1*1.3
1*1*. 8
1*2.8
1*2.5
1*1*. 5
1*2.1*
UO.U
1*1.3
U3.7
1*1*. 0
37.6
30.5
37.9
39.3
-
35.1
Uo.i*
1*1*. 8
1*1*. 3
Ul.9
1292
ll*51
1061*
ll*07
1358
1335
13U9
1218
1298
1189
1098
1139
1011*
829
957
1013
1251
1260
1167
1389
1190
ll*23
vss
ll*ll
ll*91
1293
131*6
1321*
ll*56
1503
903
963
9^2
917
960
8U8
659
775
772
9W
937
551+
1093
1053
1091
BREWERIES
OPERATION



IN
OPERATION







SHUTDOWN





IN
OPERATION


NOTE    *Milorganite production adjusted to account for either solids detention or
         withdrawal from the system.

       **Abnoraally low Milorganite production due to a holiday and the dewatering
         facilities shut down for two and a half days.

      ***High Milorganite production because the MLSS levels in the system were
         reduced from a weekly average of 2800 riR/L to the low level of
         2000 mg/L (i 1*00) for the East Plant.

-------
                 PLANT SCALE PHOSPHORUS BALANCES
          The phosphorus balances shown in Table 7 were made to check
the accuracy of phosphorus and plant flov data obtained in this project.
The influent and effluent TP contents were determined by a Ternary Acid
Digestion procedure (as described in Appendix A).  The Milorganite
phosphorus content was determined by the gravimetric AOAC Quinoline
Molybdate Method 2.023 and 2.021* (36).

          Phosphorus recovered in the Milorganite was compared with that
removed from the influent by the two plants.  The initial phosphorus
balance calculations were made with the daily data but it was found too
difficult to accurately account for phosphorus associated with the solids
in the system.  The phosphorus balances using weekly phosphorus removals,
plant flows, and Milorganite production data were considered more real-
istic.  The estimated solids storage in the system on a weekly basis
usually exhibited less fluctuation than on a daily basis.

          An average of 95.7/S of the phosphorus removed by both plants
could be accounted for in the Milorganite produced over the 37 week
period.  As evidenced by the weekly phosphorus balances as shown in
the Table 7, plant phosphorus and flow data were reasonably accurate.

          The phosphorus balances for both plants established the
high phosphorus removals by the Milwaukee Sewage treatment plants and
demonstrated that the phosphorus was removed from the process as
Milorganite produced from waste sludge.

-------
                              TABLE  7
              CALCULATED WEEKLY PHOSPHORUS RECOVERIES
                      #TP Removed/Week in 1969
Weekly
Period
Feb. 10-16
17-23
21+-2
Mar. 3-9
10-16
17-23
21+-30
31-6
Apr. 7-13
11+-20
21-27
28-1*
May 5-11
12-18
19-25
26-1
June 2-8
9-15
16-22
23-29
30-6
July 7-13
11+-20
21-27
27-2
Aug. 3-9
10-16
17-23
2U-30
31-6
Sept. 7-13
lU-20
21-27
28-1+
Oct. 5-11
12-18
19-25
26-1
Nov. 2-8
9-15
16-22
23-29
Average %
WP

29,81+0
38,559
37,355
32,113
32.91U
28,571+
31+, 805
31*, 851
33,960
36,021+
30,261
33,297
30,33**
29,696
31,257
29,851
22,135
36,266
2l+,8l9
18,120
17,325
16.1U2
21,1+71+
_
21,762
29,779
3U.007
30,575
23,81*5
17,906
21+.1+21
22,690
26,993
9,1*79
10,551*
30,682
37,657
30,508
33,277
31*, 707
35,758
28,857
Recovery
EP

1*0,026
32,206
1*9,009
37,828
1*1,058
1*5,337
U, 857
Ul+,903
J+l+,1+52
1*6,81*1
1*5,568
1*6,195
1*3,771
1*5,568
1*5,971*
1*6,1+22
38,708
149,028
1*1,953
30,653
22,268
21,U67
31,392
_
3U ,216
1*0,796
U5.022
1*8,187
1*3,1*96
29,777
1+3,529
37,858
1+2,01+1
1*6,953
38,166
1*6,181
59,887
1+1+ , 977
1+9,807
1*9,251
1*8,1*12
1*1,398

Both Milorganite
Plants
69,866
70,765
86,361*
69,91*1
73,972
73,911
79,662
79,751*
78,1*12
82,865
75,829
79,1*92
71+.105
75,261+
77,231
76,273
60,81+3
85,291*
66,772
1*8,773
39,593
37,609
52,866
-
55,978
70,075
79,029
78,762
67,31*1
1*7,683
67,950
6o,5l+8
69,031*
56,1*32
1+8,720
76,863
97,5U1*
75,1*85
83,081+
83,958
81*. 170
70,255


69,388
69,056
72,338
66,709
66,1+39
69,572
67,910
65,582
71,610
78,71+1*
7!*, 802
70,800
69 ,986
68,1*59
69,51*1*
77,982
1*8,1+1+5
86,939
72,105
52,837
1+0,795
36,681
1*6,336
-
63,760
69,29!*
7U.771
75,871*
71*. 090
51,729
6U, 1*97
57,753
6U, 691
58,232
56,726
61+, 1+00
70,896
67,691
78,371
76,175
71,562
61+, 377

                                                            Phosphorus
                                                            Recovery
                                                                .3
                                                                .6
                                            99.
                                            97.
                                            83.8
                                            95.1+
                                            89.8
                                            9l*.l
                                               ,2
                                               ,2
                                               ,3
                                                              85
                                                              82
                                                              91
                                                                .0
                                                                .2
                                            95.0
                                            98.6
                                            89.1
                                            9U.U
                                            91.0
                                            90.
                                            102.
                                            T9.6
                                            101.9
                                            108.0
                                            108.3
                                            103.0
                                             97.5
                                             87.6

                                            113.9
                                                               95.7
(»)  ^Recovery
(#TP removed in Milorganite-f-#TP removed in
the plant) X 100
                                      37

-------
RELATIONSHIP BETWEEN TOTAL BOD REMOVAL AND TSP REMOVAL IN AN
ACTIVATED SLUDGE PLANT (BODR/TSPR)


             Sawyer (20) studied the removal of BOD in conjunction
vith soluble phosphorus removal by the activated sludge process.
He demonstrated in the laboratory, that by adding additional BOD
(as glucose) he could obtain increased soluble phosphorus removal.
From this work he concluded that 100 pounds of BOD were removed for
each pound of soluble phosphorus in the activated sludge process.
Hall and Engelbrecht (22) concluded from their studies that 80 to
110 pounds of COD were removed per pound of soluble phosphorus.
It was decided to determine how applicable this concept was on a
plant scale*

             The BOD to TSP removal ratios (i.e., BODj^/TSPp) for
both plants were calculated from the daily 2U hour sewage and
effluents composites data.  The calculated removal ratios from
2/9/69 to 11/30/69 are presented as frequency diagrams in Figures
number 6 and 7.  The data used in these diagrams are for periods
of normal operating conditions.

             The magnitude of the BODR/TSPR ratio appears to be
dependent on the day of the week as shown  in Table 8.

                              TABLE   8

                       Average BODp/TSPR Ratios

     Plant               Weekdays              Weekend Days

                    Monday thru Friday    Saturday   Sunday

  West Plant                86                60        kk

  East Plant                90                6U        50

The  data appears to indicate that in  the Milwaukee activated
sludge plants  the  removal of soluble  phosphorus from sewage is
not  dependent  on the removal of total BOD  as we always observed
greater than 90% BOD removals.
                               38

-------
vo
            24



            20



            16



            12
          UJ 8
          O
          Z
          UJ 4
          (K
          O
            0
            V
0 32



> 28

2
^ 24

O
UJ .

u.

  16



  12



  8


  4
        WEST  PLANT DATA
                                      AVERAGE  86LBS  BODR/LB.  TSPR
                           r-m
                  EAST PLANT  DATA
                       1
                                                  -AVERAGE 90LBS BODR/LB TSPR
                                             r
                                                             -t-
                                                                              -I-
               6  10  20  30  40  50 60  70  80 90  100 110  120  130 140  150  160 170  180  I9O 200
               9  19  29  39  49  59 69  79  89 99  109 119  129  139 149  159  169 179  189  199 209
                           POUNDS   BOD REMOVED/POUND  TSP  REMOVED

              FIGURE 6   FREQUENCY  DISTRIBUTION  BODR/TSPR  WEEKDAY  DATA

-------
8 •
6 •
4 •
2 •
6 •
A
IRRENCE
3 l\5 4
^ w
O
o
o
Q .
u. B
o
6
O
5 4
O o-
Ul 2
QC
8
6
4
2
SATURDAYS
WEST PLANT





EAST PLANT
1

I 	
SUNDAYS
WEST PLANT
x


If
1
EAST PLANT

0
9



10 20 30 40
19 29 39 49




AVER/
r~



N
^AVERAGE 60


I , ,
1 1

!*•: . 	 AVLRAGt 64
1
1
1
\GE 44
I 1 1
""-•—- AVERAGE 50

1 1
50 60 70 80 90 100 110 120 130
59 69 79 89 99 109 119 129 139
          POUNDS BOD REMOVED/POUND TSP REMOVED
FREQUENCY DISTRIBUTION BODR/TSFk WEEKEND DATA
                FIGURE  7
                         40

-------
STUDY OF SOLUBLE PHOSPHORUS UPTAKE IN EAST PLANT AERATION TANKS
(GENERAL)

             Eight separate studies were made during the course of tvo
years on soluble phosphorus uptake in the aeration tanks.  The ML de-
tention time and air application rates were kept fairly constant at 6
hours and 3300 to 3500 cfm respectively.  No attempt was made to control
the MLSS levels and the F/M and TP/M loadings.  Thus, they were the
varying parameters which affected the ML-DO level and phosphorus re-
moval efficiencies.

             ML Spot samples  (over a six hour period) were taken at
each hour along the aeration  tank and "brought immediately to the labora-
tory and filtered.  At the location from which the ML samples were taken
the ML-DO was also measured.   The ML filtrates were analyzed for SOP
and/or TSP,  soluble BOD, and  pH.  The SS were also determined on the ML
samples.  In addition, the zero hour detention grab samples of screened
sewage and RS samples were analyzed for SOP or TSP.

             The  data  from the majority of these  studies were incon-
clusive because the  studies were  conducted on influent  arriving at 8
to 9 AM when the  influent  BOD, TP and SOP  concentrations were near
their lowest average concentration in the  twenty  four hour period
(see Figure  2).   As  a  result, practically  no  dramatic differences  in
effluent residual SOP  were observed which  could be  related to the  pro-
cess parameters under  investigation.

              It was  consistently observed in these  studies,  that  the
SOP  concentration of ML resulting from the mixing of screened sewage
and  RS  in  the  mixing and ML feed channel as  well as at  zero  hour
aeration time  in  the aeration tanks was usually 2 to 3  times greater
than the expected calculated SOP concentration in a corresponding
mixture of sewage and RS.   Also, at times the concentration  of ML-SOP
was  greater than  the sewage TP.   It is unlikely that all the sewage
 insoluble  phosphorus could be instantly converted to SOP when sewage
 is mixed with RS.  Also, it is well known and easily demonstrated
 that the RSSS readily release SOP under anaerobic conditions.  The
 RS was  therefore  considered as the logical source for the SOP in-
 crease  in the ML.

              Sewage and effluent samples were also analyzed for SOP
 and TSP in several studies.  The difference between TSP concentration
 and SOP concentration in the  sewage was consistently greater than
 1 mg/L-P.   In the aeration tank effluent, however, as well as in
 the plant effluents, the difference between TSP  concentration and SOP
 concentration was consistently only 0.2 - O.H mg/L-P.  This indicated,
 that in the activated sludge  process the MLSS rapidly  degrade or
 remove and retain soluble poly-and organic-phosphorus  compounds.
                                41

-------
EFFECT OF MLSS-Og UPTAKE RATES AND AIR APPLICATION RATES ON SOLUBLE
PHOSPHORUS UPTAKE IN AN AERATION TANK.


             In the activated sludge process the aerobic microorgan-
isms require C, P, N, etc., from sewage in order to maintain their
metabolic and reproduction activity.  The amount of dissolved oxygen
in the ML is dependent on the air application rate, the oxygen trans-
fer efficiency of the aeration devices employed, and the oxygen
demand rate of the microorganisms.  The aerobic microorganisms in the
ML also require sufficient amounts of dissolved oxygen for these
activities.

             Numerous reports in the literature have shown that the
ML dissolved oxygen level is a significant activated sludge process
parameter affecting soluble phosphorus removal (2,3,5,22). Accord-
ingly, the effect of air application rate was evaluated using three
tanks of the East Plant.  This experiment was not performed on a
plant scale because the MLSS level and plant loadings could not be
controlled from day to day.

             Oxygen utilization rate measurements have been frequently
used to assess the metabolic activity or proportion of viably active
cells in MLSS.  In the literature no information was discovered on the
relation of MLSS-02 uptake rate to ML-soluble phosphorus  levels.  The
establishment of such a relationship would provide a means to assess
the MLSS capability to remove  soluble phosphorus  in the  activated
sludge process.

             Preliminary DO-profile  studies  of aeration  tanks resulted
in the  selection of tanks  8,  9,  and 11  of the  East Plant  for this
study because these tanks  had similar air distribution patterns
 (Figure 8).  The ML flows  to  the three  tanks were maintained at 7.5
mgd each with  3C# RS to provide  6 hours detention time  in each tank.
The experiments were started  at  2 PM when the  ML oxygen  demand rate
 due to high sewage BOD was usually at its peak.   The  air application
 rates tested during this  four day study were as  follows  in Table  9.

                              TABLE 9

                       AIR APPLICATION RATES

    Tank No.   CFM     Cu.  ft./gal sewage

       8      2300            0.57              33% below normal

       9      3500            0.86              Normal Rate

      10      U700            1.16              33% above normal
                                42

-------
i
1
         5.0
         4.0
         3.0
      o
         2.0
         1.0
              TANK 8

              TANK 9
              AIR
CFM

CFM
              TANK II -- AIR 3500 CFM
  0 I  23456789 10 I  234 15 6789

INLET

                          HEADER
                                                   19 8 7 6 5 ,4 3 2 I 10 9  8 7 6 5 4  3



                                                   NUMBER
        FIGURE  8  AERATION TANKS  DO PROFILES      ( 9-30-1969, 8:00 A.M. )

-------
             The changes observed in the tank DO-profiles resulting
from these air application rates are shown in Figure 9.  The difference
in the DO-profiles given in Figure 8 and Figure 9 is partly due to the
different BOD loadings on these tanks when the DO-profile data was
taken.  At the start of each daily run, the 1 PM to 2 PM hourly
composite of screened sewage was taken to the laboratory for BOD, SS,
TP and TSP analyses.  In addition a 7 liter grab sample of EPRS was
taken at the same time and analyzed for SS and TSP.  At 2 PM (zero
detention time) ML-DO readings and a 7 liter grab sample of ML was
taken at the inlet  of each tank.  The ML samples were immediately
filtered and analyzed for TSP and soluble BOD.  A portion of the un-
filtered ML sample from each tank was analyzedfor SS^jHancl MLSS-02
uptake rate.  This procedure was repeated every hour at sampling
locations along the aeration tanks based on the detention time to
follow the plug flow of ML through the aeration tank.

             The ML final pH levels did not change significantly due
to the changes in air application rates as shown below in Table 10.

                               TABLE 10

               Effect of Air Application Rate on ML pH

               Air Rate             Average ML pH

               eu.ft./gal      Initial

                  0.57            7.^0

                  0.86            7.**0

                  1.16            7.^1

             The process parameter  data for these  runs as presented
 in Table 11  are based on 6 hours  detention, 115.5 mgd  sewage flow,
 30?  RS,  and  a MLVSS content of 68.92.  The data, listed  in Table 11,
 showed that  in an aeration tank  at  a given time the air  application
 rate of  0.57 cu.  ft./gal of sewage  was inadequate  for  good phosphorus
 removal.   However, an aeration rate of 0.86 cu. ft./gal  of sewage or
 greater  exhibited significantly  improved phosphorus removals as
 indicated by the  low TSP residuals  in the aeration tank  effluent.

             The  hourly data  from the  four runs showed little  vari-
 tion.  As a  result, the daily data  was averaged and plotted  in
 Figures  10,  11, 12, and 13.   Figure 10 indicates,  that to maintain
 a DO of  at least  2.0 mg/L  in  the aeration tank beyond  the turnpoint,
 an air application  rate of at least 0.86 cu.  ft./gal.  was required.
                               44

-------
o
o
ci
  8.0
  6.0
  4.0
  2.0
        TANK 8--
        TANK 9 -
        TANK II —
 AIR 2300 CFM
•AIR 3600 CFM
•AIR 4800 CFM
    01  23456789 10 I 23456789 20 I TP 10 19
   INLET                                TURN POINT
                               HEADER         NUMBER
                                7654321 10 98765432  I
                                                          OUTLET
FIGURE  9   AERATION  TANKS  D.O. PROFILES     (10-6-1969, 12:30RM. )

-------
Date
                                     TABLE   11



            DAILY PROCESS PARAMETER DATA (Detention time controlled to 6 hours)



                                                                        At Tank Outlet
Aeration



  Tank
10-6
Mon.

10-7
Tues

10-8
Wed.

10-9
Thurs.

8
9
11
8
9
11
8
9
11
8
9
11
F/M
                     0.517
                     0.635
TP/M
                      0.03^9
                               0.0196
                       0.0215
                                0.0159
MLSS
mg/L


2530


2610


2770


2910


Air
cu. ft. /gal.


0.57
0.86
1.16
0.57
0.86
1.16
0.57
0.86
1.16
0.57
0.86
1.16
ML-DO
mg/L


1.0
6.0
7.8
«
«
*
0.5
1.2
3.5
0.5
1.0
2.5
ML-TSP
mg/L-P


6.U
0.3H
0.28
lU.U
0.2U
0.18
11.5
0.20
0.16
9.7
0.2U
0.2U
ML
Soluble
BOD
mg/1
9.U
U.U
k.k
1U.U
5.U
U.2
15. U
5.6
5.8
1^.0
6.2
5.U
           * D. 0. meter inoperative

-------
      A  2300 C.FM. AVE.  4 RUNS
      O  3500  <•   "   4  "
      X  3600  "   "   6  "
      •  4700  »   »   4
O
I
_J
v.
O
O
O
         1234
              DETENTION   HOURS
FIGURE 10  EFFECT OF AIR APPLICATION
         RATE  ON  ML-DO LEVEL
                       47

-------
   60
 cc
 CO
 CO
   50
A   2300 CFM AVE. 4 RUNS
O   3500  "   »  4  ii
X   3600  ••   ••  6
•   4700  n   i.  4  .,
                2      3
                DETENTION
                     4
                  HOURS
FIGURE 11  EFFECT OF AIR  APPLICATION RATE
     ON  MLSS-02   UPTAKE  RATE
                      48

-------
  20
     A 2300 CFM AVE. 4 RUNS
     O 3500  "   "  4  "
     X 3600  "   "  6
     • 4700  "   "  4  "
               234
               DETENTION   HOURS
FIGURE 12 EFFECT OF AIR  APPLICATION RATE
            ON  ML-TSP LEVEL
                      49

-------
o
Q

O
03

LJ
_l
CO
            2300 CFM AVE 4 RUNS

            3500  "   ii  4  'i

            3600  "   ii  6  '•

            4700  »   »  4  "
          1234

               DETENTION  HOURS


FIGURE 13 EFFECT  OF AIR APPLICATION RATE

       ON ML-SOLUBLE BOD LEVEL
                      50

-------
             Aa plotted in Figure 11, MLSS-Og uptake rates observed in
this study at 0-hour detention time in the aeration tank vere about
half of the values reported by Eckenfelder (37).  This may be due to
approximately 20 minutes aeration of the ML in the long feed channels
prior to entrance of the ML into the aeration tanks.

                               TABLE 12

               MLSS-02 UPTAKE RATE AFTER 6 HOURS AERATION

AIR APPLICATION RATES               mg 02/gm VSS/hr.
  CFM  cu. ft./GAL.

  2300       0.5T

  3500       0.86

  UJOO       1.16
The  above  values  in Table 12 compare favorably with  those reported by
Okum and Lynn (38)  of 22 to 28 mg 02/gm VSS/hr.   At  no  time vere the
endogeneous  oxygen  uptake rates of 1.9 to 9.8 mg 02/hr/1000 mg  sludge
as reported  by Eckenfelder (37) observed.  An examination of Figures
12 and 13  indicates that an aeration rate of 0.57 cu.ft./gal. of
sevage was insufficient for soluble phosphorus  removal  but did  not
affect the BOD removals.
AVERAGE
(H RUNS)
32. U
25.1
23.8
RANGE
LOW
28.9
22.3
19.5

HIGH
36.0
27.1
26.1
                                  51

-------
EVALUATION OF MLSS METABOLIC ACTIVITY BY GLUCOSE DEHYDROGENASE ASSAY

               Observations of the daily process parameters data
indicated that they are sufficient to explain why poor or good
soluble phosphorus removal occurs in the Milwaukee activated sludge
plants.  Ford, Young and Eckenfelder, (39) investigated the use of a
glucose dehydrogenase assay for evaluating the biological activity of
sludges.  It was then thought that if the removal of soluble phospho-
rus in the activated sludge process could be related to the biological
activity of the MLSS, this additional information could probably
explain the observed deviations.

               In an aeration tank, the oxygen uptake rate of the
MLSS decreases with increasing detention and air application rate
(Refer to Figure 11).  Thus, the metabolic or oxidative activity as
represented by the MLSS-glucose dehydrogenase activity could be ex-
pected to decrease from the tank inlet to the tank outlet and perhaps
coincide with the SOP being removed by the MLSS.

               The data of Ford, et. al. (39) showed that the MLSS-
glucose dehydrogenase activity within a sampling location exhibited
a very large coefficient of variation (C.V.).  They performed one
hundred triplicate analyses on samples from three sampling locations
and obtained C.V.'s of 31.6#, 2U.5JJ and 23.85? respectively.

               For this study to be worthwhile it was necessary to
determine whether the large variation in MLSS-glucose dehydrogenase
activity reported by Ford was caused by the assay itself or was
caused by the samples that were taken from a specific sampling site.
In this study, seven liter ML samples taken from the inlet, turn-
point and outlet of an aeration tank were each analyzed in triplicates
for MLSS and MLVSS (Appendix B) and glucose dehydrogenase activity.

               The standard deviation of the dehydrogenase assay was
calculated from the grand average range of the range of triplicate
analyses per sample (19 samples from each of three sampling sites)
according to the procedure given by Natrella (^0).  The values
used in this calculation were the range of triplicate determinations
per sample as shown in Table 13.
                            52

-------
                              TABLE 13

                 DEHYDROGENASE ASSAY VARIABILITY

                      ( jiM TPF/5 ml of ML)

   SAMPLING       RANGE OF TRIPLICATES              STANDARD

     SITE           AVERAGE  HIGH  LOW              DEVIATION

   INLET              .032    .072  .013               .0189
   TURNPOINT          .OU9    .097  .000               .0289
   OUTLET             .050    .18U  .000               .0295

The actual value from the assay used in calculating MLSS-glucose
dehydrogenase activity for each sample was the average of the
triplicate analyses for each sample.  These values exhibited
wide variations for the ML samples analyzed as shown in Table lU.


                            TABLE lU

                   DEHYDROGENASE ASSAY DATA

                         TPF/5 ml of ML)
   Sampling         Average                   Range
     Site                                  High    Low

   INLET              0.822                 1.150   O.U15
   TURNPOINT          0.762                 1.0U3   0.285
   OUTLET             0.729                 1.051   0.212

The comparison of  data in Tables  13 and lU indicated  that the
reproducibility  of the assay was  fairly good and  that the vide
variations in MLSS-glucose  dehydrogenase activity was due to
the samples which  were taken within a sampling site for analyses.
                             53

-------
         The variability of the MLSS-dehydrogenase activity according
to sample sources (same 19 runs) vas also determined as shown in
Table 15.  The MLSS-dehydrogenase activity vas expressed as juM TPF/mg
MLVSS (jiM Triphenylformazin produced/mg MLVSS).

                               TABLE 15
      VARIABILITY OF ML - DEHYDROGENASE ACTIVITY AMD MLVSS

                  AT DIFFERENT SAMPLE LOCATIONS
Aeration Tank ML-Dehydrogenase Activity
                                 MLSS
                      MLVSS
   Sample
Location
Inlet
Turnpoint
Outlet
Average
    Average
uM TPF/mg MLVSS
     0.072
     0.068
     0.063
Standard
Deviation
0.01^9
0.0130
O.OlUl

%
CV
20.
19.
22.
20.


7
1
U
7
Ave.
mg/1
3030
3160
3130

Ave.
?VSS
75.2
7^.3
73.9

Std.
Dev.
0.89
0.89
0.79

i
CV
1.18
1.20
1.07
1.15
     Std. Dev. at Standard Deviation

The above data continued to show that the large variation in the
glucose dehydrogenase activity within a sampling site was due to the
variation from sample to sample.  The CV of the MLSS-glucose
dehydrogenase activity at different sample locations conform to those
reported by Ford as shown in Table 16.
                            TABLE 16

        COMPARISON OF COEFFICIENTS OF VARIATION (C.V.)
Milwaukee Data

Sample Location         % C.V,
Aeration Tank Inlet     20.7/5
Aeration Tank Turnpoint 19.1?
Aeration Tank Outlet    22.U?
Average
          20.7?
Ford's Data

Sample Location       ? C.V.
Contract Tank         31.6?
Stabilization Tank
(Sampling Point A*)   2U.5?
Stabilization Tank
(Sampling Point B«)   23.8?
•Sampling Location Not (39)
 Specified in Reference
         The usage of the glucose dehydrogenase assay to evaluate
the metabolic or oxidative activity of the MLSS in an activated
sludge plant was found to be of little practical value as a large
number of samples would have to be analyzed to provide significant
                                54

-------
data.  It should be noted that the data on the average did show that
the MLSS-glucose dehydrogenase activity decreases with increasing
detention time,  (see Table 15).

         Jones and Prasad (Ul) made a detailed study on the use of
tetrazolium salts as a measure of sludge activity.  They concluded
that, "The TTC dehydrogenase test in mixed cultures and complex
substrates at best can be considered as a gross measurement of
activity.  The interpretation of the data should be approached with
caution particularly if it is being used as a research tool."
                              55

-------
X-RAY DIFFRACTION STUDIES OF SEWAGE SUSPENDED SOLIDS AND WASTE SLUDGE
SOLIDS

         In the literature, the removal of sewage phosphorus by the
activated sludge process has been attributed to cationic precipi-
tation or biological uptake, or a combination of both.  Therefore, a
knowledge of the mechanism or mechanisms prevailing vould not only
enable us to obtain a better understanding of the phosphorus removal
process but also to develop concepts for the improvement of phosphorus
removal in the activated sludge system.  Many cations (iron, aluminum,
calcium and magnesium) have been successfully added to aeration units
by many investigators to enhance the removal of soluble phosphorus.
If a qualitative and quantitative procedure to determine the presence
of these inorganic phosphate compounds in sewage suspended solids and
vaste sludge solids were available, the mechanism of phosphorus re-
moval by the activated sludge process could be better explained.

         Accordingly, staff members of Marquette University, Milwaukee
were consulted on the use of X-Ray diffraction analysis to determine
if these inorganic phosphate compounds were present in the sewage
suspended solids and waste sludge solids.

         The preliminary X-Ray diffraction studies  (U2, U3, UU) re-
vealed that a crystal-like compound in the 103°C oven dried RS gave
an X-Ray diffraction pattern very similar to that of Iron  (ill)
orthophosphate  (FePOjj).  This observation could not be confirmed and
studied further because of the appearance of too many background lines
in the X-Ray diffraction patterns obtained in the subsequent studies
due to amorphous material in the sludge.  The sludge samples were
then heated at different temperatures to see if the background dark-
ness could be decreased.  Heat treatment of the samples  (500°C to
600°C) decreased the background darkening considerably, but this high
temperature heat treatment changed the nature of the compound formed
and resulted in a homogeneous mass.

         Freeze drying of the sample was tried.  This did  not help
in decreasing the background but did result in a heterogenous mass
containing  some black crystals.  These black crystals were separated
and found to give patterns similar to vivianite, Fe3  (POj^  • 8H20.
Further research will be conducted in an attempt to purify and
evaluate the concentration of these black crystals.  Magnetic
separation  techniques are currently under study and show promise of
success.  These X-Ray studies are being continued under Project
Grant Number 11010,  FLQ, "Phosphorus Removal With Pickle Liquor
In A 115 MOD Activated Sludge Plant".
                                  56

-------
            CATIONIC REMOVAL OF PHOSPHORUS FROM SEWAGE

         A number of investigators have studied the ability of
certain cations (Fe+++, Fe++, Al***, Ca^, and Mg**) to enhance  the
soluble phosphorus removals in the activated sludge process.  Very
little information is available in the literature on the concentrations
of these soluble cations in sewage and their effect on sewage phospho-
rus removal.  Studies were undertaken to assess the role of Fe,  Al,
Ca and Mg ions, normally present in Milwaukee sewage, in the removal
of SOP by the two Milwaukee activated sludge plants.

         Currently, it was assumed that the insoluble cations (i.e.,
the cations present in the sewage suspended solids) are tied up
possibly as Fe(OH)3 and are not available  for reaction with SOP to
form insoluble phosphate compounds during  the activated sludge
process.  A comparison of the  influent and of the effluent soluble
cation concentrations would indicate if these cations were removed in
the activated sludge process.   It was hypothesized that if a decrease
in the soluble cation concentration was observed, this decrease was
due to the formation of an insoluble phosphate  compound through its
reaction with SOP.

         The cation  analyses were performed on  the unneutralized
ternary acid digestate of  2H hour composite samples  of screened
sewage, EP and WP effluents by atomic  absorption.   The initial work
was carried out  using  the  2H hour composite samples  to determine  if
there was a significant  change in the  soluble cations concentrations
on a daily basis during July  of 1969.   The daily data exhibited
marked  fluctuations  because of the  limited experience on  the atomic
absorption unit  by laboratory personnel.   Therefore, only monthly
averages  are presented in Table IT
                               57

-------
                           TABLE 17

      AVERAGE CATION CONCENTRATIONS  (mg/L)  FOR JULY,  1969

  TOTAL CATION CONCENTRATIONS      TOTAL  SOLUBLE  CATION CONCENTRATIONS
            Screened Effluent
Fe  & Fe

Al

Ca
             5.00*   0.71   0.59

             2.00    0.53   0.41

            52.4    48.8  47.9
Screened

 Sewage

  0.55

  0.44

 48.6
                                                          Effluent
WP
0.32
0.33
47.7
EP
0.29
0.27
47.2
Mg++        31.8    30.7  30.2            30.4         30.5    30.3

           ^Partly influenced by filtrate from vacuum filters

        The above data showed that both activated  sludge plants
removed very little of the  soluble cations of Fe,  Al, Ca and Mg.
Based on this data, the removal of SOP in the Milwaukee activated
sludge plants by the  sewage soluble cations would  be very insignifi-
cant   From the above data  one could assume that the cationic fix-
ation of soluble phosphorus probably takes place in the sewage prior
to its reaching the plant.   The consistently low amount of total
soluble iron in Milwaukee sewage  (usualljK 1.0 mg/l-Fe) may be due
to the low solubility of the iron phosphate compound present in the
sewage suspended solids.

        The initial X-Ray diffraction studies on the 103°C dried
sludge samples indicated that one of the insoluble cation phosphate
compounds was possibly FeP04 which in the wet  sludge may be present
as FePOA . 2H00 or FeP04 .  4H20.  The theoretical  solubility product
of FePoZ - 2Hfo is 1  x 10'33 in distilled water according to Chang
and Jackson  (45).  The solubility product of FeP04 • 2H20 in  sewage
was  calculated  from the observed  data and was  found to  average  6.7 x 10
at pH 8.0.  This higher value would be expected  since  sewage  contains
 substances,  such as detergents, polyphosphates,  chelating agents,  salts
and  other  unknown  compounds which could  increase  the solubility of
FePOA .  2H90  in sewage.  The above  assumptions are reasonable  because
 the  calculated  solubility product agreed with  that reported by Galal-
Grochev and  Stumm (46) of 1 x  lO"23 at  a PH greater than 7.0  at 25°C
 for  FeP04.
                               58

-------
         Since the activated sludge process removes polyphosphates,
surfactants, etc., from sewage the solubility product of ferric
phosphate vould be expected to decrease.  The calculated solubility
product of FePOii 4 2H2° in ^ afterp£ nours aeration was found to
decrease to an average of 1.3 x 10~ ' at pH 7«0.
                                 59

-------
EFFECT OF IRON ADDITION TO AN AERATION TANK ON SOLUBLE PHOSPHORUS
REMOVAL

         During June and July of 1969 the TSP and SOP removal
efficiencies for both plants dropped from an average of 80$ to an
average of Uo#.  The period of reduced removals coincided with the
breweries shutdown which was discussed in a previous section.  This
was an opportune time to begin a cationic addition experiment, since
this period of extremely reduced SOP and TSP removals could provide
more reliable and significant data on the cationic removal of soluble
phosphorus.

         This phase of the study was a cooperative venture with the
A. 0. Smith Corporation of Milwaukee, who supplied the cationic com-
pound, ferrous sulfate as waste pickle liquor needed for the addition
of iron to the ML.  The industrial waste used contained from O.U to
1.0 pound of iron per gallon and usually had a pH of about 1.0.
Neutralized and unneutralized pickle liquor were used in this study.

         The initial work was limited to the addition of iron to one
of the aeration tanks of the EP.  This approach was taken to determine
the effective  iron dose, the desired addition site, and the material
handling problems associated with the pickle liquor addition.  We
were  also interested in determining if this waste product would have
any detrimental influence on the activated sludge process or on the
air diffuser plates.

         The waste pickle liquor was first added to the aeration tank
at the turning point, providing 3 hours detention, and then at the
inlet, providing  6 hours detention.  The ML flows to the aeration
tanks were  held at 7.0 to 7«5 mgd to provide about 6 hours detention,
and the air application rate was maintained at approximately 3200 cfm.
The iron was added 2k hours'/day from Monday to Friday and the pickle
liquor addition rate was manually controlled.  This study was conducted
for two periods of three weeks each.  An adjacent aeration tank with
the same ML flow  and aeration pattern was used as a control.  The
experimental and  control tanks ML were sampled at the inlet, turn-
point and outlet  every 2 to 3 hours continuously.  The ML samples
were  analyzed  for total iron, total soluble iron, TP, TSP, MLSS, pH,
and ML-SDI, and ML-DO at the tank outlets.

         The iron dosing rates maintained were approximately 7.5, 15,
and 30 mg/L-Fe based on the hourly ML flow.  The averages of the bi-
hourly and  trihourly data by week are presented in Table 38.  The
data  such as given in Table  18 showed that the addition of ferrous iron
in the form of waste pickle liquor was very effective in the reduction
of ML-TSP.  Actual iron dosing rates of 11.0 to 27.k mg/L-Fe (based on
ML flow) resulted in average ML-TSP residuals between 0.23 to O.U9 mg/
L-P and reduced the inlet ML-TSP levels (3.5 to 8.5 mg/L) by 77.3 to
                               60

-------
                                                       TABLE  18

                                        EFFECT OF IRON DOSAGE ON  ML-TSP LEVEL
Cr>
Run
No
1
2

3

U
5
6
Date Iron Add!
1969 Dosage
mg/L-F
7/1 to 7/3
7/8 to 7/11

7/15


to 7/18

8/U to 8/8
8/11
8/18
to 8/15
to 8/22
11.0
6.8
27. U
30.0
15.0
13.3
15.5
17.0
tion Average ML-T
(1) Site Inlet (2)
'e
TP (U)
TP
TP
(5) past TP (6)
(5) past TP
Inlet
Inlet
Inlet
'SP mg/L-P
Outlet (3)
Exptl. Control
Tank Tank
3.
k.
U.
U.
2.
5.
6.
8.
5
85
65
l
8
U
9
5
0.
1.
0.
0.
0.
0.
0.
0.
U6
1
U6
31
23
HO
U5
U9
1.9
2.8
2.5
2.0
0.76
0.88
1.2
1.1
% Reduction
ML-TSP
Exptl.
Tank
86.9
77.3
90.1
92. U
91.8
92.6
93.5
9U.2
Control
Tank
H5.7
H2.3
U6.3
51.2
72.9
83.7
82.6
87.1
              (l)  Dosage based on Pickle Liquor iron analyses
              (2)  Average of experimental and control tanks inlet ML-TSP
              (3)  Outlet ML samples (6 hours detention)
              (k)  TP * tank turnpoint and is 1/2 of tank length
              (5)  In run 3 these dosages are estimates
              (6)  Past TP (2 hours detention)

-------
        All three iron addition sites (2,3 and 6 hours detention)
were found to be effective, provided there was sufficient ML-DO.
The role of ML-DO level on the effectiveness of ferrous iron in TSP
removal was observed in run 6 and a typical observation at an aeration
rate of 3600 cfm. is given below in Table 19
                              TABLE 19

                        RUN 6 OBSERVATION DATA


                               Turnpoint              Outlet
                       D.O. MG/L  ML-TSP MG/L  D.O. MG/L  ML-TSP MG/L

 Control Tank              2.7       1.1           5.0         0.35
 Experimental Tank          0.5       5.2           6.6         0.22


         In Table 18 it can be seen that the average removal of TSP
 by the MLSS in the control tank was much better in runs U, 5 and 6
 than in runs 1, 2 and 3, even though the inlet average ML-TSP levels
 were much higher in runs U,  5 and 6 compared to the early runs.  This
 difference is attributed to  the effect of the breweries waste water on
 the Milwaukee plants.  First, the initial iron addition runs (7-1-69
 to 7-18-69) were carried out during the breweries shutdown period
 (6-9-69 to 7-15-69) when the daily soluble phosphorus removals
 averaged less than H0#.  In  the second set of runs (8-U-69 to 8-22-69)
 the breweries were back in operation and the daily soluble phosphorus
 removals improved to an average of greater than 80%.  The results in-
 dicated that the addition of ferrous iron as pickle liquor to ML was
 effective in maintaining low residuals of TSP in ML after 6 hours of
 aeration.

         Added soluble ferrous sulfate as pickle liquor was rapidly
 incorporated into the MLSS.  This was found by the analysis of ML
 samples for total  soluble  iron taken at ten foot interval sampling
 points from the iron addition site at the tank turnpoint as shown in
 Table 20.
                                  62

-------
                             TABLE 20

     REDUCTION OF SOLUBLE IRON CONCENTRATION IN AN  AERATION TANK

(Iron * was added as waste pickle liquor at the aeration tank turnpoint)
            DISTANCE FROM                 TOTAL SOLUBLE IRON
            TANK TURNPOINT                 FOUND IN THE ML
                (FEET)                        (mg/L-Fe)

                  10                             l.lU
                  20                             l.lU
                  30                             0.58
                  UO                             0.50
                  50                             0.56
                  60                             0.58
                  70                             O.M
                  80                             O.UU
                  90                             O.U3

* Iron dosing rate 7.5 mg/L - Fe based on ML flow.

The average ML total soluble iron concentrations at the inlets
and outlets were practically the same, 0.23 to 0.39 mg/L-Fe
respectively during the 6 test runs in the experimental tank.

                  The iron added, as obtained by calculation,  from
the pickle liquor data compared favorably with the average total
iron found in the inlet and outlet MLSS as shown in Table 21 •

                  The clarifier detention times are approximately
2 to 3.5 hours.  During this time period it has been previously
shown that soluble phosphorus is released from the solids.  Ten
iron and phosphorus tests were performed in the laboratory with
the samples of ML from the control and experimental tanks outlet
and then the release of phosphorus and iron after two  hours
detention was determined.  The average results of the  ten test
runs as given in Table 22 , indicate that in a period of 2 hours
the MLSS treated with iron release less TSP than the untreated MLSS
from control tanks and that the iron treated MLSS released more
soluble iron than the untreated MLSS.
                              63

-------
                                   TABLE  21

                         AVERAGE   IRON   RECOVERIES
                                                                     Observed Average
Run
Ho.

1
2
3
U
5
6
Planned iron ca
Addition Rates Ad
gprn

1.0
0.5
2.0
2.0
1.0
1.0
0.5(b)
1.0
1.0
mg/L-Fe


15
7.5
30
30(a)
15(a)
15
15
15
15
icuiatea iron
dition Rates
mg/L-Fe


11.0
6.8
27. U

13.3
13.2
15.5
17.0
/iW UU«*J. J.X 1/4* i Wfc****-* sxi
In the Outlet MLSS R<
m«t/L-Fe
Exptl
Tank
70.6
55.0
80.5
8U.3
75.1
68.5
78.1
90. U
Control
Tank
59.2
U9.9
56.7
60.8
60.0
55.9
59.8
7U. U
scovery of Added
Iron Dose
rag/L-Fe

11. U
5.1
23.8
23.5
15.1
12.6
19.0(c)
16.0
(a)  Iron dosing rate estimated from pickle liquor specific gravity.

(b)  Concentrate (undiluted pickle liquor)

(c)  The large difference in run 5 may be partly due to  inadequate manual
     control of pickle liquor flow.

-------
                               TABLE 22

               SOLUBLE IRON AND TSP RELEASE BY MLSS
                       (average of 10 tests)
                       Control Tank

Detention Hours      0 hour    2 hours
 Total soluble Iron  0.21      0.30
         mg/L-Fe
TSP mg/L-P           1.61*      3.01
                                                Experimental Tank
                                              0 hour
                                              0.27

                                              0.29
2 hours
0.71

1.15
                  In general, the neutralized and the unneutralized
waste pickle liquor were observed to have no detrimental effect on
the activated sludge process.  This was shown by the experimental
and control tanks ML having similar pH's, MLSS-02 uptake rates, SDI
values.  Microscopic examinations showed no changes in the biota.
In this limited study no apparent clogging of aeration tank diffuser
plates was observed.
                                65

-------
                   PLANT SCALE IRON ADDITION STUDY
     This was a feasibility study of plant scale iron addition for
improved soluble phosphorus removal during a two week period.   The
EP was used as the experimental plant and the WP as the control.

     The iron was added in the form of ferrous sulfate as unneutral-
ized pickle liquor, a waste product which was supplied by the A.  0.
Smith Corp. Milwaukee, in a cooperative venture.  The A. 0. Smith
Corp. also provided personnel to monitor the pickle liquor iron
concentrations and to control the iron dosing rate 2U hours a day.

     The pickle liquor was added to the EP sewage feed channel 65
feet upstream from the EP RS feed pipe.  The ferrous iron concent-
ration in the pickle liquor was determined by titration with 0.10N
potassium dichronate.  The iron addition rate was then based on the
pickle liquor iron content and the hourly ML flow rate.  A dosing
rate of about 15 mg/L-Pe based on the ML flow was used from 11/3
to 11/7 (2U hours/day for U-l/3 days) during which a total of
110,898 gallons of pickle liquor (7^,300 pounds of iron) was added
to the ML.  From 11/10 to 11/lU (2U hours/day for U-l/3 days),
52,3^5 gallons  (37,200 pounds of iron) of pickle liquor was added
to ML for  a dosing rate of about 7.5 rag/L-Fe.  The sampling pro-
cedures and the analytical methods used were as described  in pre-
vious sections.  The data from the 2U hour WP and EP composite
effluent  samples do not readily show the  effectiveness  of  the
added iron in reducing the effluent residual SOP as shown  in Table
 23.  However, a comparison of the SOP  content of the sewage and
EP  effluent  bihourly  composite  samples  (Figure  lU) illustrates
very dramatically  that a 15  mg/L-Fe dosing  rate consistently pro-
duced  an effluent  SOP residual  of 0.05 mg/L-P for U-l/3 days.
The 7.5  mg/L-Fe dosing rate  was not very  effective as  shown in
Figure  lU.

      In the  previous  section it was found that  in an aeration tank
the added soluble  iron was rapidly removed, and did not appear to
significantly increase the ML total soluble iron content.  This was
also observed during  this  study in the daily data  from both plant
effluents.  The total soluble iron in the plant effluent averaged
0.3U mg/L-Fe for the  WP and  0.31 mg/L-Fe  for the EP.

      Plotted in Figure 15  are the WP and  the EP SEE and MLSS  shift
averages on a daily basis.   The plots  show  that during this  study
period the ML settleability  fluctuated with a weekly  cycle,
improving on Sunday,  Monday  and Tuesday  and deteriorating  steadily
from Wednesday to Saturday for  both the plants. The  plot  also
shows  that an iron dosing  rate  of  15 mg/L-Fe was more effective
than the 7.5 mg/L-Fe dosing  rate in  improving the  settleability  (SDI)
                               66

-------
No Iron Addition
       TABLE 23






EFFLUENT SOP mg/L-P




       Iron Addition
No Iron Addition
10/27/69 to
11/2/69

Monday
Tuesday
Wednesday
Thursday
Friday
Saturday
Sunday
Date
10-27
10-26
10-29
10-30
10-31
11-1
11-2
WP
O.lU
0.16
O.U5
0.1*5
0.51
0.13
0.10
EP
0.15
0.21
0.1*6
0.32
0.25
O.ll*
0.11
15 mg/L-Fe
11/3/69 to
11/9/69
Date
11-3
11-1*
11-5
11-6
11-7
11-8
11-9
WP
0.17
0.10
0.19
0.53
0.82
0.31
0.10
EP
0.07
0.05
0.05
0.05
0.06
0.05
0.18
7.5 mg/L-Fe
11/10/69 to
11/16/69
Date
11-10
11-11
11-12
11-13
ll-ll*
11-15
11-16
WP
O.U6
0.59
0.60
0.70
0.99
0.27
0.13
EP
0.1*1
0.12
0.22
0.27
0.1*1*
0.19
O.U7
11/17/69 to
11/23/69
Date
11-17
11-18
11-19
11-20
11-21
11-22
11-23
WP
0.20
0.31
0.21
0.30
0.53
0.1*5
0.23
EP
1.6
0.75
0.58
0.52
0.70
0.31
O.Ul
Note:  Iron added only to the East Plant



Dosing Rate:  15  mg/L-Fe; 7 A.M.  - 11/3/69 to 3:30 P.M.  on 11/7/69



              7.5 mg/L-Fe; 7 A.M.  - 11/10/69 to 1:05 P.M.  on ll/lU/69

-------
                  10/27/69  TO  11/21/69
                                                                                                 LEGEND
                                                                                                  - SEWAOE SOP
                                                                                                	 EFFLUENT SOP
00
           o
           3
           Q
           O
           C/1
                    NO   IRON   ADDITION
                                                  IRON ADDITION
                                                  I5MG/L  -  FE
                                                 NO   IRON
                                                  ADDITION
                                            IRON   ADDITION
                                            75 MG/L - FE
                                                                                                  NO   IRON   ADDITION
                   I
                   M
           I
           M
I
M
I
M
                                                  M   M
                              I
                              M
I
M
I
M
1    I
M   M
I    I
M   M
I  '  I
M   M
I    I
M   M
I
M
SU  I M
W |  TH
  SA |  SU
                                                            TH
                                                                    SA |  SU I M
                                             T I  W  | TH
                                                                              SA | SU
                                                                                                               W | TH
                                                                                                                          SA
                                FIGURE 14   EFFECT  OF  IRON  ADDITION  ON  EAST  PLANT  RESIDUAL SOP

-------
o-.
          1.20
                                                         LEGEND
                                                       O—OWEST PLANT
                                                           EAST PLANT
            •60' T I I  I I  I  I I  I I  I I  '  I I  ' A
                            3   5   7  9  II  13   15  17  19  21  23  25  27
              26  28  30
             |	OCT.	\
          FI6UREI5  COMPARISON  OF EAST  a  WEST  PLANT  SDl'S  1969

-------
of the EP MLSS vhen compared to that of the WP MLSS.  This was
probably due to the iron accumulation in the MLSS vhich increased
the density of EP MLSS.

         The accumulation of added iron in the East Plant Return
Sludge with time is plotted in Figure l6.  The data was obtained from
RS samples taken continuously at intervals of 2 hours.

         The first iron addition (15 mg/L-Pe) began at 7 A.M.  on
11/3/69 and the accumulation of the iron in the RSSS (approximately
2.5JO was observed to begin with the U P.M. sample on 11/3/69.  From
this point, the iron continued to accumulate in the RS until 8 A.M.
on Thursday, 11/6/69 (6U hours of iron addition) and then the RS
iron content stayed at a fairly constant level (at an average of
6.01*) until midnight of 11/7/69 (next Uo hours).  This indicated that
an equilibrium condition was reached when the iron wasting rate (i.e.,
the iron in EP-WS) was equivalent to the iron addition rate.  From
k A.M. on Saturday 11/8/69 the EP-RS iron content slowly decreased due
to the cessation of iron addition.

         The second iron addition (7.5 mg/L-Fe) was started at 7 A.M.
on Monday 11/10/69*  Figure 16 shows that at this iron addition rate
the iron did not show any further buildup in the EP-RS (average 5.26JO.
This indicated that the equilibrium iron concentration was reached for
these iron dosing and sludge wasting rates. After iron addition was
stopped at 1 P.M. on Friday ll/lU/69, the RS iron content was observed
to continually decrease from 5.26j» at 10 P.M. on Friday until it
approached the initial RS iron level of 2.5# on Thursday, 11/20/69.

         The total phosphorus contents were also determined on these
bihourly RS samples.  These values are also plotted in Figure 16.  A
comparison of the RS phosphorus and iron plots reveals that the
phosphorus did not accumulate in the RS to the same extent that the
iron accumulated.

         It was anticipated that the accumulation of iron in EP-RS
would increase its ash content, and the effect of the increased ash
would be to reduce nitrogen content of the RS.

         Each day, one liter sample of WP and EP-RS were centrifuged
and the concentrated solids dried at 10H°C for 2k hours.  Ash and Total
Kjeldahl Nitrogen (AOAC-2.0U2 and 2.0U3, reference 36) analyses were
performed on the dried material.  In Figures 17 and 18 are plotted the
results of these daily analyses.  These figures show that as iron
addition continued the EP-RS ash content progressively increased as the
iron was added, and the EP-RS ash content was much higher than that of
the WP-RS.  When iron addition was stopped on ll/lU/69 the EP-RS ash
content decreased as the accumulated iron was removed from the system
as waste sludge.
                                 70

-------

'•
                         -IRON ADDITION -
                             18 MG/U
-NO  IRON-
                            -IRON  ADDITION-
                                75 MO/L
                                                                -NO  IRON
                                  NMNMNMNMNMNMNMNM    N   M15    MN5NMNBN~M	3	!j	£	J	1	1
            .| M/J MON | MM  Tue | ,,/5 WED.  | ,1/6 THUR | M/7 FR, | M/e SAT | ,,/=, SUN  | M/,0 MON  | „/,, TUE | M/B WED | ,,/,, THUR |  M/,, FR, | ,,/B  SAT | „/,. SUN | M/,7 MON |  M/B TUES | M/,9 WED | M/20THUR | ,1/3, |FR,  |


                                                           FIGURE  16    ACCUMULATION   OF   IRON  IN   EP-RS

                                                                                      1969

-------
   30
    29
 to
 <
 CD
 cc
 0
    28
 CO
 cc

 I
 (O 27
    26
    25
    24
        LEGEND
        —O WEST PLANT
      £t	A EAST PLANT
                        IRON ADDITION:
                        I5MG/L; 7AM. 11/3 TO 3:30 PM. 11/7
                        75 MG/L; 7A.M. 11/10 TO 1:05PM 11/14
                         IRON
                       15 MG/L
                             IRON
                            75 MG/L
                                              16
                      i — r— i — r— i — i
                                   i  i — i
IO/27
            i — i— i — i
            -II/I   SU 11/2- 11/8  SU  II/9-II/I5  SU  11/16-11/20 Su
FIGURE 17 RETURN  SLUDGE  ASH  CONTENT  (DRY  BASIS)
                              1969
                                72

-------
   6.7
   6.6
GO
CO
<
CD

CC
CO
oL

e>
o
cc
   6.4
   63
   e,
   6.1
 LEGEND
O	OWEST PLANT
A	A EAST PLANT
                                       IRON ADDITION:
                                       15 MG/L; 7A.M. 11/3 TO 3:30PM 11/9
                                       75MG/LJ7AM II/IOTO 1:05PM. 11/14
                                   IRON
                                  75 MG/L
                                           16
       ' ,0/27- 111/1   SU  11/2-I 1/8  SU  11/9-11/15  SU  11/16-11/20  SU

  FIGURE 18 RETURN SLUDGE NITROGEN  CONTENT
                        (DRY  BASIS)

                             1969
                                73

-------
         The effect of the increased ash content vas to reduce the
EP-RS nitrogen content as shown in Figure 18.  The magnitude of the
effect of ash content on the nitrogen content of this vaste sludge
can be obtained by a comparison of the average values of ash and
nitrogen contents of RS during the iron addition periods as shown
in Table 2k.
                                74

-------
                                TABLE 2U

                    AVERAGE RETURN SLUDOE COMPOSITION
Iron Addition
                            % Ash	* Nitrogen
                          EP  Difference    WP     EP  Difference
15 mg/L

11/3 to 11/7       25.9    29.1     3.2      6.U9   6.27     0.21

% N based  on  VSS                          (8.76)  (8.85)   (0.09)
 7.5

 11/10 to ll/U     25.2   28.8     3.6      6.59   6.32      0.27

 % *  based on VSS                          (8.82) (8.87)    (0.05)
                                 75

-------
                              SECTION VII
                            ACKNOWLEDGEMENTS
        This report was prepared by  Raymond D. Leary, Chief Engineer and
General Manager; Lawrence A. Ernest, Director of Laboratory; Roland S.
Powell, Assistant Director of Laboratory; and Lawrence H. Docta, Research
Supervisor of the Sewerage Commission  of the City of Milwaukee.

        We acknowledge the assistance  given by Mr. H. W. Boston and
Mr. C. Risley and the staff of  the Chicago office of the Environmental
Protection Agency.  Our acknowledgements are due to Dr. R. N. Kinman and
Dr. R. L. Bunch whose guidance  from  time to time as project officers led
to the completion of this project.   The Commission Staff members wish to
express their gratitude to the  Marquette University Staff who conducted
the statistical and X-Ray diffraction  studies under the guidance of the
project consultants Dr. Raymond J. Kipp and Dr. Sudershan K. Malhotra.
The Commission commends the A.  0. Smith Corp. (Milw., Wis.) for their
cooperation and contribution of the  waste pickle liquor for the iron
addition studies as well as for the  assistance and cooperation of Mr.
Milton Johnson and other A. 0.  Smith personnel in making that study
successful.

        The assistance of Laboratory Technicians, Miss Gloria Aldenhoff,
Mrs. Minne Ness, Miss Elizabeth Merscher, and Mr. Gerald Hertzfeldt in
conducting the laboratory analyses is  gratefully acknowledged.
                                    77

-------
                            SECTION VIII
                             REFERENCES
 1.   Unpublished data.   Sewerage Commission of the City  of Milwaukee
     Laboratory, Wisconsin.

 2.   Connell,  C. H., and D.  Vacker, "Parameters of Phosphate Removal
     by Activated Sludge," Proceedings of the 7th Industrial Water
     and Waste Water Conference, Univ. of Texas, Austin, (June 1
     & 2, 1967).

 3.   Witherow, Jack, L., "Phosphate Removal by Activated Sludge," A
     report by the U.S.  Depart, of Interior, FWPCA, Robert S.  Kerr
     Water Research Center, Ada, Oklahoma (May 1969).

 U.   Menar, A. B., and D. Jenkins, "The Mechanism of Enhanced
     Phosphate Removal in the Activated Sludge Process," Part  II,
     SERL Report 68-6, Univ. of California, Berkeley,  (Aug., 1968).

 5.   Levin, G. V., and J. Shapiro, "Metabolic Uptake of Phosphorus by
     Waste Water Organisms," J. Water Pollution Control Federation,
     37_,(6),800 (1965).

 6.   Vacker, D., C. H. Connell, and W. N. Wells, "Phosphate Removal
     Through Municipal Waste Water Treatment at San Antonio, Texas,"
     J. Water Pollution Control Federation, 32,(5),750 (1967).

 7.   Owen, R., "Removal of Phosphorus from Sewage Plant Effluents with
     Lime," Sew. and Ind. Wastes, 25., (5), 5**8 (1953).

 8.   Stone, T., "Iron and Phosphate Changes during Sewage Treatment,"
     Sew. and Ind. Wastes, 31, (8), 98l (1959).

 9*   Hurwitz, E., R. Beaudoin, and W. Waters, "Phosphates,  Their Fate
     in a Sewage Treatment Plant-Waterway System," Water and Sew. Works,
     112. (3), 8U (1965).

10.   Lea, W. L., G. A. Rohlich, and W. J. Katz, "Removal of Phosphates
     from Treated Sewage," Sew. and Ind. Wastes, £6, (3), 26l  (195*0.

11.   Rohlich, G. A., "Methods for the Removal of Phosphorus from
     Sewage Plant Effluents," Inter. J. of Air and Water Pollution, J_
     U27 (1963).
                                 79

-------
12.  Malhotra, S. K. , G. F. Lee, and G. A. Rohlich, "Nutrient Removal
     from Secondary Effluent "by Alum Flocculation and Lime Precipi-
     tation," Inter. J. of Mr and Water Pollution, £, 1*87 (196U).

13.  Nesbitt, J. B., "Removal of Phosphorus from Municipal Sewage
     Plant Effluents," Eng. Research Bulletin B-93, Penna. State Univ.,
     College of Eng., University-Park, Penna., (1966).

lit.  Tenney, M. W. , and W. Stumm, "Chemical Flocculation of Micro-
     organisms in Biological Waste Treatment," J. Water Pollution
     Control Federation, 37.. (10), 1371 (1965).

15.  Barth, E. F. , and M. B. Ettinger, "Mineral Controlled Phosphorus
     Removal in the Activated Sludge Process," J. Water Pollution
     Control Federation, 3£, (8), 1362 (1967).

16.  Eberhardt, W. A. and J. B. Nesbitt, "Chemical Precipitation of
     Phosphorus in a High Rate Activated Sludge System," J. Water
     Pollution Control Federation, jj£, (7), 1239 (1968).

17.  Rudolf, W. , "Phosphates in Sewage and Sludge Treatment. II.
     Effect on Coagulation, Clarification and Sludge Volume*',
      Sewage Works J., 19.,  (2), 178 (19^7).

18.  Neil, J. H., "Problems and Control of Unnatural Fertilization of
     Lake Waters," Proceedings of the 12th Ind. Wastes Conf . , Purdue
     Univ.,  (May 13-15, 1957).

19.  Schmid, L. A. , and R. E. McKinney, "Phosphate Removal by Lime-
     Biological Treatment Scheme," J. Water Pollution Control Feder-
     ation, la, (7), 1259 (1969).

20.  Sawyer, C. N. , "Biological Engineering in Sewage Treatment,"
     Sewage Works J. , l£, (9), 925
21.  Sekikawa, Y. , S. Nishikawa, M. Okazaki, and K. Kato, "Release
     of Soluble Phosphates in the Activated Sludge Process," 3rd
     International Conference on Water Pollution Research, Munich,
     Germany, (Sept., 1966).

22.  Hall, M. W., and K. Engelbrecht, "Uptake of Soluble Phosphate
     by Activated Sludge; Parameters of Influence," Proceedings of
     the 7th Industrial Water and Waste Water Conference, Univ. of
     Texas, Austin, p. II, 8, (1967).
                               80

-------
23.  Borchardt, J. A., and H. S. Azad, "Biological Extraction of
     Nutrients," J. Water Pollution Control Federation, UP,   (10),
     1739 (1968).

2U.  Srinath, E. G., C. A. Sastry, and S. C. Pillai, "Rapid  Removal
     of Phosphorus from Sewage by Activated Sludge," Experientla,
     15, 9 (1959).

25.  Alarcon, G. 0., "Removal of Phosphorus from Sewage," Masters
     Essay, The John Hopkins Univ., Baltimore, Maryland, (l96l).

26.  Feng, T. H., "Phosphorus and the Activated Sludge Process,"
     Water and Sewage Works, 109* (ll),  ^31 (1962).

27.  Campbell, L. A., "The Role of Phosphate in the Activated Sludge
     Process," Proceedings of the 21st, Purdue Industrial Waste
     Conference,  (May, 1966).

28.  Leary, R. D., and L. A. Ernest,  "Industrial  and  Domestic  Waste-
     water Control in the Milwaukee Metropolitan  District," J. Water
     Pollution Control Federation, 32.  (7), 1223  (1967).

29.  "Instructions For YSI Model  53 Biological Oxygen Monitor,"
     Yellow Springs  Instrument  Co. Inc., Yellow Springs, Ohio.

30,  "Instruction Manual Hach  C R Surface Scatter Turbidimeters
     Model 1889," Hach Chemical Company, Ames, Iowa.

31.  "Instruction Manual Hach  Laboratory Turbidimeter  Model  2100,"
     Hach Chemical  Company,  Ames, Iowa.

32.  "Procedure  Manual For  Atomic Absorption Spectrophotometry,"
     Instrumentation Laboratory Inc., Lexington,  Mass.

33.  "Standard Methods  for  the Examination of Water and Wastewater."
     12th Ed. Amer.  Pub. Health Assn.,  New York  (1965).

3U.  Goodman, B. L., and J.  W. Foster,  "Notes On Activated  Sludge ."2nd
     Edition, Smith and Loveless Division of Union Tank Car Company,
     Lenexa, Kansas.

 35.  Kipp,  R. J., "Statistical Analysis  of Phosphate Removal Data
      for 1968, 1969; Jones Island Sewage Treatment Plant, Milwaukee,
     Wisconsin," Marquette Univ. (May 1970).
                               81

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36.  "Official Methods of Analysis of the Association of Official
     Agricultural Chemists." 10th Ed., Aasn.  of Official Agricultural
     Chemists, Washington, D.C."Tl965).

37.  Eckenfelder, Jr., W. W., and D. J. Q'Connor."Biological Waste
     Treatment."  Pergamon Press, New York, New York (1961).

38.  Okun, D. A., and W. R. Lynn, "Preliminary Investigations^into the
     Effect of Oxygen Tension on Biological Sewage Treatment,  in J.
     McCabe and W. W. Eckenfelder Jr., "Biological Treatment of Sewage
     and Industrial Wastes." Volume I, Rheinhold, New York, New York
     (1956).

39.  Ford, D. L., J. T. Young, and W. W. Eckenfelder Jr., "Dehydro-
     genase Enzyme as a Parameter of Activated Sludge Activities,
     Proceedings of the 21st_ Ind. Waste Conf., Purdue Univ., Part I,
     (May 3 to 5, 1966).

HO.  Natrella, M. G., "Experimental Statistics".NBS Handbook No. 91,
     U.S. Government Printing Office,  Wash., D.C.  (1963).

Ul.  Jones,  P.H., and D.  Prasad, "The Use of Tetrazolium Salts as a
     Measure of Sludge  Activity," J.  Water Pollution Control Feder-
      ation,  Ul, (11, Part 2), R M»l (1969).

 U2.   Gopalakrishna, E.  M., J. Winters, and L.  Gartz "Report on the
      X-Ray Analysis of Sludge Material," Marquette, Univ.  (June  1969).

 H3.   Natarajan, Dr., M. Seitz.  J. Winters, and R. J. Riedner,  "Sludge
      X-Ray Analysis Report," Marquette Univ. (December 1969).

 UU.   Seitz, M. A., R. Riedner,  and J. Winters, "X-Ray Diffraction
      Studies of Sewage Sludge Residue," Marquette Univ. (March 1970).

 U5.   Chang, S. C., and M. L. Jackson, "Solubility Product  of Iron
      Phosphate," Soil Science of America Proceedings, 21,  (3), 265
      (1957).

 U6.  Galal-Grochev, H., and W.  Stumm, "The Reaction of Ferric Iron
      with Ortho-Phosphate," J.  Inorg. Nucl, Chem., 2£, 576 U9&3).
                               82

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                               SECTION IX

            PHOSPHORUS NOMENCLATURE AND ABBREVIATION'S GLOSSARY

PHOSPHORUS NOMENCLATURE

         1.  Total Phosphorus (TP).
             All the phosphorus present in sample (whether in the
             soluble or insoluble state and present as ortho, poly,
             organic, etc., phosphorus compounds) which is converted
             by ternary acid digestion to soluble ortho-phosphate.

         2.  Soluble Ortho - Phosphate (SOP).
             All phosphorus measured by direct colorimetric analysis
             of sample filtrate.   (Angel Reeve Glass Fiber Pad No.
             93UAB).

         3.  Total Soluble Phosphorus  (TSP).
             All the phosphorus compounds in the sample filtrate
             converted by ternary  acid digestion to ortho-phosphate.

         1*.  Suspended Solids Phosphorus  (SS-P).
             Represents the phosphorus present in the  sample
             suspended solids.  (SS-P  = TP - TSP).

 ABBREVIATIONS  GLOSSARY

         1.  BOD -  five day biochemical  oxygen demand.

         2.  BOD/TSP -   ratio of BOD removed/day to TSP removed/day.
          3.   CV - coefficient of variation (standard deviation
              divided by the average, multiplied by 100).

          U.   CFM - cubic feet per minute.

          5.   COD - chemical oxygen demand.

          6.   DO - dissolved oxygen.

          T.   EP - East Plant.

          8.   EPML - East Plant mixed liquor.

          9.   EPRS - East Plant return sludge.

         10.   EPWS - East Plant waste sludge.

         11.   F/M -  (Ratio  of  food to microorganisms) /Day.
                                83

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            iEBOD/DAY
#MLVSS in the Aeration Capacity

12.  MOD - million gallons/day.

13.  ML - mixed liquor.

lU.  ML-DO - mixed liquor dissolved oxygen.

15.  ML-SDI - mixed liquor sludge density index.

16.  MLSS - mixed liquor suspended solids.

17.  MLSS-0- - mixed liquor oxygen uptake rate.
               mg 02/mg VSS/hour).

18.  MLVSS - mixed liquor volatile suspended solids.

19.  N - nitrogen.

20.  P - phosphorus.

21.  RS - return sludge.

22.  RSSS - return sludge suspended solids.

23.  SOP - soluble ortho-phosphate.

2k.  SS - suspended solids.

25.  TP - total phosphorus.

26.  TSP - total soluble phosphorus

27.  TP/M - (ratio of total phosphorus to Microorganisms)/Day,

           	jfTP/DAY	
           #MLVSS in the Aeration Capacity

28.  MM TPF/5 mis of ML - micro-moles of triphenylformazin/
      5mls of mixed liquor.

29.  VSS - volatile suspended solids.

30.  WP - West Plant.

31.  WS - vaste sludge.
                       84

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                              SECTION  X

                              APPENDIX A


        PHOSPHORUS DETERMINATION WITH TECHNICON AUTOANALYZER


Sample Preparation

      A«  Total Phosphorus

            1.  Pipette unfiltered sample into a 100 ml. volumetric
                flask (20 mis effluent, 5 mis for sewage).

            2.  Add 5 mis of Ternary Acid Mixture and 3 glass "beads.

            3.  Heat on hot plate to dense fumes of perchloric acid,
                plus 5 minutes, cool.

            U.  Add 20 mis of distilled water, bring to a boil, boil
                5 minutes, cool.

            5.  Add 1 drop of phenolphthalein. neutralize vith 10 NaOH
                to a faint pink color.
            6.  Just discharge pink color with INHgSO^, dilute to
                100 ml, mix.

            7.  Place solution from step 6 in the sampling cup of
                the aut oanaly zer .

            8.  Obtain the phosphorus  concentration of the sample
                from the  standard  curve.

      B.  Total Soluble Phosphorus

            1.  Same as total phosphorus, except the aliquot is
                filtered  through an Angel Reeves glass fiber pad
                93UAH.

      C.  Soluble  Ortho-Phosphate

            1.  Filter through Angel Reeves  glass fiber pad 93UAH.

            2.  Dilute filtrate  if needed.

            3  Place in  sampling  cup  of the autoanalyzer.
                                  85

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Reagents

     A.  Afflmonium Molybdate - Dissolve 200 gm of (MHj,)/- Mo7 0
     mmonum  oyae -                       jg   ?   .  .g
    in 10 liters of distilled vater.  Add 1680 ml of con57H2soU
    and dilute to 20 liters.

B.  ANSA Stock Solution - Dissolve 219 gm Na2S20  and 8 gm Na2
    SO- in 700 ml of distilled water (temperature <50° C), add
    1* gm of 1-amino- 2-naphthol -U- sulfonic acid.  Dilute to
    2 liters.  For daily use, prepare a 1:10 dilution.

C.  Phosphorus Standard Curve use standards, both digested and
    undigested from 0.1 to 1.2 mg/L-P in increments of
    0.1 mg/L-P from a 1000 mg/L-P stock (U.386 gm of
    oven dried at 103°C for U hours, in one liter).
D.  Ternary Acid Mixture - Add 100 mis of 96% HgSO^ to 500 mis
    of 1Q% HK03, mix.  Add 200 mis 70? HCIO^, mix and cool.
                            86

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oo
          SAMPLER II
          RATE.40_pERHR.
             1:2 CAM
          WATER RINSE EVERY
             4tb SAMPLE
TO WELL
                                   O
TUBE  SIZE
  (INCHES)
0.090  WATER
                                                                       QO73  ANSA
                 FIGURE 19    TECHNICON   AUTOANALYZER   SCHEMATIC

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                     APPENDIX B


    PROCEDURE USED FOR MLSS AND RSSS DETERMINATION:


A.  Determination of SS concentration by weight.

      1.  Mix sample veil, pour (100 mis for ML., 50 mis for RS)
          into a 100 ml graduate cylinder.

      2.  Add 5J& chlorhydrol solution (6 drops for ML and 12
          drops for RS) mix 3 times by inversion, let sit for
          5 minutes.

      3.  Filter under vacuum thru tared filter paper (9cm, S and
          S Sharkskin for ML, Whatman No. 3 for RS) placed on a
          buechner funnel.

      U.  Dry the paper  for 1 hour at 103° C in a Forced
          Draft Oven.

      5.  Cool it for  5  minutes in a dessicator and weigh back.

      6.  For MLSS subtract from  this weight the tare weight of
          the paper.   This gives  solids in units of grams which
          in turn is equivalent to per cent by weight.   (For
          RSSS since we  used  50 ml sample, therefore multiply
          the above weight by a factor of two  to get per cent
          RSSS by weight).

 B.   Determination of MLVSS

      1.  Place the filter paper  with MLSS  (use low ash S and S
          filter paper)  after step 5 in a previously ashed and
          tared silica dish,  and  then ash for  15 minutes at 600°C.

       2.  Cool for 30  minutes in  a dessicator  and then  weigh back.

       3.  The MLSS less  the MLSS  ash divided by the MLSS when
          multiplied by  100 equals per cent MLVSS.
                                  88

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                             APPENDIX  C

                          BOD DETERMINATION
Dilution Water

  1.  Add 1 ml of the following solutions (33) to each liter of aged
      distilled water, 5 or more days.

                       Phosphate Buffer Solution
                       Magnesium Sulfate Solution
                       Calcium Chloride Solution
                       Ferric Chloride Solution

  2.  Aerate this mixture for 5 minutes.

  Meter Setting

  1.  Place probe in aerating distilled vater for 5 minutes.
  2.  Check zero and adjust if necessary.
  3.  Check red line and adjust if necessary.
  1*.  Determine barometric pressure.
  5.  Read temperature on meter.
  6.  Determine DO  setting vith pressure-temperature chart.
  7.  Adjust calibration for DO of the day.

  Procedure

  1.  Discharge stale water in buffer line.
  2.  Siphon dilution water into BOD  bottle  for blank.
  3.  Place probe in BOD bottle and read DO  when meter stabilizes.
  U.  Stopper with  rubber  seal and incubate  for 5 days, dilution
      vater blank.
  5.  Determine dilutions  to be made  (set  of 2) for samples.
  6.  Siphon dilution water to cylinder, filling to required mark.
  7.  Add sample  desired with pipette or siphon.
  8.  Mix well with plunger and siphon to  BOD bottles.
  9.  Determine DO, stopper and seal, and  incubate 5  days.
  10.  After  5 days  remove  from incubation  and determine DO  as before,
                                89

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Calculations
1.
2.
Initial DO - 5 day
Conversion factors
5 day BOD, dividing
x dilution factor = 5 day
BOD
of U and 6 day sevage and effluent BO]
by appropriate factor listed below.
U day
Sewage .875
Effluent .796
parts
Sample
1
1
1
1
1
1
1
1
parts
dilution H20
+ 1
* 3
+ 9
+ 19
+ 39
+ 1*9
+ 79
+ 99
DILUTION TABLE
ml
dilution H20
150 ml
225 "
270 "
285
292.5 "
204
296.25 "
297 "
6 day
1.076
1.231
add ml
of Sample
150 ml
75
30
15
7.5 "
6
3.75 "
3
                             90

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                            APPENDIX D
DISCUSSION OF MATERIAL FOUND FLOATING ON THE SURFACE OF THE EP AERATION
TANKS AND THE AEROBIC DIGESTION OF WASTE SLUDGE.

        The principal microorganism found in this material floating
on the surface of the E.P. aeration tanks was identified as belonging
to Actinomycetaceae and to the Genus Nocardia. A sample of this
material was found to contain 85? volatile matter and 31% hexane  solu-
bie materials.  Regular defoaming agents as mentioned before were
ineffective in breaking this foam.  Vacuum skimming of aeration tanks
and clarifier feed channels reduced the amount of foam and aided in
overcoming this problem.  This floating material did not appear during
all this time in the WP.

        The effect of extended aeration on the stability of the
Actinomycetaceae foam was also investigated.  The East Plant Reserve
Return Sludge channel was filled with approximately 286,000 gallons
of waste sludge.  This waste sludge was vigorously aerated for 21 days
(3-25-69 to lt-15-69).  The air application rate could not be defined
because the air supply to this RS channel was not metered.  At no
time during this lengthy aeration period was a decrease in the
quantity or the density of the Acti nomy cetaceae foam observed.

        During this study it was also decided to observe the effect
of extended aeration on the aerobic digestion of the waste sludge
containing this floating matter.  Seven liter composite samples were
taken out of the aerated sludge for several days during this experiment
and analyzed for TP,TSP, SOP, S3, VSS, pH and total Nitrogen.  The
results of these analyses are presented in Table 25.  Some of the
variation in the data was caused by sampling and analytical errors.
Further, a part of the reduction of SS and TP in the aerated waste
sludge was due to the dilution caused by some waste water entering
the reserve RS channel.

        The following general observations were made regarding the
aerobic digestion of sludge in the reserve RS channel.

        1.  There appeared to be an acclimatization period of approxi-
            mately 2 to 3 days before the aerobic digestion of the
            solids began.

        2.  After the acclimatization period, aerobic digestion of the
            sludge solids was significant as  indicated by a sudden
            increase in the soluble phosphorus  and  a decrease in the
            $VSS and % nitrogen in the waste  sludge solids.
                                 91

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                                  TABLE 25




                        AEROBIC DIGESTION OF SLUDGE
Date
1969
3-25
3-27
3-28
3-31
U-2
U-3
H-7
l*-9
1*-11
U-lU
U-15
Day
Tu
Th
F
M
W
Th
M
W
F
M
Tu
* Phosphorus

0
2
3
6
8
9
13
15
17
20
21
TP
-
280
270
266
2U6
258
238
226
239
220
205
TSP
-
2.1*
3.1*
-
25.U
32.8
1*8.6
51.6
58.3
56.0
53.1
SOP
-
2.1
2.8
1U.6
lU.7
32.5
1*6.9
1*9.1
53.1*
53.6
52.9
Sludge
Solids
PH
in
% Sludge
MG/L VSS (Dry)
-
10,000
9,1*30
8,31*0
7,890
7,180
5,910
6,300
5,560
5,010
U.350
-
61*. 5
63.8
56.6
59.3
56.U
55.3
56.2
55.7
53.5
-
-
7.1
7.3
7.2
7.0
7.1
7.1
7.0
7.0
7.1
-
-
6.61*
-
6.70
-
5.95
5.86
-
6.05
-
5.90
in
Sludge
(Dry)
-
2.78
2.83
3.13
2.80
3.11*
3.20
2.78
3.25
3.27
3.1*9
"Number of days    aerated.
                                 92

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        3.   In a period of  6  to  8 days over k$% of the volatile
            matter  in the waste  sludge solids was reduced and
            after that the  %  reduction of volatile matter did
            not increase  significantly.

        H.   During  aerobic  digestion of  sludge  solids, the solids
            appeared to hold  the remaining  phosphorus very strongly.
            This was shown by the increase  in the % phosphorus in
            the  solids on a dry basis as the  digestion progressed.

        5.   Aerobic digestion of sludge  solids  had no effect on the
            pH value of the sludge.

        It was observed that similar floating material  started to
reappear in November (1969) in small quantities and on limited
occasions in both plants when no changes in loading  or  other process
parameters were made.  This foam then continued to build up to the
extent where it started affecting the operation of both the plants.
The cause or causes of the appearance of this floating material
and the controlling of this material by process parameters changes
is not yet  fully known but we did  seem to have limited success in
overcoming  this floating material by increasing F/M loadings.
                                 93

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                                              APPENDIX  E


1967

1968

1969

SCREENED SEWAGE CHARACTERISTICS
Flow
BOD
SS
TP
TSP
SOP
% of TP in SS
PLANT OPERATION
Plow
BOD
SS
TP
TSP
SOP
mgd
mg/L
mg/L
ng/L
mg/L
mg/L


mgd
mg/L
mg/L
mg/L
mg/L
mg/L
DETENTION TIME UNDER AIR HOURS
Air Applied Cu. ft
Food/Microorganism
MLSS MG/L
< RS
./gal. Sewage
Ratio

183.
297
301*
8.
...
...
—
WEST
71*. 5
15.1
22
1.2
...
—
6.8
l.Uo
O.U25
2800
28.0
i*


u



EAST
109.0
18.2
25
1.3
...
...
6.6
1.22
0.1*53
2700
25. U
183.1*
306
311*
9.6
...
2.8
...
WEST
76.3
26.8
1*7
2.2
—
0.87
6.8
1.37
O.U25
2900
28.2







EAST
107.2
19.2
30
1.7
...
0.83
6.8
1.21
0.1*1*0
2800
25. U
181.6
239
227
81
.1*
3.5
2.3
57.2
WEST
76.1*
21.3
1*1
2.0
0.99
0.86
6.6
1.36
0.391
2600
27.5







EAST
105.2
1U.8
23
1.1*
_ rt /*
0,86
0.73
6.8
1.20
0.388
2600
25.1*
Lbs. BOD per 1000 cu. ft. of
Aeration Tank Capacity
58.1
60.2
59.
60.5
                                                                                 1*7.8
1*7.5

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                                         APPENDIX  F

          TOTAL PHOSPHORUS REMOVAL AT THE JONES ISLAND PLANTS BASED ON PLANT FLOWS

                  The values used in the calculations are yearly averages.
Flow MOD
TP mg/L-P
TP pounds

Lant Effluent
Flow MOD
TP mg/L-P
TP pounds
Dtal TP pounds
Removal
183. U
8. It
12.8U8
W E

7U.5 109.0
1.2 1.3
7U6 1182
1928
85.0
183. U
9.6
1H.68H
W E

76.0 107.2
2.2 1.7
ll*00 1520
2920
80.1
181.6
8.U
12,722
W E

76. U 105.
2.0 1.
127H 1228
2502
80.3





2
U



W » West Plant

E = East Plant
                                                                           7350
                                                                             81.7

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   Accession Number
 w
Subject Field & Group
                            05
                  SELECTED WATER RESOURCES ABSTRACTS
                        INPUT TRANSACTION  FORM
   Organization
             Sewerage Commission of the City of Milwaukee,
             Milwaukee, Wisconsin
   Title
             Phosphorus Removal By An Activated Sludge Plant
10
   Authors)
            Leary, R. D.
            Ernest, L. A.
            Powell, R. S.
            Docta, L. H.
            Malhotra, S. K.
            Kipp, R. J.
           Project Designation pj.ogram # IJQIO DXD

                Grant # WPD  188-01-67, 188-02-68, 188-03-69
        21
           Note
22
    Citation
              Water Resources Research Catalog.
              Vol. 3, Dec. 1967, p 585, Abstract 5.1362
23
    Descriptors (Starred First)
              •Phosphorus removal, * Activated Sludge Process,
               Process parameters, Wastewater treatment,
              •Biological treatment.
 25
    Identifiers (Starred First)
 27
    Abstract
 jo«    tb. actirtea sludge plants elsewhere in this country.  A detailed plant-





                                         -rs sLss^sr^s^-at
                                         vithout «r apparent detri^ntal e«ect on
the process or equipment.
Abstractor
                    J. Kil
                            Institution
              Marquette University, Milwaukee, Wisconsin
  WR:102 (REV. JULY 1969)
  WRSIC
                          "SEND, WITH COPY OF DOCUMENT,
                        ' U.S. DEPARTMENT OF THE INTERIOR
                         WASHINGTON. D. C. 2024O
                                                                         * GPO: 197U-389-930

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