Environmental Protection Technology Series
Alum  Addition  To Activated  Sludge



With Tertiary Solids Removal
                                               \

                                                LU
                                                CD
                                Office of Research and Development


                                U.S. Environmental Protection Agency


                                Washington, D.C. 20460

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                        RESEARCH REPORTING SERIES
Research reports of the Office of Research and Monitoring, Environ-
mental Protection Agency, have been grouped into five series.  These
five broad categories were established to facilitate further develop-
ment and application of environmental technology.  Elimination of
traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields.  The five series
are:

     1.  Environmental Health Effects Research
     2.  Environmental Protection Technology
     3.  Ecological Research
     4.  Environmental Monitoring
     5.  Socioeconomic Environmental Studies

This report has been assigned to the Environmental Protection Technology
Series.  This series describes research performed to develop and demon-
strate instrumentation, equipment and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution.
This work provides the new or improved technology required for the
control and treatment of pollution sources to meet environmental
quality standards.
                           EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and Monitoring,
EPA, and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.

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                                                           EPA 670/2-73-037
                                                           August 1973
             ALUM  ADDITION TO ACTIVATED  SLUDGE WITH
                      TERTIARY SOLIDS REMOVAL
                                By
                          Alan  B.  Hais
                        John  B.  Stamberg
                       Doll off  F.  Bishop

           D.C. Department of Environmental  Services
                               and
                       EPA-DC Pilot Plant
                     Washington, D.C.  20032
                      Contract No. 14-12-818
                        Project 11010 EYM
                      Program Element  1B2033
                         Project Officer

                        Dolloff F, Bishop
          Advanced Waste Treatment Research  Laboratory
             National  Environmental Research Center
                     Cincinnati, Ohio  45268
                           Prepared for
                OFFICE OF RESEARCH AND MONITORING
              U.S.  ENVIRONMENTAL PROTECTION AGENCY
                      WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, V.S. Government Printing Office, Washington, D.C. 20402 - Price 66 cents

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                              ABSTRACT


Pilot treatment of District of Columbia primary effluent in the EPA-DC
Pilot Plant consisted of four pass step aeration, alum addition in the
final aeration pass for phosphorus removal, secondary clarification
and multi-media filtration for tertiary solids separation.

The activated sludge system was operated with 4.0 hours aeration time
(based on the influent flow) and an overflow rate in the secondary
settler of 425 gal/(day)(sq.ft.).   Alum (A12(SO.)3.14 H^O)  was  dosed
assuming an influent phosphorus concentration of 8.15 mg/1  as  P.   Lime
(25 mg/1) was added to the mixed liquor to stabilize the wastewater
during periods of low alkalinity.   The dual-media filter (24-inch  bed
depth) and the tri-media filter (40-inch bed depth), each loaded at
2.4 gal/(min.) (sq.ft.), regularly exhibited filter  runs between 24
and 32 hours.

When operating with the usual  final stage mixed liquor pH (6.7-6.9),
the complete system with tri-media filtration removed 92% of the
suspended solids, 96% of the BOD and 93% of the phosphorus  from the
primary effluent.  Daily fluctuations in the final pass pH,  however,
corresponded to similar fluctuations in phosphorus removal.  Further-
more, the removal of suspended solids, BOD and phosphorus all increased
to 97% during those periods when the final  pass pH was  between  6.3 and
6.6.  Operation with a relatively  low mixed liquor pH (less  than 6.2),
caused an upset in the activated sludge.

This report is submitted in partial fulfillment of Project  11010 EYM
and Contract No.  14-12-818 by  the  Department of Environmental Services,
Government of the District of Columbia under the sponsorship of the
Office of Research and Monitoring, Environmental  Protection  Agency.
Work was completed as of October 1971.

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                              CONTENTS
                                                              Page
Abstract                                                      ii
List of Figures                                               iv
List of Tables                                                v
Acknowledgments                                               vi
Sections
I       Conclusions                                           1
II      Recommendations                                       2
III     Introduction                                          3
IV      Description of Pilot Plant and Procedures             4
V       Operation of Activated Sludge Process                 7
VI      Results and Discussions                               11
          Pollutant Residuals                                 11
          Filter Media Comparison                             16
          Effect of pH                                        16
          Summary                                             18
VII     References                                            22
VIII    Publications                                          23
IX      Glossary                                              24

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                               FIGURES
No.                                                            Page
1    Pilot Process for Phosphorus Removal                        5
2   Settling Test Interface Versus Settling Time                9
3   BOD Removal                                                 13
4   Suspended Solids Removal                                    14
5   Phosphorus Removal                                          1~
6   Phosphorus Removal and pH Variation                         19
7   Correlation Between Phosphorus Residual and
    Fourth Stage pH                                             20
                                   IV

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                            TABLES





No.                                                            Page



1        Operating Conditions for Pilot System                   6



2       Activated Sludge Characteristics                         8



3       Occurrence of Nitrification in Step Aeration            10



4       Residuals in Effluents                                  12



5       Filtration Residuals                                    17

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                           ACKNOWLEDGMENTS


The pilot system was constructed,  maintained  and  operated by the
EPA-DC pilot plant staff under the direction  of Robert A. Hallbrook,
chief mechanic; Walter W.  Schuk, head  instrument  technician;
George D. Gray, chief operator; and Howard  P. Warner, chief analytical
chemist.

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                              SECTION I

                             CONCLUSIONS
1.  Step aeration with alum addition followed by secondary
sedimentation and tri-media filtration with the fourth  pass  mixed
liquor pH typically between 6.7 and 6.9 produced filtered effluent
residuals of 5 mg/1 of BOD (96% removal),  8 mg/1  of suspended solids
(92% removal) and 0.6  mg/1  of total  phosphorus (as  P, 93% removal)
for three months of stable operation.

2.  When operating with a fourth pass  pH between 6.3 and 6.6 the
system (with tri-media filtration)  removed 97% of the suspended solids,
BOD and total phosphorus from the primary  effluent.   The pollutant
residuals after filtration for twenty  days of continuous operation  in
this pH range were 4 mg/1 of suspended solids, 3.6  mg/1  of BOD and
0.23 mg/1 as P of total phosphorus.

3.  Dual-and tri-media filtration both provided effective tertiary
solids separation; however, the tri-media  filter consistently removed
between 5% and 10% more of the pollutant residuals  from the  secondary
effluent than did the  dual-media filter.

4.  Filter runs between 24 and 32 hours were maintained on a regular
basis, while filter runs exceeding 48  hours were possible with a
high quality secondary effluent.

5.  Fluctuations in the residuals of suspended solids and phosphorus
corresponded to similar fluctuations in the fourth  pass  mixed liquor
pH.  A definite relationship between pH and phosphorus  residual was
established indicating that above pH 6.6 a rapid increase in the
phosphorus residual occurred with increasing pH at  a given Al/P ratio.

6.  Inasmuch as operation with a mixed liquor pH of less than 6.2
caused an upset in the activated sludge, it appeared that optimum
performance of the mineral  addition  activated sludge process is
achieved by maintaining an average  final  pass pH between 6.3 and  6.6.

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                              SECTION II

                            RECOMMENDATIONS
In the present study the feasibility of mineral  addition to the
activated sludge process for phosphorus removal  was  demonstrated.  A
sequence of unit processes was established and information concerning
basic operational parameters and chemical  dose rates  was determined.

The study, however, was not intended to provide  complete design
criteria due to the nature of the pilot system itself.   It is  therefore
recommended that mineral addition to activated sludge with pH  control
and filtration included in the system be operated on  a  larger  scale to
determine important design parameters such as  realistic clarifier
overflow rates, air requirements and the effect  of a  diurnal flow  and
loading variation on the system (i.e. parameters which  cannot  be
meaningfully evaluated in a 2000 gallon per day  pilot system.)

Maintenance of the final pass pH in the relatively narrow range between
6.3 and 6.6 was required to produce consistently'low  phosphorus
residuals.  Equipment to automatically monitor and adjust pH to the
proper value will have to be developed and piloted to establish the
controllability of pH and chemical  requirements, as well as ,to confirm
the product quality observed in this study.   In  areas of relatively
low wastewater alkalinity, such as  the District  of Columbia, pH control
will require facilities to dose with both acid and base.  For
applications in areas where the wastewater alkalinity is sufficiently
high to insure that an excessive drop in pH will not  occur at  the
normal alum dosing rates, provisions for the addition of acid  will  be
all that is required.

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                              SECTION III

                             INTRODUCTION
The insolublization of phosphate ions in wastewater by the addition of
aluminum salts to the activated sludge process is a low capital  cost
method for phosphorus removal.  Barth and Ettinger (1) reported  that
sodium aluminate added to the aeration basin of an activated sludge
pilot plant removed 95% of the phosphorus from a supplemented waste-
water (0.5 mg/1 as P in the clarified effluent) at an aluminum to
phosphorus weight ratio of 1.5:1.  While an aluminum dose somewhat
in excess of the stoichiometric weight ratio of 0.87:1 was necessary
to obtain low phosphorus residuals, aluminum salt (mineral) addition
to activated sludge had the advantage of a lower precipitant dosage
than was required for an aluminum salt process incorporating a
separate tertiary step for phosphorus removal.  The improved settling
characteristics of the combined biological and chemical sludge was
also an advantage of mineral  addition.

In a similar bench-scale pilot study, Eberhardt and Nesbitt (2)
observed the effect of pH and filtration on phosphorus removal during
mineral  addition to the activated sludge process.  In studies with
domestic wastewater, operation with a mixed liquor pH of 6.0 and an
aluminum to phosphorus weight ratio of 1.8:1 produced the greatest
phosphorus removal after secondary clarification, averaging residuals
of 0.5 mg/1 as P (96% removal).

Greater phosphorus residuals  in the secondary effluent were recorded
when operating with a mixed liquor pH between 6.1 and 6.8.  However,
laboratory filtration of the  effluent samples increased phosphorus
removals to greater than 99%, except when the pH was 6.8.

Miele (3) further confirmed the observation that phosphorus removal
efficiency depended on pH.  Short-term operation of a 1.8 million
gal/day activated sludge plant with an average aluminum to phosphorus
weight ratio between 1.4:1 and 1.8:1 produced phosphorus removals in
excess of 95%.  Jar tests indicated that greater phosphorus removal
occurred with decreasing pH in the pH range of 5-8.

In the present study, alum (aluminum sulfate) was dosed at a constant
rate to a 2,000 gal/day activated sludge pilot plant.  In addition to
conventional secondary settling, filtration was used to remove
residual organic solids and particulate phosphorus.  The effect  of pH
on phosphorus removal was established.

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                              SECTION IV

              DESCRIPTION OF PILOT PLANT AND PROCEDURES

The pilot plant process (Figure 1) consisted of step aeration, clari-
fication, and filtration.  Primary effluent from the main District
of Columbia sewage treatment plant was fed at a constant rate of
2QQO gpd to a four pass step-aeration system.  A splitter box
distributed equal portions of the primary effluent to each of the
final three aeration passes.  The fourth pass mixed liquor flowed
by gravity to a circular settler, where it entered through a single
port on the periphery of the clarifier and was baffled downward.
The secondary settled solids were returned to the head of the first
pass for reaeration.  Because of the relatively small capacity of
the clarifier, solids were wasted from the first pass.

The overflow from the secondary clarifier was pumped to two pressurized
plexiglas filter columns (6.5-inch i.d.) which were operated in parallel.
One filter had a dual-media bed, packed with 18 inches  of 0.9 mm.  coal
on top of 6 inches of sand (equal quantities 0.40-0.45  mm.  sand and 0.8-
1.20 mm. sand).  The other filter was a "Neptune Microfloc"* multi-media
filter consisting of 25 inches of coal followed by ten  inches of sand
and five inches garnet (manufacturer's designation MF197).   The flow
rates, detention times, and hydraulic loadings for the  processes  are
described in Table 1.

Alum (A12(S04)3 ' 14O) in an aqueous solution was added to the  fourth
pass mixed liquor to precipitate phosphate ions from the sewage.   With
the exception of one short period, alum was dosed at a  constant rate
for the entire operation.  The alum dose was based on a 2:1  A1:P  weight
ratio and an influent phosphorus concentration of 8.2 mg/1  as P.   An
emergency lime feed system was installed after the third month of
operation to increase the buffer capacity of the wastewater during
periods of low alkalinity by adding 25 mg/1 of lime to  the first  pass
mixed liquor.

Analytical  Procedures

All samples for analysis were manually composited over  24 hours.   During
compositing, all samples were stored at 3°C to minimize additional
biological  activity.

In the laboratory, the total phosphorus were determined by the
persulfate method (4), BOD's by the probe method (5), ammonia (5)
and nitrate-nitrite (6) were determined on the Technicon Automatic
Analyzer, and the total organic carbon (TOC) was measured on a Beckman
Carbonaceous Analyzer (7).  All other analyses employed Standard  Methods
(8).

*  Mention  of a product does not constitute EPA endorsement of the
   product.

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 PRIMARY
Fl
~i
      •ALUM
                                                      WASTE
                       * EFFLUENT*
             Figure 1. Pilot Process for Phosphorus Removal

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           Table 1.   Operating Conditions for Pilot System






Process                      Flow                Loading Rate







Secondary Settling       1.45 gal/min.        425 gal/(day)(sq.ft.)



Filtration               0.56 gal/min.        2.4 gal/(day)(sq.ft.)
  Aeration Time - 4.0 hours (based on 1.45 gal/min.  flow)



  Return Solids Rate - 42%

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                              SECTION V

               OPERATION OF THE ACTIVATED SLUDGE PROCESS
The alum activated sludge process was started in August 1970,  using
primary effluent from the District of Columbia plant and seed
biological  solids from an existing step aeration process.   Two weeks
later, alum addition was begun; scheduled wasting of secondary settled
solids began in the last week of August.

The operation of the activated sludge for the five-month period
following the month of start-up is summarized in Table 2.   During  the
study, the Solids Retention Time (SRT) in aeration was operated at or
above 5 days because operation of activated sludge on the  District
of Columbia wastewater produced filamentous growth and bulking solids
for operation with SRT's between two and five days.   The average MLSS
for the first four months t>f operation was 6,600 mg/1.  In January,
increased solids wasting reduced the MLSS to less than 5,000 mg/1.
and the SRT to 5.0 days.  The percent volatile solids in the mixed
liquor stabilized at approximately 60%.  With an average sludge volume
index of 45 for the entire operation, the.solids were readily  settleable,

Because of the relatively small scale of the system, meaningful
clarification rates were not produced in the secondary clarifier.
Settling rates were determined in one liter graduate cylinders. In a
typical settling test, at a mixed liquor temperature of 48°F(lowest
operating temperature), the initial  portion of the subsidence  was
characterized by unhindered settling (Figure 2).  After approximately
3.5 minutes, zone settling developed with a rate (based on the initial
portion of hindered .settling) of 13.2 ft/hr. (2,380 gal/(day)(sq.ft.)).

The presence of almost 8 mg/1 of NO^-N in the secondary effluent
during September (Table 3) indicated that substantial nitrification was
possible in a mineralized activated sludge with a final  stage  pH of
less than 7.  Gradually decreasing nitrate concentrations  with
corresponding increases in NH3-N were recorded as the temperature
dropped during October and November.  An upset in the activated sludge
system in November destroyed many of the nitrifying organisms  and
nitrification was greatly reduced.  The cold temperatures  experienced
during December and January prevented the recovery of the  nitrifiers
and nitrification never returned to the levels seen prior  to the upset.

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                                  Table 2.  Activated Sludge Characteristics
         September, 1970
         October, 1970
         November, 1970
         December, 1970
         January, 1971
Temp.
°F
81°
75°
680
630
54°
MLSS
(% volatile)
mg/1
6900 (59%)
6560 (59%)
5720 (60%)
7080 (59%)
4930 (60%)
SVI
65
36
37
44
44
SRT
days
6.5
8.7
6.4
7.4
5.0
F/M
(Ib.BOD used/day
Ib. MLVSS
0.15
0.16
0.19
0.18
0.24
CO

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   1000


    800

 CO
 £ 600



    400
i


    200


      0
i  i  i  i
T  I  n|~~l I  I  I  |  I  I   I  TT
                                                  I  I  I  iTT
         I  i  i  i  i  I
                            1000 ML = 1.15 FT.
                            TEMPERATURE - 9°C.
                            MLSS = 3980 MG/L
i  i  i   i  I  i  i  i  i   I  i  i  i  i  I  i  i  i  i  I  i  i   i  i  I  i  i  i   i
        5
                   10
                                       15
                                   MINUTES
                              20
25        30
         Figure 2. Settling Test Interface Versus Settling Time

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                             Table 3.  Occurrence of Nitrification in Step Aeration
        September, 1970



        October, 1970



        November, 1970



,_»       December, 1970
o


        January, 1970
Temp.
°F
81°
75°
68°
63°
54°
SRT
days
6.5
8.7
6.4
7.4
5.0
Total Nitrogen
Primary Influent
mg/1
25.8
27.8
26.2
27.1
26.5

TKN
mg/1
8.5
12.6
13.2
16.8
16.6
Residuals
NH--N
mg/i
6.9
10.2
11.0
15.1
14.3

NO--N
mg/1
7.9
7.4
6.5
3.8
3.4

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                               SECTION VI

                      TEST RESULTS AND DISCUSSIONS
 Pollutant  Residuals
The activated sludge system with mineral addition performed well during
the entire operation (Table 4).  The slightly reduced performance of the
system in November was caused by an upset in the activated sludge.

Good secondary treatment with filtration on stream was obtained during
October, December and January.  During these three months, secondary
treatment alone removed 89% of the primary effluent BOD with filtration
increasing the total removal to 96%.  These treatment efficiencies
produced average BOD values of 11.9 mg/1 in secondary effluent and
5.0 mg/1 in the filtered (tri-media) effluent.   An average TOC residual
of 17.1 mg/1 in the secondary effluent represented 82% removal from the
primary effluent.  Filtration (tri-media) increased the TOC removal by
5% producing water containing an average of 11.8 mg/1 of TOC.   Similarly,
secondary treatment and filtration (tri-media)  removed 82 and 90% of
the influent COD, respectively, with COD residuals of 48.9 mg/1 in the
secondary effluent and 27.4 mg/1 in the filtered effluent.

Secondary treatment removed 68% of the suspended solids from the primary
effluent for an average residual of 33 mg/1.  Filtration (tri-media)
removed an additional 24% of the suspended solids with an average
residual of 8 mg/1.  Total phosphorus residuals averaged 1.9 mg/1 as P
(78% removal) in the secondary effluent and 0.61 mg/1 (93% removal)
after filtration (tri-media).

Operations during December provide an indication of typical variability
in pollutant removal.  BOD residuals ranged from 6.8 to 19.2 mg/1 in the
secondary effluent with an average of 12.0 mg/1 for the month (Figure 3).
Similarly, daily BOD residuals in the filtered (tri-media) effluent
varied from 10.5 to less than 1 mg/1 for a monthly average of 4.9 mg/1.
The suspended solids in the secondary effluent (Figure 4) exhibited
greater daily variability than residual BOD ranging between 12 and 54
mg/1 (33 mg/1 average).  Filtration (tri-media) reduced the solids to an
average of 8 mg/1, although the quality of the  filtered (tri-media)
effluent (daily residuals from 1 to 29 mg/1) reflected the variation in
amount of suspended solids carried over from the secondary clarifier.
The phosphorus removal exhibited an even greater daily variability than
did the solids removal, with residuals ranging  between 0.9 and 4.6 mg/1
as P in the secondary effluent and between 0.07 and 2.9 mg/1 as P after
tri-media filtration (Figure 5).  Nevertheless, phosphorus residuals
averaged 1.9 mg/1 as P in the secondary effluent and 0.65 mg/1 as P in
the filtered effluent.
                                  11

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                     Table 4.   Residuals in Effluents
September
  Primary
  Secondary
October
  Primary
  Secondary
  Filtered (tri-media)
November
  Primary
  Secondary
  Filtered (tri-media)
December
  Primary
  Secondary
  Filtered (tri-media)
January
  Primary
  Secondary
  Filtered (tri-media)
BOD
mg/1
107
12.2
121
16.2
5.2
128
17.8
8.1
140
12.0
4.9
127
13.5
5.0
TOC
mg/1
99
11.3
101
17.5
12.1
92
20.8
13.6
91
16.4
11.4
85
17.7
11.9
COD
mg/1
260
33.9
304
54.3
28.1
280
58.7
32.6
260
47.0
26.0
255
45.5
28.1
SS
mg/1
105
19
120
41
9
97
50
16
94
33
8
96
26
7
P
mg/1
8.2
1.4
9.1
2.2
0.58
8.7
2.9
0.97
8.5
1.9
0.65
8.2
1.6
0.61
                                  12

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160

140

120

100

 80

 60

 40

 20

  0
    1
       15        20
      DECEMBER
Figure 3.  BOD Removal
30

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5
10
  15          20
DECEMBER
30
          Figure 4.  Suspended Solids Removal

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10
 0
                      10          15         20
                                DECEMBER
                        Figure 5.  Phosphorus Removal
25
30

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Filter Media Comparison

Comparing the different filters, tri-media filtration removed between
5 and 10% more of the pollutant residuals from the secondary effluent
than did dual-media filtration (Table 5).  For the four months of filter
operation, the tri-media effluent averaged 10 mg/1 of suspended solids
and 0.7 mg/1 as P of total phosphorus; the dual-media effluent,13 mg/1
of suspended solids  and 0.89 mg/1  as P of total  phosphorus.  The
phosphorus concentration in the tri-media filter effluent regularly
duplicated the "soluble" phosphorus residual  as determined by 0.45 >u
millipore filtration.

Similar differences in effluent quality from the two types of filters
were observed with respect to the organic residuals (BOD, TOC, and COD).
The residuals of BOD, TOC, and COD in the tri-media filter effluent
averaged 5.8, 12.2, and 28.7 mg/1,  respectively,  the same residuals
after dual-media filtration averaged 6.9, 13.2, and 34.4 mg/1.

With good quality secondary,effluent (25-40 mg/1  suspended solids),
filter runs between 24 and 32 hours occurred regularly.  Filter runs in
excess of 48 hours were possible during those periods when good
phosphate precipitation and effective secondary solids capture in the
settlers produced a very high quality secondary effluent (15-20 mg/1
suspended solids).  During high solids carryover from the settlers
(> 50 mg/1), filter runs of 24 hours permitting solids breakthough
still selectively removed phosphorus.

The Effect of pH

The fourth pass mixed liquor pH for the five months of operation
normally varied between 6.7 and 6.9.  However, lower residuals of
suspended solids and prganics, as well as phosphorus, were recorded
in the secondary and filtered effluents when operating with a fourth
pass mixed liquor pH of less than 6.6.  As an example of favorable pH
operation, the twenty-day period from October 21 to November 9, at a
pH of approximately 6.5 in the fourth pass mixed liquor, averaged
filtered residuals of 4 mg/1 for suspended solids, 3.6 mg/1 for BOD,
and 0.23 mg/1 as P for total phosphorus.

As the fourth pass pH increased to 7 and above, a deterioration of
effluent quality was observed visually as well as by increased
pollutant residuals.  Operation at a relatively high pH (greater than
6.9) generally produced a fine turbid haze in the secondary effluent
which was difficult to remove by filtration.   During periods of high
pH operation, the greatest increases were recorded in the residuals of
suspended solids and phosphorus while the residual organic concentrations
were less affected.

Using the January fourth pass pH and filtered phosphorus residual- as
references, a steady increase in the phosphorus residual corresponded


                                  16

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October
                     Table 5.  Filtration Residuals
                      BOD       TOC       COD       SS        P
                      mg/1      mg/1      mg/1     mg/1     mg/1
   Dual-media          5.2      11.7      35.5      14      0.68
   Tri-media           5.2      12.1      28.1       9      0.58

November
   Dual-media         10.4      15.6      36.8      19      1.2
   Tri-media           8.1      13.6      32.6      16      0.97
December
   Dual-media          6.3      12.6      28.6      11      0.97
   Tri-media           4.9      11.4      26.0       8      0.65
January
   Dual-media          5.8      12.8      32.6       8      0.75
   Tri-media           5.0      11.9      28.1       7      0.61
                                  17

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to a similar rise in pH (Figure 6).   Furthermore, many local  peaks in
the residual phosphorus concentration reflected similar peaks in the
pH.  Inasmuch as alum was fed at a constant rate, the only changes in
the A1:P ratio were caused by normal  fluctuations in the influent
phosphorus concentration and the A1:P ratio randomly oscillated about
the 2:1 value chosen for the study,  averaging 1.99:1 for the  month.

A definite relationship between the  fourth pass pH and the filtered
phosphorus residual is indicated by  the smooth curve drawn through the
data (Figure 7).  The figure clearly defines the steady rise  in
phosphorus residual with pH.  Furthermore, this increase in phosphorus
residual is particularly rapid above pH 6.6.

Operation at pH below 6.2, however,  produced an upset in the  biological
system.  This upset occurred in November when the decreased buffer
capacity of a rain-diluted sewage caused an excessive drop in pH at the
2:1 A1:P ratio being used for the study.   Fourth pass pH values of 6.1
or less were recorded on several  occasions during the second  week in
November.  The pH values of the other mixed liquor passes, which
normally exhibited the pH of the influent wastewater, were also reduced
to the same level as the fourth pass pH.

On November 12, the A1:P ratio was reduced to stabilize the pH above
6.5 until the buffer capacity of the sewage returned to normal levels.
However, the activated sludge mixed  liquor had already been upset.
When viewed under a microscope, the  mixed liquor during this  period
appeared to be poorly bio-flocculated and the MLSS dropped from
7200 mg/1 to a low of 3850 mg/1 on November 22.  The emergency lime
feed system was installed shortly thereafter and prevented a  similar
occurence during a period of heavy rainfall in December.

The information derived from this study indicates that pH control is
essential to consistently produce low phosphorus residuals from the
alum addition activated sludge process.  The control of pH in the
relatively narrow range between 6.3  and 6.6 would necessitate alternate
dosing of acid and base as required  by the prevailing conditions of pH
and alkalinity.  With proper pH control,  it is likely that efficient
phosphorus removal can be achieved using an Al:P ratio considerably
less than 2:1.

Summary

Step aeration with alum addition followed by secondary-sedimentation
and tri-media filtration with the fourth  pass mixed liquor pH typically
between 6.7 and 6.9 produced filtered effluent residuals of 5 mg/1 of
BOD, 12 mg/1 of TOC, 27 mg/1 of COD, 8 mg/1 of suspended solids, and
0.6 mg/1 of total phosphorus (as P)  for three months of stable operation.
These  residuals correspond to removals of 96, 87, 90, 92 and  93%,
respectively, of the pollutants in the influent primary wastewater.
                                18

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   7.0
   6.5
     ,'    DOSED MIXED LIQUOR
cs
ts>
    1.0
       1         5
   15
JANUARY
20          25
30
                      Figure 6.  Phosphorus Removal and pH Variation

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6.0       6.2
        Figure 7.  Correlation Between  Phosphorus  Residual
                       and Fourth Stage pH
                                   20

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When operating with a fourth pass pH between 6.3 and 6.6,the pilot
system (with tri-media filtration) removed 97% of the suspended solids,
BOD, and total phosphorus from the District of Columbia primary
effluent.  The pollutant residuals after filtration for the twenty days
of continuous operation in this pH range were 4 mg/1 of suspended solids,
3.6 mg/1  of BOD and 0.23 mg/1 as P of total phosphorus.

Dual and tri-media filtration both provided effective tertiary solids
separation, however, the tri-media filter consistently removed between
5 and 10% more of the pollutant residuals from the secondary effluent
than did the dual-media filter.  Filter runs between 24 and 32 hours
were maintained on a regular basis.   Furthermore, with high quality
secondary effluent, filter runs exceeding 48 hours were possible.

Fluctuations in the residuals of suspended solids and phosphorus
corresponded to similar fluctuations in the fourth pass mixed liquor
pH.  A definite relationship between pH and phosphorus removal was then
established, indicating that above pH 6.6 a rapid increase in the
phosphorus residual occurred with increasing pH.   However, operation
with a mixed liquor pH of less than 6.2 caused an upset in the
activated sludge.  Therefore, it appears that optimum performance of
the mineral addition activated sludge process is  achieved  by main-
taining an average fina1 stage pH between 6.3 and 6.6.
                                 21

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                              SECTION VII

                               REFERENCES
1.  Barth, E.F., and Ettinger,  M.B.,  Journ.  Water Poll.  Control  Fed.,
    39, 1362, 1967.

2.  Eberhardt, W.A., and Nesbitt,  J.B.,  Journ.  Water Poll.  Control
    Fed., 40_, 1239,  1968.

3.  Miele, R., "PO^  Removal  by  Aluminum  Addition  to  Activated Sludge."
    Report from FWPCA at Pomona Water Renovation  Plant No.  1
    (July 1968).

4.  Gales, M., Julian, E.,  and  Droner, R., Journ.  of Am.  Water Wks.
    Assoc., 58, 1363 (1966).

5.  "FWPCA Methods for Chemical  Analysis  of  Water and Wastes", U.S.
    Dept. of the Interior,  Fed.  Water Poll.  Control  Adm.,  Cincinnati
    (November 1969).

6.  Kamphake, L.,  Hannah, S., and  Cohen,  J.,  Water Res., ]_,  205  (1967).

7.  Schaeffer, R.B., et al.,  Journ. Water Poll. Control  Fed.,  37_, 1545
    (1965).

8.  "Standard Methods for the Examination of Water and Wastewater."
    12th Ed., American Public Health  Association,  New York  (1965).
                               22

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                            SECTION VIII


                            PUBLICATIONS
Hais, A.B., Stamberg, J.B., and Bishop,  D.F.,  "Alum Addition  to  Activated
Sludge with Tertiary Solids Removal."  Presented  at the  68th  National
Meeting of the AIChE, Houston (March  1971).

Hais, A.B., Stamberg, J.B., and Bishop,  D.F.,  "Alum Addition  to  Activated
Sludge with Tertiary Solids Removal,  "Chemical  Engineering  Progress
Symposium Series, 68, (1972).
                                 23

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                              SECTION IX


                               GLOSSARY

Biochemical Oxygen Demand (5 day, BODr) - Measure of the quantity of
carbonaceous organic material usable 3s a source of food by aerobic
organisms present in a water.

Chemical Oxygen Demand (COD) - Measure of the Quantity of chemically
oxidizable compounds present in a water.

Total Organic Carbon (TOC) - Measure of the soluble and particulate
organic carbon present in a water as determined by the amount of COg
formed by combustion at 950°C.

Total Kjeldahl Nitrogen (TKN) - Measure of the ammonia-nitrogen and
organic nitrogen present in a water.

Suspended Solids (SS) - Measure of the solids retained by a standard
glass fiber filter and dried to constant weight, at 180°C.

Activated Sludge - The contacting of a liquid waste with  a biological
floe to convert one or more of the soluble wastewater components  to a
particulate form.

Mixed Liquor - The mixture of biological  floe and wastewater in an
activated sludge reactor.

Mixed Liquor Volatile Suspended Solids (MLVSS) - Measure  of the mixed
liquor suspended solids combusted after ignition at 600°C; measures
the organic fraction of the suspended solids  concentration and is  an
approximation of the quantity of micro-organisms present.

Step Aeration - An activated sludge process in which the  influent
wastewater is fed in equal volumes at 1/4, 1/2 and 3/4 points  along
the length of the reaction basin.

Sludge Volume Index (SVI) - The volume in mi Hi liters occupied by
1 gram of activated sludge after settling the mixed liquor for
30 minutes.

Zone Settling - The type of sedimentation displayed by flocculant
suspensions of intermediate concentration in  which the particles  are
close enough together to permit interparticle forces to hold the
particles in a fixed position relative to each other.

Bulking Solids - An activated sludge mixed liquor which,  primarily due
to the shape of the particles in the floe, displays poor  compaction
characteristics upon settling.
                                  24

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   Primary Effluent - Raw wastewater from which  the  settleable and
   floatable matter has been removed by sedimentation.

   Nitrification   A biological process in which  ammonia  is  converted
   first to nitrite and then to nitrate.

   Solids Retention Time -            Ib. VSS under  aeration
                               (Ib. VSS leaving system  in  underflow
                                wasting and secondary effluent)/day
U. S. GOVERNMENT PRINTING OFFICE : 1973--5I»6-310/79
                                     25

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SELECTED WATER
RESOURCES ABSTRACTS

INPUT TRANSACTION FORM
                                              | !„ Report No,
                                          3. Accession No.
                                          w
 4. Title
       Alum Addition  to  Activated Sludge with  Tertiary
       Solids Removal
 ?. Author(s)
   Hais, Alan B., Stamberg,  John B. and Bishop,  Dolloff F.
   EPA-DC Pilot Plant
   Department of Environmental  Services
   Government of the District of Columbia
   5000 Overlook Ave.  S.W.
   Washington, ..P.p.... .2.0032.. _,,,„„ ....... „..,
                                           5. Report Date

                                           6.

                                           8. Perfofinittg Organization
                                             Repoyf Na,
                                           10.- Project No.
                                             11010 EYM
12.
15. Supplementary Notes
                                           11. Contract/Grant No.

                                          .^ 14-12-818.

                                           I', fyjje of-Report and
                                             IHsied Covered
                  Environmental Protection Agency report number  EPA-670/2-73-037,
                  August 1973.
  'the activated sludge system was operated with 4.0 hours aeration  time (based on the
   influent flow) and  an overflow rate  in  the  secondary settler of 425 gal/(day)(sq.ft.).
   Alum was dosed assuming an influent  phosphorus concentration, of 8.15 mg/1 as P.  Lime
   (25 mg/1) was added to the mixed liquor to  stabilize the wastewater during periods of
   low alkalinity.   The dual-media filter  (24-inch bed depth) and the tri-media filter
   (40-inch bed depth), each loaded with secondary effluent at 2.4 gal/(min.)(sq.ft.),
   regularly exhibited filter runs between 24  and 32 hours.

   When operating the  step aeration with the usual final stage mixed liquor pH (6.7-6.9),
   the complete system with tri-media filtration removed 92% of the  suspended solids,
   96% of the BOD and  93% of the phosphorus from the primary effluent.  Daily fluctu-
   ations in the final pass pH, however, corresponded to similar fluctuations in
   phosphorus removal.  Furthermore, the removal of suspended solids, BOD and phosphorus
   all increased to  97% during those periods when the final pass pH  was between 6.3 and
   6.6.  Operation at  pH below 6.2 caused  an upset in the activated  sludge.
 17a. Descriptors

   Hydrogen Ion Concentration
   Activated Sludge
   Filtration
   Phosphates
 17b. Identifiers

   Aluminium Phosphate Precipitation
   Alum Addition*
   Step Aeration*
   Filtration of Secondary Effluent*
   Multi-media Filters
 lie. COWR.R Field & Group
   05D
             Wastewater Treatment
             B.O.D.
             Suspended Solids
 3.8, Availability
19, Security Class.
   (Report)

20. Security Class,
   (Page)
21, No. of
   Pagss

22. Price
Send To:


WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D.C. 20240
 Abstracts Dolloff  F.  Bishop
              Institution
   Environmental  Protection Agency
WRSIC 102 (REV. JUNE 1971}

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