EPA-600/2-76-231
  September 1976
Environmental Protection Technology Series
TREATING WOOD PRESERVING PLANT WASTEWATER
                                      BY  CHEMICAL AND
                                   BIOLOGICAL  METHODS

                                      I
                                      55
                                      \

                                  Industrial Environmental Research Laboratory
                                       Office of Research and Development
                                       U.S. Environmental Protection Agency
                                              Cincinnati, Ohio 45268

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have  been grouped  into five series. These five broad
categories were established to facilitate further development 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
demonstrate  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.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                             EPA-600/2-76-231
                                             September 1976
  TREATING WOOD PRESERVING PLANT WASTEWATER
     BY CHEMICAL AND BIOLOGICAL METHODS
                     by

               John T. White
             T. A. Bursztynsky
               John D. Crane
             Richard H. Jones
Environmental Science and Engineering, Inc.
           Gainesville, FL  32604
            Grant No. 12100 HIG
              Project Officer

               Victor Dal Ions
Industrial  Environmental  Research Laboratory
          Con/all is, Oregon  97330
INDUSTRIAL ENVIRONMENTAL  RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S.  ENVIRONMENTAL PROTECTION AGENCY
          CINCINNATI,  OHIO  45268

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                             DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, 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 co-mercial products constitute
endorsement or recommendation for use.
                                ii

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                                 FOREWDRD
     When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on
our health often require that new and increasingly more efficient pollution
control methods be used.  The Industrial Research Laboratory - Cincinnati
(IEKL-CI) assists in developing and demonstrating new and improved methodo-;
logics that will meet these needs both efficiently and economically.

     "Treating Wood Preserving Plant Wastewater By Chemical And Biological
Methods" was a part of the Industrial Pollution Control Division's program
to develop and demonstrate new technology for the treatment of industrial
wastes.  This project demonstrated the biological treatment of wood pre-
serving wastes containing pentachloropenols and creosote using complete
mixed activated sludge.  The study showed that the system could obtain BOD
removals of 90 percent and phenol removals of 99 percent.  The information
will be of value to consultants and industry concerned with installation of
treatment facilities to meet more rigid effluent standards.  For further
information, please contact the Food and Wood Products Branch of the In-
dustrial Environmental Research Laboratory, Cincinnati.
                             David G. Stephan
                                 Director
              Industrial Environmental Research Laboratory
                                Cincinnati
                                     in

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                                 ABSTRACT
     A completely mixed activated sludge system was designed for a wood
preserving plant with an average daily wastewater flow of 27,000  /day
(7,150 gal/day), a BOD concentration of 1,100 mg/], and a phenol concen-
tration of 120 mg/1.  Included in the design were capabilities for pre-
chlorination and post-chlorination.  The activated sludge system  lone was
capable of removing 90 percent BOD, 75 percent COD, 99 percent phenol, and
76 percent pentachlorophenol.  Shock loadings had minor effects on BOD and
COD removals but reduced the phenol removal and completely prevented penta-
chlorophenol removal.

     Post-chlorination dosages of over 50 mg/1 resulted in reductions of
50 and 52 percent for phenol and pentachlorophenol, respectively, during
the study.  The Safranin method was used for measuring penta.  Later fol-
low-up work by Kbppers using vapor phase chromatography with electron de-
tection showed penta reductions of 5 mg/1 to 0.1 mg/1.  There was no reduc-
tion of COD.  A pre-chlorination study showed no removal of phenol, penta-
chlorophenol, or COD at the level studies in the full scale plant.  Labora-
tory pre-chlorination studies showed removal of phenol and pentachloro-
phenol at chlorine dosages in excess of 250 mg/1.

     This report was submitted in fulfillment of EPA Grant No. 12100 HIG
by Environmental Science and Engineering, Inc., Gainesville, Florida, for
Kbppers Company, Inc., Pittsburgh, Pennsylvania, under partial sponsor-
ship of the Water Quality Office, Environmental Protection Agency.  The
study was completed as of July 1974.
                                      IV

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                       TABLE OF CONTENTS





SECTION                                                        PAGE NO.



               ABSTRACT                                            iv



               ACKNOWLEDGEMENTS                                     x



   I           CONCLUSIONS                                          1



  II           RECOMMENDATIONS                                      2



 III           INTRODUCTION                                         3



  IV           LITERATURE REVIEW AND PRELIMINARY STUDIES            8



   V           MATERIALS AND METHODS                               40



  VI           RESULTS AND DISCUSSION                              54



 VII           REFERENCES                                          77



VIII           GLOSSARY                                            83



  IX           APPENDIX                                            85

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                               TABLES


No.                                                                Page

 1         Efficiencies of Oil Separation Processes                  8

 2         Effect of Lime Flocculation on COD and Phenol
           Content of Treating-Plant Effluent                       11

 3         Threshold Toxic Levels for Continuous Dosages  in
           Aerobic Treatment Processes                              11

 4         Chlorination of Phenolic Materials                       14

 5         Effect of Chlorination of Pentachlorophenol  Waste
           on COD                                                   21

 6         Substrate Removal at Steady-State Conditions in
           Activated Sludge Units Containing Creosote Wastewater    24

 7         Reduction in Pentachlorophenol and COD in Wastewater
           Treated in Activated Sludge Units                        26

 8         BOD,  COD, and Phenol Loading and Removal Rates for
           Pilot Trickling Filter Processing a Creosote
           Wastewater                                               29

 9         Relationship between BOD Loading and Treatability
           for Pilot Trickling Filter Processing a Creosote
           Wastewater                                               30

10         Sizing of Trickling Filter for a Wood Preserving Plant    31

11         Average Monthly Phenol and BOD Concentrations  in
           Effluent from Oxidation Pond                             34

12         Results of Laboratory Tests of Soil Irrigation Method
           of Wastewater Treatment                                  36

13         Reduction of COD and Phenol Content in Wastewater
           Treated by Soil Irrigation                               37

14         Analytical Data from Pre-Design Study                    42

15         Revised Operating Schedule                               51

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                         TABLES CONTINUED

No.                                                                Page
16         Schedule of Analyses                                     52
17         Startup and Stabilization Data                           55
18         Effects of Shock Loading                                 57
19         Results of Loading Rate Variation                        59
20         Laboratory Post-Chlorination Studies                     64
21         Effects of Full  Scale Post-Chlorination                  67
 A         Daily Log Summary                                        90
 B         Post-Chlorination                                        97
                                  vii

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                             FIGURES
 No.                                                                 Page

  1          Original  Wastewater  Treatment  Flow  Diagram,
            Koppers  Company,  Carbondale            "                    6

  2          Effect of Detention  Time on Oil  Removal  by Gravity
            Separation                                                9

  3          Reaction  Scheme for  the Chlorination of  Phenol           13

  4          Observed  Rates of Chlorination of Phenol and
            Chlorophenols                                            16

  5          Chlorination of Phenol and the Chlorophenols Formed
            at pH7                                                   17

  6          Chlorination of Phenol and the Chlorophenols Formed
            at pH 8                                                  18

  7          Chlorination of Phenol and the Chlorophenols Formed
            at pH 9                                                  19

  8          Determination of Reaction Rate Constant for a Creosote
           Wastewater                                               23

  9         COD Removal from a Creosote Wastewater by Aerated
           Lagoon without Sludge Return                             25

10         Phenol Content in  Oxidation Pond Effluent before and
           after Installation in June 1966 of Aerator               33

11         Relationship between  Weight of Activated Carbon Added
           and Removal of COD and Phenols from a Creosote
           Wastewater                                               39

12         Flowrate  Variation with Time                             41

13         Percent Dilution vs.  BOD                                 45

14         Schematic of "Package" Treatment System                  %Q

15         Influent  and Effluent Phenol Concentration                63
                                 vm

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                        FIGURES CONTINUED

No.                                                                Page
16         Chlorine Residuals with Time                             65
17         Effects of Chlorine on Pentachlorophenol  Concentrations
           as Measured by Safranin Method                           66
18 (a,b)   Chlorine Persistence                                     69,70
19         Effect of Chiorination on Phenolic Concentration
           of Raw Wastewater with Activated Carbon                  71
20         Effect of Chiorination on Penta Concentration of Raw
           Wastewater with Activated Carbon                         72
21         COD Removal in the Activated Sludge Process              75
                                   ix

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                         ACKNOWLEDGEMENTS
ENVIRONMENTAL SCIENCE AND ENGINEERING, 1C.

     Environmental Science and Engineering, Inc.,  (ESE) of Gainesville,
Florida, as a consultant to Koppers Company/ provided overall supervision
of the project.  The concepts of the program and the treatment facilities
were developed by Dr. Richard H. Jones, P.E.  The Project Manager for
the first year of the project, Mr. T. A. Bursztynsky, P.E., was respon-
sible for planning the technical program.  Mr. John T. White supervised
much of the program and contributed substantially to preparation of this
report.  Mr. John D. Crane, P.E./ supervised preparation of the final
report and coordinated reviews by EPA and Koppers personnel.  Dr. W. S.
Thompson of the Forest Products Research Laboratory, Mississippi State
University, provided valuable consulting services to ESE.

KOPPERS COMPANY

     The program was partially funded by Koppers Company, Pittsburg,
Pennsylvania.  Mr. Marvin D. Miller, P.E., provided engineering
coordiviation for the project.  Mr. Roy Burke served as chief operator
for the treatment plant.  Considerable input to the project was also
provided by Mr. G. R. Tallon, Mr. C. W. Fisher, and Mr. Paul A. Goydan
and other members of the Environmental Engineering Section of the
Forest Products Division.  Mr. X. P. Laskaris served as Grant Director.

ENVIRDNMENTAL PROTECTION AGENCY

     The Project Officer was Mr. Victor Dallons.  Technical review
and assistance were provided by Mr. Ralph Scott and Mr. James H. Phillips.
The program was partially funded by EPA" under Grant No. 12100 HIG.

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                             SECTION I

                            CONCLUSIONS


     It was demonstrated that wastewater from a wood preserving process
utilizing creosote and pentachlorophenol (penta) as preservatives
can be effectively treated by a biological  system.   The process employed
was the complete mix activated sludge process.  The process obtained
a BOD reduction of 90 percent and a phenol  removal  efficiency of
99 percent.

     Pre-chlorination was effective in reducing both penta and phenol
in laboratory tests.  However, in the full  scale plant, a chlorine/
penta ratio of 300:1 was required to achieve an 80 percent reduction
in penta and the resulting excessive chlorine residuals caused operation-
al problems in the biological treatment system.

     Post-chlorination provided considerable color removal and reduced
the penta concentration from about 5 mg/1 to less than 0.10 mg/1.
It also accomplished slight reductions in phenol concentrations.  There
was no apparent reduction of COD.

     Shock loading tests showed a noticeable decrease in treatment
efficiency.  A doubling of the hydraulic loading rate resulted in
a decrease in phenol removal from 99 to 89 percent, in COD from
80 to 72 percent, and penta from 79 to 0 percent.  There was little
apparent effect on BOD removal efficiency.

     The usefulness of BOD as a pollutant parameter was limited as
the characteristics of the wastewater apparently inhibited the test,
e.g., an increase in dilution in the BOD test from 99.8 to 99.9 percent
resulted in an increase in BOD from 1000 to 2000 mg/1.

     The Safranin method for measuring pentachlorophenol was of
questionable reliability in testing the biological treatment effluent;
an increase in penta was indicated across the activated sludge unit.
It should be noted  that near the end of the study, vapor  phase
chromatography using electron capture  detection  was found  to be a
relative method for penta detection at low levels and  indicated that
the Safranin analyses were  generally high.

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                             SECTION II


                          RECOMMENDATIONS
      The activated sludge process provides a potential means as a
viable treatment alternative for the treatment of wood preserving
wastewater where limited land is available for spray irrigation and
lagooning.  For plants which have limited land available for spray
irrigation or lagooning, the activated sludge process could represent
the most cost-effective treatment alternative.  The activated sludge
process should be recommended to the wood preserving industry as a
potential means of meeting increasingly stringent effluent limitation
standards.

      A properly designed and operated preservative recovery system is
recommended before activated sludge treatment.  Also, a surge basin is
imperative for successful operation of the activated sludge system.

      The key design parameters for the complete mix system are as
follows:

      1.  Maximum BOD Loading =0.2 kg/day/kg MLSS
      2.  Maximum COD Loading =0.5 kg/day/kg MLSS
      3.  Maximum Penta Loading = 6.5 gm/day cu m
      U.  Minimum hydraulic detention time = Uo hours

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                            SECTION III

                            INTRODUCTION
     The Koppers Company, Inc., wood preserving plant at Carbondale,
Illinois, was selected by the Environmental  Protection Agency in 1971
as a site for a demonstration project to determine the design and
operating parameters for chemical and biological  treatment of both
creosote and pentachlorophenol  (penta) wastewaters generated by a wood
preserving operation.  The wastewater from the Carbondale plant is
representative of wood preserving wastewater in that it has a high
Biochemical Oxygen Demand (BOD) and contains wood preserving compounds
and extractives.  The successful  development and  operation of treatment
facilities at the Carbondale plant alleviates a specific pollution
problem at that plant and, more importantly, provides design parameters
for similar wood preserving plants.

BACKGROUND

     A number of methods have been developed to increase the service-
ability of wood*under conditions that promote decay, weathering, insect
destruction, or exposure to fire.  Treated or preserved wood is used  in
almost every facet of the construction industry.   Included among the
various wood materials that are treated with preservatives or fire
retardants are general lumber and timber, bridge  ties, foundation piles,
posts, crossties, utility poles, and marine construction wood.

Preservative and Fire Retardant Chemicals

     The various preservatives in common use throughout the industry
include creosote, creosote-coal tar, creosote-petroleum and pentachloro-
phenol solutions, as well as water-borne preservatives and fire retardants,
Creosote, creosote-coal tar, and pentachlorophenol-oil preservatives
are used at the Koppers Company facility at Carbondale; however, creosote
is the principal preservative used.

     Creosote, a distillate of tar produced by the carbonization of
bituminous coal, is used as a wood preservative both because it protects
wood against wood destroying organisms and has a  high degree of perse-
verance.  The main constituents of creosote are tar acids.

     The mixture of creosote with coal tar is primarily for railroad
ties and marine installations that require a preservative with water-
repelling properties.  Common ratios of creosote  to coal  tar are 80:20,
70:30, 60:40, and 50:50.

     Pentachlorophenol, frequently called "Penta", has a relatively low
solubility in water of about 15 mg/1 at normal water temperatures.
It is normally applied with a carrier petroleum oil.

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      Water-borne  preservatives  are  basically  heavy metal   compounds of
 copper,  chromate,  arsenite or arsenate, and zinc.  One of  the chief
 advantages  of this treatment is  that  the wood is  paintable.  Water-
 borne preservatives are not used at the Carbondale plant.

      Fire retardant formulations are  designed to  slow the  spread of
 fire  in  treated wood.  There are generally four formulations used in
 the  industry, with water used as the  preservative carrier.  Prior to
 the commencement  of the investigation, the Carbondale Facility used
 a  formulation containing a borate.

 Description of the Wood Preserving  Process

      The wood preserving process consists of  two basic steps:
 (1) preconditioning the wood to  reduce its natural moisture content
 and (2)  impregnating it with the desired preservatives.  The moisture
 reduction step may consist of (1) seasoning or drying the wood in
 large, open yards,  (2) kiln drying, or (3) steaming the wood for
 several  hours at elevated pressures to raise  the temperature of the
 moisture in the wood cells, and  subsequently  applying a vacuum to
 reduce the boiling point of the  water and evaporate it.  Nearly
 70 percent of the  wood produced  at  the Carbondale plant consists of
 crossties and switch ties which  are air seasoned in a storage yard.
 Approximately 10 percent of the  production at the Carbondale plant
 is pretreated by steaming.  Kiln drying requires from four to ten
 days  for pretreatment as compared to approximately 12 hours for
 steaming.

      Pretreatment  of wood by steaming may be done in one of three
 ways:  (1) open steaming, (2)  closed steaming, and (3) semi-closed
 steaming.  Open steaming consists of placing the wood in retorts and
 applying steam under pressure to the retorts for a period of several
 hours after which  vacuum is applied to remove wood water to the
 effluent system.    As the applied steam condenses on the wood and on
 the sides of  the retort, it drains down and is eventually removed
 as wastewater.  This condensate  tends  to collect preservatives  deposited
 in the retort from previous processing.

      In the closed teaming cycle, water is introduced into the  retort
 and the wood  is heated by steam generated by heating coils in the
 bottom of the retort.  At the end of the cycle ,  the water is with-
 drawn to a storage tank from which it  may be reused.   Eventually a
 blowdown of the steaming water is necessary because of the buildup
 of wood extractives.  At Carbondale this blowdown goes to the treatment
 system.

     The Carbondale plant uses four retorts for the application  of the
 semi-closed steaming cycle for wood pretreatment.   In this process,
 steam is added to the retort under vacuum to reduce the condensation
 temperature and lower the boiling temperature of water entrained in the
wood.   As steam condenses  in the retort, the liquid level  is allowed
 to build up until  it covers the heating coils  in the bottom of  the

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retort.  Live steam is then turned off and heat is applied to the coil.
At the end of steaming all water is discharged to waste and a vacuum
continues to be drawn to remove additional moisture from the wood.

     After the initial pretreatment step, there are several possible
ways to impregnate wood with preservatives.  For all creosote and
pentachlorophenol treatments not requiring a heavy saturation of pre-
servatives, the Carbondale plant uses the empty-cell Rueping process.
The full-cell process is used for treatment applications requiring
heavy saturations and for applications of fire retardant.

     The empty-cell Rueping process provides greater penetration of
preservative for net amounts of preservative absorbed and allows a
relatively high recovery of excess preservative.  The full-cell process
allows a higher saturation of preservative within the wood cells.

Wastewater Sources from the Wood Preserving Process

     The  basic wood preserving process generates wastewater .streams
consisting of condensed water from steaming, barometric leg cooling
water or surface condenser condensate, boiler blowdown, miscellaneous
wash water, p/ipe and tank leakages, and door pit drips.

     In the semi-closed steaming process, by which condensate is
allowed to accumulate in the retort until it covers the heating coils,
the condensate is wasted after oil recovery.  The wasted condensates
contain oil, phenolic compounds, and various wood extractives.

     When barometric legs or wet-type vacuum pumps are used to produce
vacuum, a water contaminated with the preservative used is generated.
The Carbondale facility employs a vacuum pump preceded by a surface
condenser.  Volatile gases are condensed on the surface condenser and
are discharged to waste.  The pump is sealed and lubricated by water
circulated through a small pond.

     Boiler blowdown is usually a stream of small volume, but one that
can be contaminated with various chemicals such as chromates and phos-
phates used for boiler water conditioning.

     Water used to clean equipment is normally contaminated with pre-
servative chemicals, oil and grease, and possibly detergents.

Existing Wastewater Treatment Facilities at Initiation of Project

     The wastewater treatment system in employment at the Carbondale
plant at the time of project initiation is illustrated in Figure 1.
Since specific preservatives are used in a retort, it is possible to
segregate wastewaters for pretreatment.  Wastewater from the penta-
chlorophenol oil  retorts is pumped to a decanter from which the
floating oil fraction containing pentachlorophenol is recovered. The
water fraction, after addition of a polymeric flocculant, is pumped

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                                           POND 4
                                 POND 3
POND 2
 POND  I
(RESERVE)
                                                                         SPRAY IRRIGATION  FIELD
                                                                   CREOSOTE SETTLER


x\
PENTA SEPAR
PENTA-OIL TO WORK TANK
^ DRAINAGE TROUGH
KTQR^/^
~\
i
S WORK AREA CONTRIBUTORY S
DRAINAGE FIELD
3
COMMON
SUMP
POLYMERIC
FLOCCULANT
.ADDITION
\
--
>
WORK TAf


^ AND SKI
	 ^- CREOSOTE
Ml Ml
TC
\ /SUMP
...
I 4 CREOSOTE


1 3 CREOSOTE




| Z PENTA

* 1

WS^

PENTA

^
Viy
RETORT

RETORT


RETORT

RETORT

^~&£
=^^-

I

1


1

1

.-•-'
«AO
                                                                            \
                                                                              DIVIDING WALL
                                                                      PRIMARY PENTA-OIL
                                                                         DECANTER
FIGURE 1.  Original Wastewater Treatment Flow Diagram  -  Koppers Company, Carbondale

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to a secondary recovery tank for further separation.  The  water from
the second tank is transferred to a common sump.

     Wastewaters are collected and handled separately in a similar manner
as the penta-oil wastewaters with recovered creosote returned to the
system.  The clarified water is discharged to the common wet well.

     The wastewater from the common sump is pumped to the set of four
lagoons which provides equalization, evaporation, and biological
oxidation.  A spray irrigation field provides final  treatment.

PROJECT OBJECTIVES

     The project objectives were to determine the design and operating
parameters of chemical  and biological  treatment of creosote and penta-
chlorophenol-oil wastewaters from a wood preserving plant.   The plan
of operation consisted of design, construction, and operation of treat-
ment facilities for the wastewaters generated by the Koppers Company
wood preserving plant located at Carbondale,  Illinois.   The operation
and  sampling and testing program would be supervised by Environmental
Science and Engineering, Inc.,  of Gainesville, Florida.
                                   -7-

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                            SECTION IV

            LITERATURE REVIEW AND PRELIMINARY STUDIES
     In order to best meet the objectives of the project, an extensive
review of the literature and other previous work related to the
treatment of wood preserving wastes was conducted.

PHYSICAL TREATMENT

     The first step in treating wastewater from a plant using creosote
or creosote solutions is usually settling and skimming, not so much for
treating wastewater, but to recover valuable preservatives.  The most
common type of separator in use by the industry is modeled after the
separator developed by the American Petroleum Institute (1) which
basically consists of a horizontal tank divided into three or more
compartments.  Heavy oils settle to the bottom of the tank and are
removed by a pump to a dehydrator.  Floating oils are removed by a
skimmer.

     The amount of entrained oils removed by separation equipment
depends in part on whether the oil is in a free or emulsified form.
Data on the percent efficiencies of several separators are presented
in Table 1 (2).   The variability of oil removal as a  function of
detention time was shown by Wallace, e_t. al_. (3), as illustrated in
Figure 2.

TABLE 1.  EFFICIENCIES OF OIL SEPARATION PROCESSES
                            Source of
                            Influent
                       Percent Removal
               Free Oils
              Emulsified Oils
API Separator
Raw Waste
60 - 99
Not applicable
Air Flotation without
Chemicals
Air Flotation with
Chemicals
Chemical Coagulation and
Sedimentation
API
Effluent
API
Effluent
API
Effluent
70
75
60
- 95
- 95
- 95
10
50
50
- 40
- 90
- 90
     The conventional oil-water separators discussed above remove only
free oils.  Emulsions may be broken by rotary vacuum filters or by
centrifugation.  Both of these methods have been tested at a few wood
preserving plants, but chemical methods involving flocculation and
sedimentation are the most widely used.

                                   -8-

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    10
   20
   30

h-

UJ
o

g 40

Q.
   50
UJ
ce

-J 60
o
   70
   80
  AVERAGE TEMPERATURE - 38° C
INITIAL OIL CONCENTRATION- 45 PPM. * 4P.P.M.
      0     40      80     120     160     200

       SEPARATION  TIME   IN  MINUTES
                    FIGURE 2
Effect of Detention Time on Oil Removal by Gravity Separation
                        -9-

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 CHEMICAL  TREATMENT

 Chemical  Precipitation

      The  effluent from  the settling and skimming tanks contains a
 considerable  amount of  emulsified oil and creosote.  This emulsion
 represents a  large portion of  the BOD in the wastewater; wastewaters
 containing emulsified oils often have oil concentrations in excess
 of  1000 mg/1  after separation  (4).

      Middlebrooks and Pearson  (5) found that 79 percent of the BOD
 and 80 percent of the COD in this type of wastewater could be removed
 by  chemical coagulation with the addition of approximately 2000 mg/1
 of  lime and alum.  However, the volume of sludge produced was almost
 40  percent.   Frank and  Eck (6) found similar results with sodium
 hydroxide and lime after polyelectrolytes alone failed to produce
 flocculation.  Although the treatment efficiencies were high, the
 problem of sludge disposal would suggest that another type of treat-
 ment  for  breaking the emulsion might be more feasible.

      Jones and Frank (7) achieved COD and BOD reductions of 83 and
 73  percent, respectively, in creosote wastewater using a single
 cationic polymer at a rate of 40 mg/1.  Anionic polymers failed to
 break the oil emulsions.  However, Simonsen (8) was successful in
 obtaining oil reductions in refinery wastewater of more than 95 percent
 by  the use of both anionic and cationic polyelectrolytes in combination
 with  bentonite clay.  There was no difference between the two types
 of  polymers in the results obtained.

     Thompson and Dust (9) found ferric chloride to be an effective
 flocculant for both creosote and pentachlorophenol  wastewaters with
 very narrow pH limits.   In the same study, from 0.75 to 2.0 gm/1  of
 lime appeared to be an optimum dosage for reduction of COD and phenol,
 as  shown in Table 2.

     Lime was also employed by Middlebrooks (10) in dosages of 2  gm/1
 to obtain reductions in COD of up to 70 percent in  creosote wastewater.
 Similar results were obtained with alum.   Both lime and alum were used
 by Gaspin (11) for treatment of creosote  wastewater previously de-
 emulsified with sulfuric acid.

     Treatment of wastewater containing heavy metals has been success-
 fully practiced for many years in various industries.   Chromium is
 found in wastes from metal  plating and finishing operations.   It  is
 present in rinse waters and chromic acid  baths and  in  spent baths
 from electroplating and anodizing processes.   Wastewaters from similar
 processes also contain  copper and zinc.

     Heavy metals  contained in  salt-type  preservatives and  fire
 retardants are toxic to microorganisms, even  when the  metals  are  in
 relatively low concentrations  (12)  (see Table 3).   Other studies  (13),
using a combination  of metals,  showed that the aeration phase  of  bio-
logical  treatment  can  tolerate  chromium,  copper, nickel,  and  zinc,  up

                                 -10-

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TABLE 2.  EFFECT OF LIME FLOCCULATION ON COD AND PHENOL CONTENT
          OF TREATING-PLANT EFFLUENT
COD
Lime
(qm/1)
0.0
0.25
0.50
0.75
1.00
1.25
1.50
PH
5.3
6.8
7.9
9.7
10.5
11.4
11.8
Cone.
(mg/1)
11,800
9,700
7,060
5,230
5,270
5,210
5,210
Percent
Removal
—
23
39
56
55
56
56
Phenol
(mg/1)
83
81
72
78
80
84
83
TABLE 3.  THRESHOLD TOXIC LEVELS FOR CONTINUOUS
          DOSAGES IN AEROBIC TREATMENT PROCESSES
Metal
Chromium (VI)
Copper
Nickel
Zinc
Wastewater Concentration
(mg/1)
10
1
1-2.5
5-10
                            -11-

-------
 to  a  total  heavy  metal  concentration  of  10 mg/1, either  alone or  in
 combination,  with about 5  percent  reduction  in  overall plant efficiency.
 Various  other studies  (14,  15,  16), both in  the laboratory  and  in the
 field, reached similar conclusions.

      Chemical  analyses to  determine heavy metal concentrations  should
 be  conducted  on the wastewater  from wood preserving  plants  using
 water-borne preservatives.   If  heavy  metal removal is necessary,
 chemical  treatment related  to the  specific ions present  is  applied.
 Usually  precipitation  of heavy  metals from wastewater is accomplished
 with  lime;  however, hexavalent  chromium  must be reduced  to  a trivalent
 state by ferrous  sulfate or sulfur dioxide prior to  lime precipitation.
 The use  of  sulfur dioxide has been described in detail by Chamber!in
 and Day  (17)  and  Fisher (68).

      A   bibliography dealing with  the removal of heavy metals was com-
 piled in  1949  by  Dodge and  Reamms  (18) and it has been estimated by the
 American  Wood  Preserver's Association  (19) that by 1959 some 500 addi-
 tional articles had been published on  the subject.   Detailed discussions
 of  heavy  metal removal  have also been  presented by Eckenfelder  (20)
 and Bliss (21).

 Chemical  Oxidation

      While  some information is  available on oxidation of phenols using
 peroxide, ozone,  and other chemical oxidants (22, 23), the vast majority
 of  literature  is  concerned with the oxidation of phenolics with chlorine,
 especially  as  related  to the water supply area.  It  has long been common
 knowledge that chlorination of  phenols may produce tastes and odors in
 water supplies.   Early  studies on  chlorination of phenols centered on
 chlorine  residuals and  removal of  tastes from water.   Based on ratios
 of  chlorine to phenol,  Ingols and  Ridenour (24) concluded that a quinone-
 like  substance was the  basic cause of  "phenol" tastes.  Their work
 postulated  a succession  of chlorination products which ultimately ended
 in  dichlor-quinone.  Further chlorination of dichlor-quinone was postu-
 lated to  rupture  the benzene ring  and  form maleic acid rather than
 completely  eliminate any residual  taste problems.

      Subsequent studies  by Ettinger and Ruchhoft (25) substantiated
 early work  showing increasing taste intensity with increasing chlorina-
 tion of phenols and then decreasing taste until no taste was noticeable
 and a chlorine residual  began to develop.  Comparative information was
 provided on the chlorination of various phenolic compounds and quantities
of  chlorine needed to eliminate detectable taste products.   Table 4
 indicates that a  chlorine to cresol ratio of 5:1 would be adequate to
 completely  form chlorination end products.  Pentachlorophenol  could
 be  oxidized by chlorine  at a 1:1 ratio.

     The first fact substantiated from early work of researchers was  the
progression of chlorination products  as illustrated in Figure  3.  In
more recent studies,  R. G.  Burttschell and co-researchers (26)  at the
 Robert A. Taft Sanitary Engineering Center uses paper chromatography  and
 infrared and ultraviolet spectrophotometry to determine  the actual  products

                                   -12-

-------
                 OH
                                                             Oxidation
FIGURE 3.   Reaction Scheme for the Chlorination of Phenol
                                 -13-

-------
 involved  in  the chlorination of phenols.  According to these studies,
 the  chlorination of phenol proceeds by  stepwise substitution of the
 2, 4, and 6  positions of the aromatic  ring.  Initially,  phenol is
 chlorinated  to form either 2- or 4- chlorophenol.  Then 2- chloro-
 phenol  is chlorinated to form either 2, 4- dichlorophenol or 2, 6-
 dichlorophenol while 4- chlorophenol forms 2, 4- dichlorophenol.
 Both 2, 4- and 2, 6- dichlorophenol are chlorinated to form 2, 4, 6-
 trichlorophenol.  The 2, 4, 6- trichlorophenol reacts with aqueous
 chlorine  to  form a mixture of non-phenolic oxidation products.

 TABLE 4.  CHLORINATION OF PHENOLIC MATERIALS
Material
@ 1 mg/1
Phenol
0-Cresol
M-Cresol
P-Cresol
1 -Naphthol
2-Chlorophenol
4-Chlorophenol
2-, 4-Di chlorophenol
2-, 4-, 6-Trichlorophenol
2-, 4-, 5-Trichlorophenol
2-, 3-, 4-, 6-Tetrachlorophenol
Pentachlorophenol
Chlorine Required to Chlorine Added
Eliminate Taste to Produce Free
(mg/1) Residual (mg/1)
4
5
5
3
4
3
3
2
Could Not be Tasted
Could Not 'be Tasted
Could Not be Tasted
Could Not be Tasted
7
5
5
4
5
5
6
6
3
2
1.5
1.0
     The principal taste causing compounds were found to be 2-chlorophenol,
2, 4- dichlorophenol, and 2, 6- dichlorophenol.  The development of the
chlorophenolic taste did not occur at pH values less than 7.0 and the
presence of ammonia significantly retarded the rate of reaction between
phenol and chlorine.  Of prime importance was the discovery that at a
chlorine to phenol ratio of 10:1, the aromatic benzene ring is destroyed.
An optimum pH of 8 was found to be helpful for rapid chlorination of


                                    -14-

-------
phenolic compounds using hypochlorous acid; however, reaction rates
would be different under acidic conditions using chlorine gas since
molecular chlorine is the most probable reacting agent.   Therefore no
information was provided on the mechanism of chlorination or reaction
rates using chlorine gas at low pH values.

     Later studies by Lee (27) provided information on the kinetics of
reaction of phenolic compounds and chlorine.   According to Lee, the
chlorination of phenol and each of the chlorophenols conforms to a
second-order rate expression in which the rate of change of chlorine or
phenolic compounds is proportional to the product of the formal concen-
trations of aqueous chlorine and phenolic compounds, or:

                      -dF
                      	Cl =  K   F   F
                      ~dT~     ob  Cl  PhOH

Rate constants were determined for each phenol compound at various pH
levels and are plotted in Figure 4.

     Obviously, the rates of reaction of aqueous chlorine with phenol
vary with pH with the maximum rate of reaction occurring .near neutrality
for most species.  It should be noted that the more acidic the phenolic
compound the lower the pH of maximum reaction rate, and, as stated by
Lee, those substitute groups of phenol which tend to make the substituted
phenol more acidic also tend to decrease the rate of reaction of aqueous
chlorine with  this compound.  Thus, it can be expected that the maximum
reaction rate of chlorine with pentachlorophenol will occur at a pH
somewhat less than 7, and that this reaction will be slower than the
reaction of chlorine with less highly substituted phenols.  Further,
it is stated that in reacting with aqueous chlorine, phenol and the
chlorophenols tend to undergo oxidative rupture of the benzene ring
rather than substitution and that this tendency to rupture increases
with more .highly chlorinated phenolic reactants.

     Figures 5, 6, and 7 show the reaction of aqueous chlorine with
phenol and the chlorophenols with time.  The initial chlorine dosage,
using a stock chlorine solution prepared from gaseous chlorine, was
1.0 mg/1, the initial phenol concentration 50 mg/1, and the temperature
25° C.  Figures 5, 6, and 7 represent the reactions at pH levels of 7, 8,
and 9*, respectively.  A minimum reaction time of two hours was required
before a significant decrease in total molar concentration of phenolic
compounds occurred.

     It should be remembered that these data represent the results of
reactions in distilled water.  The presence of ammonia, for instance,
interferes significantly with the reaction of phenol with chlorine.
Weil and Morris (28) indicate that for equal  initial molar concentra-
tions of ammonia and phenol at a pH of 8 and a temperature of 25° C,
ammonia chlorinates to form NH2CL about a thousand times faster than
phenol chlorinates to form monochlorophenol.   Therefore, the usefulness
of the work of Lee is only qualitatively applicable to a discussion of
chlorination of a heterogeneous wastewater.

                                    15

-------
     8000
     6000
     4000 -

     2000 -

^  1000
7E   800
 £   600
 £   400 .
 -Q
 O
 O
'•M
 fC
     200  -
o   100
o   80
o   60
«/l
40 -

20 -

10
 8
 6
 4
01
to
«§
      2 .

                                                       Phenol
                                                          2-Chlorophenol
                                                          4-Chlorophenol
                          2,4,6 Tricnloro
                                   phenol
                          2,6-Dichlorophenol
                            2,4-Dichlorophenol
FIGURE  4.
                45      6     7     8     9     10     11    12    13
                                           PH
             Observed Rates  of Chiorination of Phenol  and Chlorophenols
                                    16

-------
     20-,
     18 -
     16 _
                                Initial  Chlorine  10 ppm
                                          Phenol  50 ppb
                                     Temperature  25° C.
                                              pH  7.0
                Phenol
V
                ^2-Chlorophenol

                        4-Chlorophenol
                          \ 2,4-Dichlorophenol
                1       2

                                     TIME  hrs

FIGURE 5.   Chlorination of Phenol  and the Chlorophenols  Fonned at pH 7,

                                     17

-------
                                             Initial Chlorine 10 ppm
                                               11      Phenol 50 ppb
                                                 Temperature 25° C.
                                                          pH 8.0
                \ /2-Chlorophenol
                             2,4-Dichlorophenol
                   2,6-Dichloro-
                          phenol
                                                      i
                         0.8     1.2     1.6      2.0     2.4     2.8
                                      TIME hrs
FIGURE 6.  Chlorination of Phenol and  the Chlorophenols formed at  pH8.
                                     18

-------
         Phenol
oo
 o
_x  12 _
   01


   §
  •I-

   2
 01
 0
                                               Initial Chlorine 10 ppm
                                                        Phenol 50 ppb
                                                   Temperature 25° C.
                                                            pH 9.0
                              2,4-Dichlorophenol
                                       \2,5-Dichlorophenol
FIGURE 7
                                           T-~T — i — r
                               3456
                                   TIME hrs.

          Chlorination of Phenol and the  Chlorophenols Formed at  pH 9

                                  19

-------
      Other researchers  have  also  mentioned  the  oxidation  of   phenol
 bearing  waters  using  either  chlorine  gas  or chlorine  dioxide  (29,  30,  31).

      Glabisz  (31)  reported that chlorine  dioxide would  successfully
 convert  phenolic wastes from coke works to  quinones,  organic  acids,
 and  carbon dioxide.   Specific data on  test  conditions were not available
 for  presentation.

      Successful oxidation of phenolics by chlorine was  reported by the
 American Petroleum Institute (32).  Apparently, low dosages of chlorine
 produce  chlorophenolics which produce  taste and odor  problems.  When
 a  large  excess  of  chlorine is supplied (5 grams/liter per 100 mg/1 phenol),
 the  benzene ring is broken and a  harmless non-phenolic  compound is created.
 The  theoretical ratio of chlorine to phenol  for complete  destruction is
 6:1;  however, other organic  compounds  present in the  wastewater necessitate
 as much  as 50 parts chlorine to 1 part of phenol.  Again, the presence
 of ammonia was  noted  to retard the reaction of chlorine and phenols.
 The  ratio  of chlorine to ammonia  to oxidize the ammonia is 10:1.  Reaction
 times for  chlorination  were  reported in terms of one  to several hours.
 In conformity to the  observed chlorination  rates shown  in Figure 5, at
 a pH  less  than  7   a predominance  of chlorophenolics was noticed, while
 at higher  pH levels (above 7)  phenols were  oxidized more  rapidly and
 completely.

      In  a  study by H. R. Eisenhauer (22), chlorination  was applied to
 an artificial 80 mg/1 concentration phenol  solution and a refinery
 effluent of 78 mg/1 phenol and 627 mg/1 COD.  Chlorine  was added as
 sodium hypochlorite at  a pH  of 4  and a temperature of 50° C.  Creation
 of chlorophenols and  their destruction was  directly related to increasing
 chlorine dosages.   There was  no measurable  phenol  after the addition
 of 200 mg/1 chlorine  to  the  artificial solution, and the end products
 stabilized at dosages over 1000 mg/1  of chlorine.   In the refinery
 effluent,  1000 mg/1 of  chlorine were needed  to remove all  traces of
 phenol and the final  chlorination product was achieved with less than
 5000 mg/1  of chlorine.  A pH  in the range of 4 to 10 was not found to
 be an influencing factor.

     Work  performed by  Dust  (33)  substantiates the value of chlorination
 for pentachlorophenol removal.  Table 5 presents data on the removal
 of pentachlorophenol  from an actual  wood preserving wastewater.   Increasing
 dosages of chlorine as calcium hypochlorite were added at pH levels of
 4.5,  7.0,  and 9.5.   Similarly, gaseous chlorine was added at pH levels
 of 4.5,  7.0, and 9.5  and at dosages from 0.0 to 5.0 grams/liter.   The
 hypochlorite and gaseous chlorine were added to samples flocculated
with  lime  at 18 mg/1  and 20 mg/1  of cationic polyelectrolyte and to
 samples not pretreated.   Flocculation removed much of the  chlorine
demanding substances  from the wastewater and the chlorine  required for
 pentachlorophenol  removed appeared to decrease with increasing pH.
The reaction of gaseous  chlorine  with pentachlorophenol  appeared to be
 less  vigorous than  when  hypochlorite  was  used,  especially  at low concen-
 trations  (2.0 to 4.0 rng/1)  of pentachlorophenol.
                                    20

-------
TABLE 5.  EFFECT  OF CHLORINATION OF PENTACHLOROPHENOL  WASTE ON COD
Test Conditions
Calcium Hypochlorite
pH » 4.5






Calcium Hypochlorite
pH = 7. a







Chlorine Gas
pH = 4.5








Chlorine Gas
pH - 7.0








Available Chlorine
(g/liter)
0.0
0.5
1.0
1.5
2.0
3.0
4.0
5.0
0.0
0.5
1.0
1.5
2.0
3.0
4.0
5.0

0.0
Of
.5
1.0
1.5
2.0
3.0
4.0
5.0
10.0

0.0
Of*
.5
1.0
1.5
2.0
3.0
4.0
5.0
10.0
COD
(mg/ liter)
24,200

10,650

10,600

10,300

23,800-

10,300

10,200


10,050

20,400



10,250

10,600

10,200

23,600



9^60

10,700

11,250
                                  21

-------
 BIOLOGICAL TREATMENT

 Activated Sludge

      Cooke and Graham  (34) performed  laboratory scale studies on the
 biological degradation of phenolic wastes by the complete mixed acti-
 vated sludge system.  While many of the basic parameters needed for
 design  such as MLSS were not presented, the final results were conclu-
 sive,   The feed liquors contained phenols, thiocyanates, ammonia, and
 organic acids.  Aeration varied from  8 to 50 hours.  Influent concentration
 and percentage removal of phenol averaged 281 mg/1 and 78 percent,
 respectively at a volumetric loading  of 144 to 1609 kg/100 m3/day
 (9 to 100 lb/1000 ft3/day).

      Badger and Jackman (35), studying bacteriological oxidation of
 phenols in aerated reaction vessels on a continuous flow basis, with
 a loading of approximately 1600 to 2400 kg/1000 m3/day (100-150 Ib
 phenol/1000 ft3/day) and a MLSS of 2000 mg/1, found that with wastes con-
 taining up to 5000 mg/1 phenol, a two day retention period could produce
 removal efficiencies in excess of 90  percent.  Because the investigators
 were  working with a coke gasification plant waste, the liquor contained
 thiocyanates.  Higher oxidation efficiencies could be achieved with a
 reduction of the thiocyanate in the waste.  Gas chromatography indicated
 no phenolic end products of degradation with original waste being a
 mixture of 36 percent monohydric and  64 percent polyhydric phenols.

      Pruessner and Mancini (36) obtained a 99 percent oxidation efficiency
 for BOD in petrochemical wastes.  Similarly, Coe (37) reported reductions
 of both BOD and phenols of 95 percent from petroleum wastes in bench-scale
 tests of the activated sludge process.  Optimum BOD loads of 2247 kilo-
 grams/1000 m3 per day (140 pounds/1000 ft3 per dayjwere obtained.  Coke
 plant effluents were successfully treated by Ludberg and Nicks (38),
 although some difficulty in start-up of the activated sludge system was
 experienced because of the high phenol content of the water.

      The complete mixed, activated sludge process was employed to process
 a high-phenolic wastewater from a coal-tar distilling plant in Ontario (39).
 Initial phenol and COD concentrations of SOO and 6,000 mg/1Her, respec-
 tively, were reduced in excess of 99 percent for phenols and 90 percent
 for COD.

     Coal  gas washing liquor was successfully treated by Nakashio (40)
 using activated sludge at a loading rate of 0.116 kg of phenol/kg MLSS/day.
 An influent phenol concentration of 1200 mg/1  was reduced by more than
 99 percent in this year-long study.   Similar phenol  removal rates were
 obtained by Reid and Janson (41), in treating wastewaters generated by
 the washing and decarbonization of aircraft engine parts.  Other examples
 of biological treatment of phenolic  wastes include work by Putilena (42),
Meissner (43) and Shukov,  et.  al. (44).

     Of particular interest is a specific test on the biological  treat-
ment of coke plant wastes  containing phenols and various organics.   In


                                     22

-------
(O
a:
o


o
       1  _
                                        Slope = K = 0.30 day"1
                                             Le  =
                                                     La
                                                   1  + O.SOt
                         5             10              15

                              Aeration Time  (Days)
                                                                       i
                                                                      20
           FIGURE 8.  Determination of Reaction Rate Constant for a
                      Creosote Wastewater
                                   23

-------
a report of pilot scale and full scale studies performed by Kostenbader
and Flacksteiner (45), the complete mixed activated sludge process
achieved greater than 99.8 percent oxidation efficiency of phenols.
Successful results were achieved with phenol loadings of 0.86 kg phenol/
kg MLSS/day with an equivalent BOD loading of 2 kg BOD/kg MLSS/day.  In
comparison, a typical activated sludge loading is 0.4 kg BOD/kg MLSS/
day.  Effluent concentrations of phenol from the pilot plant were 0.2
mg/1 in contrast to influent concentrations of 3500 mg/1.  Slight varia-
tions in process efficiency were encountered with varying temperatures
and loading rates.  Phosphoric acid was added to achieve a phosphorus-to-
phenol ratio of 1:70.  At the termination of pilot plant work, a similar
large scale treatment plant processing of 424 m3/day (112,000 gpd) was
installed and resulted in an effluent containing less than 0.1 mg/1 of
phenol.

    Dust and Thompson (46) conducted bench-scale tests of complete-mixed,
activated sludge treatment of creosote and pentachlorophenol wastewaters
using 5-liter  units and detention times of 5, 10, 15, and 20 days.  The
operational data collected at steady-state conditions of substrate removal
for the creosote waste are shown in Table 6.  A plot of these data showed
that the treatabUHy factor, K, was 0.30 days -1 (Figure 8).  The
resulting design equation, with t expressed 1n days, is:

                                Lo
                      Le *  -
                               + 0.30*

    A plot of percent COD removal versus detention time in the aerator
based on the above equation, shown 1n Figure 9, Indicates that an oxidation
efficiency of about 90 percent can be expected with a detention time of
20 days 1n units of this type.

TABLE 6.  SUBSTRATE REMOVAL AT STEADY-STATE CONDITIONS IN ACTIVATED
          SLUDGE UNITS CONTAINING CREOSOTE WASTEWATER
Aeration Time, Days        5.0          10.0          14.7          20.1
COD Raw, mg/1
COD Effluent, mg/1
% COD Removal
COD Raw/COD Effluent
447
178
60.1
2.5
447
103
76.9
4.3
442
79
82.2
5.6
444
67
84.8
6.6
    Work was conducted to determine the degree of biodegradabillty of
pentachlorophenol  waste.   Cultures of bacteria prepared from soil  removed
from a drainage ditch containing pentachlorophenol waste were used to
inoculate the treatment units.   Feed to the units contained  10 mg/liter

                                    24

-------
              o
              o
90
                   80
               o   70
               o
               e
IN}
en
              a
              o
              o
               «
               a.
                   60
               2   50
                                                         Lo

                                                         0.30*
                   40
                                                          10


                                              Aeration   Time  (Days)
                                                         15
20
                                                    FIGURE 9.

                     COD Removal from a Creosote Wastewater by Aerated lagoon without Sludge  Return

-------
of pentachlorophenol and 2,400 mg/1iter COD.   For the two 5-liter units
(A and B) the feed was 500 and 1000 ml/day and detention times were, in
order, 10 and 5 days.  Removal rates for pentachlorophenol  and COD are
given in Table 7.   For the first 20 days. Unit A removed only 35 percent
of the pentachlorophenol added to the unit.  However, removal increased
dramatically afterward and averaged 94 percent during the remaining 10
days of the study.  Unit B consistently removed over 90 percent of the
pentachlorophenol  added.  Beginning on the 46th day and continuing through
the 51st day, pentachlorophenol loading was increased at two-day intervals
to a maximum of about 59 mg/liter.  Removal rates for the three two-day
periods of increased loadings were 94, 97, and 99 percent.   COD removal
for the two units  averaged about 90 percent over the duration of the study.

     Also working with the activated sludge process, Kirsh and Etzel (47)
obtained removal rates for pentachlorophenol in excess of 97 percent
using an 8-hour detention time and a feed concentration of 150 mg/liter.
The pentachlorophenol was supplied to the system in a mixture that included
100 mg/liter phenol.  Essentially complete decomposition of the phenol
was obtained, along with a 92 percent reduction in COD,

TABLE 7.  REDUCTION IN PENTACHLOROPHENOL AND COD IN WASTEWATER TREATED
          IN ACTIVATED SLUDGE UNITS       	
                          RAW                         EFFLUENT FROM UNIT
                         WASTE                           (% Removal)
 DAYS                    (rag/1)                       "A"           "B"


                          COD
1-5
6-10
11-15
16-20
21-25
26-30
31-35
2350
2181
2735
2361
2288
2490
2407
78
79
76
82
90
—
83
78
79
75
68
86
84
80
                   PENTACHLOROPHENOL

 1-5                      7.9                         20            77
 6-10                    10.2                         55            95
 11-15                    7.4                         33            94
 16-20                    6.6                         30            79
 21-25                    7.0                         -            87
 26-30                   12.5                         94            94
 31-35                    5.8                         94            91
 36-40                   10.3                         --            91
 41-45                   10.0                         ~            96
 46-47                   20.0                         ~            95
 48-49                   30.0                         —            97
 50-51                   40.0                         -            99
                                    -26-

-------
     Cooper and Catchpole (48) reported greater than 95 percent oxidation
of phenols using activated sludge units treating coke plant effluents
containing phenols, thiocyanates, and sulfides.  Adequate^data were not
available on the detailed operating parameters of the activated sludge
plant.

Trickling Filters

     Hsu, Yany, and Weng (49) reported successful treatment of coke plant
phenolic wastes with a trickling filter, removing over 80 percent of the
phenols.  It was stated that influent phenol concentrations should not
exceed 100 mg/1.
     Using a Surfpac trickling filter, Francingues  (50) was able to remove
80 to 90 percent of the influent phenol from a wood preserving creosote
wastewater at a loading rate of about 16 kg/1000 m3/day  (1 Ib phenol/
1000 ft3/day).
      Sweets,  Hamdy, and  Weiser (51)  studied the bacteria responsible for
phenol  reductions  in  industrial  waste  and  reported  good  phenol  removal
from  synthesized waste containing  concentrations of 400  mg/1.   Reductions
of 23 to  28  percent were  achieved  in a  single  pass  of the wastewater
through a  pilot trickling filter having a  filter bed  only 30  centimeters
(12 inches)  deep.

      Waters  containing phenol  concentrations of up  to 7500 mg/1 were suc-
cessfully  treated  in  laboratory  tests  conducted by  Reid  and Libby  (52).
Phenol  removals of 80 to  90  percent  were obtained for concentrations  on
the order  of 400 mg/1.  Their  work confirmed that of  Ross and  Shepard
(531 who found that strains  of bacteria isolated from a  trickling  filter
could survive  phenol concentrations  of  1600 mg/liter and were  able  to
oxidize phenols in concentrations  of 450 mg/liter at  better than 99  percent
efficiency.   Reid, Wortman,  and  Walker  (54) found that many pure cultures
of bacteria  were able to  live  in phenol concentrations of up to 200 mg/1,
but few survived concentrations  above 900  mg/1,  although  some were grown
in concentrations  as high as 3700  mg/1.

      Harlow,  Shannon.and  Sercu (55)  described  the operation of a
commercial-size trickling filter containing "Dowpac"  filter medium that
was used to  process wastewater containing  25 mg/1 phenol  and 450  to
1900 mg/1  BOD.  Reductions of  96 percent for phenols  and  97 percent
for BOD were obtained in this  unit.  Their results  compare favorably
-with  those reported by Montes, Allen, and  Schowell  (56) who obtained  BOD
reductions of 90 percent  in a  trickling filter using  a 1:2 recycle
ratio,  and Dickerson and Laffey  (57), who  obtained  phenol  and BOD reduc-
tions of 99.9 and  96.5 percent,  respectively,  in a  trickling filter used
to process refinery wastewater.

     A  combination biological  waste-treatment  system  employing a trickling
filter  and an oxidation pond was reported  on by  Davies, Biehl, and
Smith (58).  The filter, which was packed  with a plastic  medium, was
used for a roughing treatment  of 10.6 million  liters  (2.8 million gallons)
of wastewater per  day, with final  treatment occurring  in  the oxidation
pond.   Removal rates of 95 percent for phenols and  60  percent for BOD
                                     -27-

-------
were obtained in the filter, notwithstanding the fact that the pH of
the influent averaged 9.5.

     A study of biological treatment of refinery wastewaters by Austin,
Meehan, and Stockham (59) employed a series of four trickling filters
with each filter operating at a different recycle ratio.  The waste
contained 22 to 125 mg/liter of oil and this adversely affected BOD
removal.  However, phenol removal was unaffected by oil concentrations
within the range studies.
     Prather and Gaudy (60) found that significant reductions of COD,
BOD, and phenol concentrations in refinery wastewater were achieved
by simple aeration treatments.  They concluded that this phenomenon
accounted for the high allowable loading rates for biological treatments
such as trickling filtration.

     The practicality of using trickling filters for secondary treatment
of wastewaters from the wood preserving industry was explored by Dust
and Thompson (46).  Creosote wastewater was applied at BOD loading
rates of from 400 to 3050 kilograms/1000 m3 per day (25 to 190 pounds/
1000 ft3 per day) to a pilot unit containing a 6.4 meter (21 feet)
filter bed of plastic media.  The corresponding phenol loadings were
1.6 to 54.6 kMograms/1000 m3 per day (0.1 to 3.4 pounds/1000 ft3 per
day).   Raw feed-to-recycle ratios varied from 1:7 to 1:28.  Daily
samples were analyzed over a period of seven months that included both
winter and summer operating conditions.  Because of wastewater charac-
teristics at the particular plant cooperating in the study, the following
pretreatment steps were necessary:  (a) equalization of wastes; (b) pri-
mary treatment by coagulation for partial solids removal; (c) dilution of
the wastewater to obtain BOD loading rates commensurate with the range
of raw flow levels provided by the equipment; and (d) addition to the
raw feed of supplementary nitrogen and phosphorus.  Dilution ratios
of 0 to 14 were used.

     The efficiency of the system was essentially stable for BOD
loadings of less than 1200 kilograms/1000 m3 per day (75 lbs/1000
ft3 per day).   The best removal  rate was achieved when the hydraulic
application rate was 2.85 Ipm/m2 (0.07 gpm/ft2) of raw waste and
40.7 Ipm/m2 (1.0 gpm/ft2) of recycled waste.  The COD, BOD, and
phenol removals obtained under these conditions are given in Table 8.
Table 9 shows the relationship between BOD loading rate and removal
efficiency.  BOD removal  efficiency at loading rates of 1060 kilograms/
1000 m3 per day (66 pounds/1000 ft3 per day) was on the order of 92
percent, and was not improved at reduced loadings.  Comparable values
for phenols at loading rates of 19.3 kilograms/1000 m3 per day (1.2  pounds/
1000 ft3 per day) were about 97 percent.

     Since phenol concentrations were more readily reduced to levels
compatible with existing standards than were BOD concentrations, the
sizing of commercial  units was based on BOD removal rates.   Various
combinations of filter-bed depths, tower diameters, and volumes of
filter media that were calculated to provide a BOD removal  rate of
90 percent for an Influent having a BOD of 1500 mg/liter are shown in
Table 10 for a plant with a flow rate of 75,700 Ipd (20,000 gpd).
                                  -28-

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TABLE 8.  BOD, COD, AND PHENOL LOADING AND REMOVAL RATES FOR PILOT
          TRICKLING FILTER PROCESSING A CREOSOTE WASTEWATER
         Measurement
  BOD
                                                   Characteristics
  TOD
Phenol
Raw Flow Rate Iprn/m2
(gpm/ft2)
Recycle Flow Rate 1 pro/in2
(gpm/ft2)
2.85
(0.07)
40.7
(1.0)
2.85
(0.07)
40.7
0.0)
2.85
(0.07)
40.7
(1*0)
Influent Concentration (mg/1)
1698
3105
31
Loading Rate gm/m3/day
Effluent Concentration (mg/1)
Removal (%}
1075
(66.3)
137
91.9
1967
(121.3)
709
77.0
19.5
(1.2)
<1.0
99+
                                   29

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TABLE 9.   RELATIONSHIP BETWEEN BOD LOADING AND TREATABILITY  FOR
          PILOT TRICKLING FILTER PROCESSING A CREOSOTE WASTEWATER
BOD Loading
kg/cu m
373
421
599
859
1069
1231
1377
1863
2527
a
Based

BOD Loading
(Ib/cu ft. /day)
(23)
(26)
(37)
(53)
(66)
(76)
(85)
(115)
(156)
on the equation:
E§ = eKD/
Removal Treatability a
(«) Factor
91
95
92
93
92
82
80
75
62

Q °'5 (Germain, 1966)
0.0301
0.0383
0.0458
0.0347
0.0312
0.0339
0.0286
0.0182
0.0130


          in  which  Le  =  BOD concentration of settled effluent,
          Lp  =  BOD  of  feed, Q =  hydraulic application rate of
          raw waste in gpm/ft^,  D  = depth of media  in feet, and
          K = treatability factor  (rate coefficient).
                                 30

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TABLE 10.  SIZING OF TRICKLING FILTER FOR A WOOD PRESERVING PLANT

     (NOTE:   Data are based on a flow rate of 75,700 liters per
             day (20,000 gallons per day), with filter influent
             BOD of 1500 and effluent BOD of 150 mg/1).
Depth of
filter
bed
m
(ft)
Raw Flow
1 pm/m2
(gpm/ft2)
filter
surface)
Recycle flow
1 pm/m2
(gpm/ft2)
filter
surface)
Filter
Surface
area

(ft2)

Tower
dia
m
(ft)
Vol ume
of
media
uj3
(ft3)
3.26
(10.7)
3.81
(12.5)
4.36
(14.3)
4.91
(16.1)
5.46
(17.9)
5.97
(19.6)
6.52
(21.4)
0.774
(0.019)
1.059
(0.206)
1.385
(0.034)
1.793
(0.044)
2.200
(0.054)
2.648
(0.065)
3.178
(0.078)
29.7
(0.73)
29.3
(0.72)
28.9
(0.71)
28.5
(0.70)
28.1
(0.69)
27.7
(0.68)
27.3
(0.67)
65.8
(708)
48.3
(520)
37.0
(398)
29.3
(315)
23.7
(255)
19.5
(210)
16.4
(177)
9.14
(30.0)
7.83
(25.7)
6.86
(22.5)
6.10
(20.0)
5.49
(18.0)
4.97
(16.3)
4.57
(15.0)
213
(7617)
183
(6529)
160
(5724)
142
(5079)
128
(4572)
116
(4156)
107
(3810)
Oxidation Ponds

     The American Petroleum Institute's "Manual  on Disposal  of Refinery
Wastes" (61) refers to several  industries that have successfully used
oxidation ponds to treat phenolic wastes.  Montes (62)  reported on
results of field studies involving the treatment of petrochemical  wastes
using oxidation ponds.  He obtained BOD reductions of 90 to  95 percent in
ponds loaded at the rate of 84  kilograms of BOD  per hectare  per day
(75 pounds/acre/day).
                                   31

-------
     Phenol concentrations of 990 mg/liter in coke oven effluents
were reduced to about 7 mg/liter in field studies of oxidation ponds
conducted by Biczyski and Suschka (63).  Similar results have been
reported by Skogen (64) for a refinery waste.

     The literature contains operating data on only one pond used
for treating wastewater from wood preserving operations (65, 66, 67).
This is the oxidation pond used as part of a waste treatment system
by Weyerhaeuser Company at its DeQueen, Arkansas, wood preserving
plant.  As originally designed and operated in the early 1960's,
the DeQueen waste treatment system consisted of holding tanks into
which water from the oil-recovery system flowed.  From the holding
tanks the water was sprayed into a terraced hillside from which
it flowed into a mixing chamber adjacent to the pond.  Here it was
diluted 1:1 with creek water, fortified with ammonia and phosphates,
and discharged into the pond proper.  Retention time in the pond
was 45 days.  The quality of the effluent was quite variable, with
phenol content ranging up to 40 mg/liter.  In 1966, the system was
modified by installing a raceway containing a surface aerator and a
settling basin in a portion of the pond.  The discharge from the
mixing chamber now enters a raceway where it is treated with a floc-
culating agent.  The floe formed collects in the settling basin.
Detention time is 48 hours in the raceway and 18 hours in the settling
basin from which the wastewater enters the pond proper.

     These modifications in effect changed the treating system from
an oxidation pond to a combination aerated lagoon and polishing pond.
The effect on the quality of the effluent was dramatic.  Figure 10
shows the phenol content at the outfall of the pond before and after
installation of the aerator.   As shown by these data, phenol content
decreased abruptly from an average of about 40 mg/liter to 5 mg/liter.

     Even with the modifications described, the efficiency of the
system remains seasonally dependent.  Table 11 give phenol and BOD
values for the pond effluent by month for 1968 and 1970.   The smaller
fluctuations in these parameters in 1970 as compared with 1968 indicate
a gradual improvement in the system.

Soil Irrigation

     The principal feature of the soil irrigation method  of waste-
water treatment is its simplicity.   Water that has been freed of
surface oils and, depending upon the presence of emulsified oils,
treated with flocculated chemicals  and filtered through a sand bed
is simply sprayed onto a prepared field.   Soil microorganisms decompose
the organic matter in the water in  much the same fashion  as occurs in
more conventional waste treatment systems.

     In addition to its simplicity, soil  irrigation has the advantage
of low capital  investment (exclusive of land costs), low  operating
and maintenance costs, requires a minimum of mechanical equipment,
                                  32

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CO
co
        45
        40
         35
         30
         25
       Q>


       o
       o
       1  15
       0)
          10
                  JAN    FEB   MAR  APR   MAY  JUNE   JULY  AUG  SEPT  OCT   NOV   DEC

                                                    Month

   Figure 10. Phenol Content in Oxidation Pond Effluent Before and After Installation in June  1966 of Aerator

-------
and produces a high-quality effluent in terms of color,  oxygen demand,
and other pertinent parameters.   Its chief disadvantage  is that its
use requires a minimum of approximately one acre for an  application
rate of 13,250 Ipd (3500 gpd).   This limitation makes soil irrigation
practical only in areas where land is available and relatively in-
expensive.


TABLE 11.  AVERAGE MONTHLY PHENOL AND BOD CONCENTRATIONS IN EFFLUENT
           FROM OXIDATION POND
                             (mg/liter)
1968
Month
January
February
March
April
May
June
July
August
September
October
November
December
Phenol
26
27
25
11
6
5
7
7
7
16
7
11
BOD
290
235
190
150
100
70
90
70
110
150
155
205
1970
Phenol
7
9
6
3
1
1
1
1
1
-
-
-

BOD
95
140
155
95
80
60
35
45
25
-
-
-
     Several applications of wastewaters  containing high phenol  con-
centrations to soil  irrigation have been  reported.   One such report,
by Fisher (68) related the use of soil  irrigation to treat wastewaters
from a chemical plant that had the following characteristics:

               pH                   9 to  10

               Color                5,000 to 42,000 units

               COD                  1,600 to 5,000  mg/liter

               BOD                  800 to 2,000 mg/liter
                                   -34-

-------
     Operating data from a 0.81 hectare (2 acre) field, when irrigated
at a rate of 7570 liters (2,000 gal) per acre/day for a year, showed
color removal of 88 to 99 percent and COD removal of 85 to 99 percent.

     The same author reported on the use of this method to treat
effluent from two tar plants that contained 7,000 to 15,000 mg/liter
phenol and 20,000 to 54,000 mg/liter COD.   The waste was applied to
the field at a rate of about 9460 liters (2500 gal) per acre/day.
Water leaving the area had COD and phenol  concentrations of 60 and
1 mg/liter, respectively.  Based on the lower influent concentration
for each parameter, these values represent oxidation efficiencies
of well over 99 percent for both phenol and COD.

     Bench-scale treatment of coke plant effluent by soil  irrigation
v/as also studied by Fisher.   Wastes containing BOD and phenol concen-
trations of 5,000 and 1,550 mg/liter, respectively, were reduced by
95+ and 99+ percent when percolated through 0.9 meters (36 inches) •
of soil.  Fisher pointed out that less efficient removal was achieved
with coke-plant effluents using the activated sludge process, even
when the waste was diluted with high-quality water prior to treatment.
The effluent from the units had a color rating of 1,000 to 3,000 units,
compared to 150 units for water that had been treated by soil irrigation.
     Both laboratory and pilot scale field tests of soil-irrigation
treatments of wood preserving wastewater were conducted by Dust and
Thompson (46).  In the laboratory tests, 210-liter (55 gallon) drums
containing a heavy clay soil 60-centimeters (24 inches) deep were
loaded at rates of 32,8000, 49,260, and 82,000 liters/hectare/day
(3,500, 5,250, and 8,750 gallons/acre/day).  Influent COD and phenol
concentrations were 11,500 and 150 mg/liter, respectively.  Sufficient
nitrogen and phosphorus were added to the  waste to provide a COD:N:P
ratio of 100:5:1.   Weekly effluent samples collected at the bottom
of the drums were analyzed for COD and phenol.

     Reductions of more than 99 percent in COD content of the wastewater
were attained from the first week in the case of the two highest
loadings and from the fourth week for the  lowest loading.   A break-
through occurred during the 22nd week for  the lowest loading rate
and during the fourth week for the highest loading rate.  The COD
removal steadily decreased thereafter for  the duration of the test.
Phenol removal showed no such reduction, but instead remained high
throughout the test.   The average test results for the three loading
rates are given in Table 12.  Average phenol removal was 99+  percent.
Removal of COD exceeded 99 percent prior to breakthrough and averaged
over 85 percent during the last week of the test.

     The field portion of Dust and Thompson's (46) study was carried
out on an 0.28-hectare (0.8 acre) plot prepared by grading to an
approximately uniform slope and seeded to  native grasses.   Wood
preserving wastewater from an equalization pond was applied to the
field at the rate of 32,800 liters/hectare/day (3,500 gallons/acre/day)
for a period of nine months.  Average monthly influent COD and phenol
concentrations ranged from 2,000 to 3,800  mg/liter and 235 to 900
mg/liter, respectively.   Supplementary nitrogen and phosphorus were
                                   35

-------
not added.  Samples for analyses were collected weekly at soil  depths
of 0 (surface),30, 60, and 120 centimeters (1, 2, and 4 feet).

     The major biological reduction in COD and phenol content occurped
at the surface and in the upper 30 centimeters (1 foot) of soil.
A COD reduction of 55.0 percent was attributed to overland flow.
The comparable reduction for phenol content was 55.4 percent (Table 13),
COD reductions at the three soil depths, based on raw waste to the
field, were 94.9, 95.3, and 97.4 percent, respectively, for the 30-,
60-, and 120 centimeter (1-, 2-, and 4-foot) depths.  For  phenols,
the reductions were, in order, 98.9, 99.2, and 99.6 percent.

TABLE 12.  RESULTS OF LABORATORY TESTS OF SOIL IRRIGATION METHOD OF
           WASTEWATER TREATMENT*
Loading Rate
(Liter/ha/day)
32,800
(3,500)
49,260
(5,250)
82,000
(8,750)
Length of
Test
(Week)
31
13
14
Avg. & COD
Removal to
Breakthrough
99.1 (22 wks)
99.6
99.0 (4 wks)
COD REMOVAL
Last Week
of Test
%
85.8
99.2
84.3
Phenol
Avg. %
Removal
(All Weeks)
98.5
99.7
99.7
           Loading rates in parentheses in gallons/acre/day
 Creosote wastewater containing 11,500 mg/liter of COD and 150 mg/Hter
 of phenol was used.
Activated Carbon Filtration

     Activated carbon is used commercially to treat petroleum (69)  and
other types (70) of Industrial wastewaters.  It can also be used
effectively to remove phenolic compounds from wood preserving waste
streams.  Although carbon has a strong affinity for nonpolar compounds
such as phenols, adsorption is not limited to these materials.  Other
organic materials in wastewater are also adsorbed, resulting in a
decrease in the total oxygen demand of the waste.   Because the concen-
tration of the latter substances exceeds that of phenols in effluents
from wood preserving plants, the useful life of activated carbon is
determined by the concentration of these materials and the rate at
which they are adsorbed.
                                   36

-------
TABLE  13.  REDUCTION OF COD AND  PHENOL CONTENT  IN  WASTEWATER  TREATED
           BY  SOIL  IRRIGATION
Soil Depth (centimeters)
Month Raw Waste

July
August
September
October
November
December
January
February
March
April
Average % Removal
(weighted)

July
August
September
October
November
December
January
February
March
April

2235
2030
2355
1780
2060
3810
2230
2420
2460
2980



235
512
923
310
234
327
236
246
277
236
0
COD (mg/1)
1400
1150
1410
960
1150
670
940
580
810
2410

55.0
Phenol (mq/1)
186
268
433
150
86
6
70
in
77
172
30

••» •
—
--
150
170
72
121
144
101
126

94.9

MM
—
«
4.6
7.7
1.8
1.9
4.9
2.3
1.9
60

M m.
—
—
—
170
91
127
92
102
—

95.3

..
—
~
_.
3.8
9.0
3.8
2.3
1.9
0.0
120

66
64
90
61
46
•58
64
64
68
76

97.4

1.8
0.0
0.0
2.8
0.0
3.8
0.0
1.8
1 .3
0.8
Average % Removal
   (weighted)
55.4
98.9
99.2
99.6
                                    37

-------
      Results  of  carbon-adsorption  studies conducted by Dust and Thompson
 (46)  on  a  creosote wastewater are  shown  in Figure 11.  Granular carbon
 was used and  the contact time was  24  hours.  The wastewater was floccu-
 lated with ferric chloride  and  its pH adjusted to 4.0 prior to exposure
 to the carbon.   As shown in the figure,  96 percent of the phenols and
 80 percent of the COD were  removed from  the wastewater at a carbon dosage
 of 8  g/liter.  The loading  rate dropped  off sharply at that point, and
 no further increases in phenol removal and only small increases in COD
 removal  occurred by increasing carbon dosage to 50 gm/liter.  Similar
 results  were  obtained in tests using  pentachlorophenol wastewater.

      Results  of  adsorption  isotherms  that were run on pentachlorophenol
 wastewater, and  other samples of creosote wastewater followed a pattern
 similar  to that  shown in Figure 11.   In  some instances a residual content
 of phenolic compounds remained in  wastewater after a contact period of
 24 hours with the highest dosage of activated carbon employed, while in
 other instances  all of the  phenols  were  removed.  Loading rates of 0.16
 kilograms  of  phenol and 1.2  kilograms of COD per kilogram of carbon were
 typical, but much lower rates were obtained with some wastewaters.

 Miscellaneous Treatment and  Handling Methods

      Wastes from wood preserving plants may also be handled by containment,
 if adequate land is available, by  spray  evaporation, if a relatively
 high  operating cost can be  tolerated, or by heat evaporation or incinera-
 tion  if  the waste stream is  small.

 SUMMARY

      It was concluded that  previous laboratory and pilot work demonstrated
 that  chemical or biological  action  could be used to reduce wastewater
 pentachlorophenol concentration.   Pentachlorophenol is more toxic than
 simple creosote  but less soluble in water.  High concentrations of
 pentachlorophenol can be oxidized  to harmless, biodegradable chloranyls.
 Low concentration of pentachlorophenol,  on the order of 10 to 30 mg/1,
 can be degraded  biologically in the presence of relatively numerous
 nutrients.   Some portion of  the Carbondale plant's wastewater could,
 therefore, be degraded in an activated sludge system, probably including
 the pnetachlorophenol and creosote  fractions.

     Ample evidence was found in the literature to substantiate destruc-
 tive chlorination and biological oxidation of phenolic compounds.  Thus,
while there remained some ambiguity concerning the detailed operating
 parameters for a treatment plant for these wastes, the basic processes
were sound.  It was felt that early ambiguities arose from non-parametric
 studies with varying feed waters, few of which were specifically wood
 preserving wastewaters.   It was the intent of the Carbondale study to
 clarify the various operating parameters and provide a sound basis for
 future design work.
                                    33

-------
10CH
               10          20          30

            Activated Carbon (gm/liter)
                                  FIGURE  11
               Relationship Between  Weight of Activated Carbon
       Added and Removal  of COD and  Phenols  from a  Creosote  Wastewater
                                39

-------
                            SECTION V

                      MATERIALS AND METHODS
      Following acceptance of the grant application, laboratory and
 field studies were begun in Carbondale to establish wastewater flow
 and characteristics.  A mobile laboratory was stationed on-site for
 a five day period during which samples were collected and analyzed.
 Flow  measurements were initiated and continued for a two month period.
 A discussion of data collection methods and of development of design
 parameters are presented in this section.

 PRE-DESIGN STUDIES

      At the time of the pre-design wastewater studies, condensate
 from  the treating cylinders was pumped to primary separation tanks.
 The pentachlorophenol condensate which is isolated from the creosote
 waste stream receives polymer addition before going to the secondary
 penta  separator.  Since penta-oil is lighter than water, skimming
 allows good separation.  The creosote condensate, after polymer
 addition, was separated by settling the heavier creosote and skimming
 the light oils.  The two waste streams were then combined in a common
 sump and pumped to Pond 2 or Pond 3.  The effluents from Ponds 2 and 3
 flowed to a Pond 4 by gravity.   Pond 1 was maintained for emergency use
 only.  Previous to the present design, these ponds, together with the
 primary oil removal and preservation recovery system and a 1.05 hectare
 (2.58 acre) irrigation field constituted the waste treatment facilities
 for the Carbondale plant.

     The wastewater flow during the pre-design study averaged 27,055
 1 pd  (7,148 gpd) of which 36 percent was penta waste and 64 percent
 creosote waste.  The range and variability of the total  wastestream and
 the constituent flows is illustrated in Figure 12.  Obviously, the flow-
 rate was erratic, varying from less than one-fourth to nearly three
 times the average daily flow.   Of importance is the fact that penta flow
was non-existent for several  consecutive days and then occurred in
 slug flows.

     The analytical data collected during the five day sampling period
 is presented in Table 14.  Each pond was sampled during  this period;
 however, due to inplant modifications, it was decided that the pond data
was of little value for design.  The samples considered  to be of value
were those from the creosote decantor effluent and the common sump.
During the period of sampling,  there was no flow for at least two days
from the penta separator and,  therefore,  the concentrations determined
in the commom sump are not necessarily average concentrations.   A
better estimate of average conditions is  obtained by calculating con-
centrations based on the preparation of average flow from each waste
source.  This calculated average  is also  shown in Table 14.
                                   40

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                                        20,250
                                                                                              10,160
     COMBINED WASTE FLOW

O	PENTACHLOROPHENOL WASTE
    MISSING DATA
      POINT
                               IS  l«  17   18  19  20  21  22  23  24  25   26   27  29
                                                                                         Z9   30
         FIGURE 12.
Time/Days
Flowrate Variation with Time

-------
                            TABLE 14.  Analytical Data From Pre-Design Study
ro
Date
6-25


6-26

6-27
6-28


6-29


Sample
Point
Creosote
Effluent
Penta
Effluent
Common Sump
Creosote
Effluent
Penta
Effluent
Penta
Effluent
Creosote
Effluent
Penta
Effluent
Common Sump
Creosote
Effluent
Penta
Effluent
Common Sump
COD
(mg/1)
2,130
4,360
2,130
7,800
6,900
-
7,990
4,720
7,260
3,209
4,972
2,621
BOD5
(rag/T)
615
1,335
600
525
1,395
-
-
-
-
1,200
2,512
-
TS
(mg/1)
4,270
20,780
5,480
5,220
19,830
-
5,400
19,980
7,250
4,184
19,844
4,447
TSS
(mg/1)
147
156
181
70
138
-
58
143
56
142
158
174
Phenol
(mg/D
100
50
120
140
65
-
132
70
140
200
-
-
Oil and Grease NH3+-N Total
(mg/1) (mg/1) (mg/1) pH
89 550 3,200 5.6
4.9
5.6
96 500 3,050 5.6
178 1,750 10,200 4.7
263 1,650 11,200
5.6
4.9
5.4
275 500 2,050 5.7
4.8
5.7

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                             TABLE  14. ANALYTICAL DATA FROM PRE-DESIGN STUDY
Sample
Date Point
Average
creosote
effluent
Penta
Effluent
Common Sump
COD
(mg/1 )
5,282
5,238
4,004
BOD5
(mg/T)
780
1,747
600
TS
(mg/1)
4,769
20,109
5,726
TSS
(mg/1)
104
149
137
Phenol
(mg/1)
143
78
130
Oil and Grease
(mg/1)
153
221
_
NH3+-N
(mg/1)
517
1,700
_
Total
(mg/1)
2,767
10,700
_
pH
5.6
4.8
5.6
oo
CALCULATED
AVERAGE
CONCENTRATIONS
OF COMBINED
EFFLUENTS     5,266    1,126   10,291
                                                  121
120
178
943
5,623    5.3

-------
     The ratio of BOD to COD for the calculated average data was
relatively low, possibly indicating some degree of biological inhibition.
Figure 13 shows the effluent dilution of the BOD test.  When the dilution
factor was increased from 99.6 to 99.9 percent, the BOD of the penta
effluent increased from 1860 to 3500 mg/1.  An increase in dilution
from 99.8 to 99.9 percent for the creosote effluent resulted in a BOD
increase from 1000 to 2000 mg/1.  Assuming the samples were properly
seeded, the value of the BOD test becomes questionable.  While a limited
amount of BOD data was collected during the study and is presented
in this report where appropriate; the limitations on its usefulness
should be noted in light of the above discussion.

     The majority of the solids, as noted in Table 14, are composed
of dissolved material which resulted for the most part from salts in
fire retardant compounds which contained ammonium phosphate, ammonium
sulfate, sodium tetraborate and boric acid as their primary constituents.
Analyses performed later showed high boron levels.  Also, the nutrient
levels were relatively high due to the use of the fire retardant.  The
plant, subsequent to thepre-designed study, terminated the use of fire
retardant preservative although boron persisted in the effluent for a
period of time.

     The phenol concentration averaged 120 mg/1 during the study while
the oil and grease concentration was 178 mg/1 and pH averaged 5.3.  No
analytical  data is given in Table 14 for penta because at the time of
the pre-design study no suitable analysis technique had been developed.
Later analyses by Koppers personnel indicated that the penta concentration
was less than 20 mg/1.

DEVELOPMENT OF PARAMETERS

     The average conditions determined in the pre-design study were
chosen as the hydraulic basis for design.  The average daily flow
used for design was 27,063 Ipd (7150 gpd) or 19 1pm (5 gpm).  Further,
it was decided that by maintaining Pond 2 as a surge lagoon it would be
possible to operate the treatment facility at a constant feed rate and
minimize the problems associated with flowrate and quality variations.

     The pre-design data indicated that primary and secondary preserva-
tive recovery was efficiently removing most of the separable oils from
the effluent.  For this reason no modification of the existing oil re-
moval system was considered necessary.

     Laboratory studies by Thompson (46) and others indicated that
biological  oxidation of penta was possible.   However, due to uncertainty
with regard to the degree of reduction possible, the maximum concentration
allowable,  and the effects of penta on a biological system treating a
complex, heterogeneous wastewater, it was decided that pretreatment
with chlorine should be included in the design.  Preliminary tests
indicated that several hours detention time would reduce the chlorine
residual to minimal  levels.   For this reason no chlorine removal  facili-
ties were included in the design of the pre-chlorination section of
the treatment system.

                                    44

-------
  4000-
                                           PENTACHLOROPHENOL
                                              EFFLUENT
   3000
   2000'
a
o
m
LU
   1000-
                                                          CREOSOTE
                                                               EFFLUENT
       99.6
99.7
   ^DILUTION
                                     99.8
99.9
100.0
                         FIGURE 13,
                 Percent Dilution vs. BOD
                                   45

-------
      On the basis  of the  limited  information  in  the  literature,  recent
 laboratory data, and the  consultant's  experience with  biological  treat-
 ment, the system with the best potential  for  success was judged  to be
 complete mix activated sludge.  This process,  having a  record of  success
 in many industrial  applications,  has the  advantage of  reducing the effects
 of shock loadings.   Additionally,  it requires  relatively little  land area
 and is a viable treatment alternative  for wood preserving plants  with
 little available space.

      The determination of design  parameters was  based on experience
 with the activated  sludge process  and  on  the  limited laboratory and
 literature data relative  to wood  preserving wastes.  It was felt  that
 the design should  be based on  the  assumption  that pre-chlorination
 might not be necessary.   Therefore, all loadings, detention times, and
 capacities were based  on  the data  shown in Table 14 of  this section.
 The factor considered  most important with regard to organic loading
 rates was the penta  concentration  in the  mixed liquor.  Laboratory
 results had shown biological degradation  of penta at loadings of  1.62
 gm/m3 (0.1  lb/1000 cu  ft)  of aeration  volume  (71).  Slug loads of 6.5
 gm/nr (0.4 lb/1000 cu  ft)  had been tolerated  in  the same study.  This
 is  equivalent to an  average loading of 4.2 kg  penta/kkg MLSS with shock
 loadings  up to 16.9  kg  penta/kkg MLSS.   Considering that this waste also
 contains  phenols in  excess of 100 mg/1, a conservative loading rate of
 2  kg  penta/kkg MLSS  was chosen.  Assuming a penta concentration of 20
 mg/1  and  a mixed liquor concentration of  3000 mg/1 resulted in a required
 aeration  volume of about  83,270 liters (22,000 gallons) and a hydraulic
 detention time exceeding  three days, the  corresponding BOD loading
 (usinq  the calculated average from Table  14 which was assumed to be
 valid)  was a conservative  0.1 kg BOD/kg MLSS.   The phenol  loading rate
 was about 0.01 kg phenol/kg MLSS, which was considerably less that the
 maximum loadings recorded  in the literature for wastewaters not con-
 taining  penta.  With these conservative design parameters and with the
 further safeguard of pre-chlorination,  it was felt that satisfactory
 results  could be obtained.

      Due  to  the lack of field information on the necessary dosages of
 chlorine  for pre-chlorination and post-chlorination,  precise design
 parameters  could not be defined.  The pre-chlorination dosage capability
 was therefore designed to range from 0  to 4000 mg/1  and the post-
 chlorination from 0  to 400 mg/1.

 DESIGN AND  CONSTRUCTION

     The  basic units required for effective chemical  and biological
 treatment of the wastewater based on the  parameters  developed above and
with as much flexibility as possible due  to the experimental  nature of
 the project, were considered  to be as follows:

     1.  Surge or  equalization basin.   The existing  Pond #2  was  suitable
         for this  purpose.
     2.   Influent  pump.  A small  centrifugal  pump with  a maximum
         capacity  of 37,850 Ipd (10,000 gpd) mounted  on a  floating
         platform  in Pond  #2  was considered adequate.

                                    46

-------
      3.   Flow measurement and control device.  The small flow could be
          easily measured with a  rotameter and controlled with a valve.
      4.   Pre-chlorination unit.  Total detention time equaling 12 hours
          with baffling  for  varying detention times and by-pass capability.
      5.   Aeration  tank.  A  total volume of at least 83,290 Ipd (22,000
          gallons)  should be divided  into two or more sections for varying
          loading rates.
      6.   Final  clarifier.   An overflow rate of 8150 to 12,200 Ipd/m2
          (200 to 300 gpd/ft2) was considered necessary.
      7.   Post chlorination  tank.  A  detention time of 8 to 10 hours was
          provided.
      8.   Chlorine  injector  equipment.  A variable feed rate up to 91
          kg/day (200 Ib/day) was provided.
      9.   Aerobic digester.  A retention period of 15 to 20 days was
          allowed.
     10.   Final  sludge disposal was to be by irrigation on an existing
          field.

      A package  unit was delivered by Davco in January 1973.  As illus-
 trated in Figure 14, the treatment plant consisted of two rectangular
 tanks and a separate circular clarifier.  The first rectangular tank,
 3.66  m (12 ft)  wide by 9.75 m (32 ft) long, was divided into an aerobic
 digestion tank  and pre-chlorination tank, each approximately 1.83 m
 (6 ft) in length, and the #1 aeration tank which was about 6.1 m (20 ft)
 long.  The secorvd tank was 2.44  (8 ft) wide by 11.6 m (38 ft) long and
 was divided into two sections, the #2 aeration tank which was about
 7.9 m (26 ft) long, and the post chlorination tank which was about
 1.83  m (6 ft) long.  The clarifier had a diameter of approximately 2.44 m
 (8 ft).   Flow entered either the pre-chlorination chamber or moved
 directly  to the aeration tank.  At 19 1pm (5 gpm), the detention time
 in the pre-chlorination tank was about 15 hours.   This tank was later
 baffled to provide variable detention times.   The aeration time in the
 #1 tank was about 50 hours.   All  activated sludge was returned to this
 tank.  The flow then entered aeration tank #2 which had a detention time
 of 47 hours at  a flow of 19 1pm (5 gpm).   The mixed liquor from tank
 #2 then settled  in the clarifier which had a  surface overflow rate
 of less than 6100 Ipd/sq m 150 gpd/sq ft)  at the  average design flow of
 27,250 Ipd (7200 gpd).   The clarifier overflow could be post chlorinated
 prior to  final discharge.

     Air was supplied to the aeration tanks,  aerobic digester,  and  the
 air lift  sludge return line by a  duplex  blower driven by a  7.5 hp motor.
 The total  expected air requirement was 5.2 cu m/min at 1.34 atm (185 cfm
 at 5 psig).

     The entire plant was  placed  on a reinforced  concrete slab above
ground.   All  extension surfaces were coated with  insulating material  to
protect against severe winter weather.   Heater tape was  placed  on
exposed pipes  and valves and electric immersion heaters  were  placed  in
 the aeration tanks.
                                    47

-------
                                                                          INFLUENT
00
                                                                                   RETURN  SLUDGE
                                                                                                   BLOWER
                                                                                                   DUPLEX
                   AERATION  TANK NO.  1
                   AERATION  TANK  NO.  2  BYPASS
                                                                                                 CLARIFIER
                             AERATION TANK NO. 2
EFFLUENT
                                                FIGURE 14.
                                 Schematic of "Package" Treatment System

-------
      Due to  the  high nutrient levels observed in the pre-design study,
 no  nutrient  addition was provided  in the final design.  Control of pH,
 was not  included  in the final design.  It was found that manual addition
 of  lime  to the aeration basins on  an as needed basis would provide
 satisfactory pH control.

      In  addition  to the treatment  plant itself, laboratory facilities
 were also constructed on-site.  A  full time chemist was employed to
 perform  all  analyses on-site with  the exception of BOD tests which were
 conducted by an outside laboratory.  A treatment plant operator was
 trained  to maintain and operate the plant and also to assist in per-
 forming  daily sample collections and analyses.

 PLAN OF  OPERATION

      The original operating schedule developed for the project was
 based on the uncertainty of the effects of pentachlorophenol  on the .
 activated sludge process.  The original schedule is as follows:

 Month #1 - Chlorinate the effluent at 100 percent of chlorinator
           capacity using full detention time in prechlorination
           facility.  With BOD loading equaling 0.1 kg BOD/day/kg
           MLSS, maintain MLSS around 3,000 mg/1.  Post-chlorinate
           to produce an effluent phenol  concentration of 0.1  mg/1.
 Month #2 - Reduce pre-chlorination to 50% of capacity or chlorinate
           only half of the influent stream at 100% capacity,  other-
           wise, maintain steady-state conditions.
 Month #3 - Reduce pre-chlorination by 50% again, resulting in  a total
           decrease since initial  operation of 75%.  Maintain  con-
           stant conditions.
 Month #4 - Based on the previous three months of operation, dis-
           continue pre-chlorination entirely or operate at the miniumum
           level apparently required.   Determine this level by ex-
           amining the condition of the biological  process during the
           first three months.  Also,  study the effect of detention time
           on chlorination by collecting  samples from each section
           of the baffled pre-chlorination tank.
 Month #5 - Maintain pre-chlorination at the minimum level  determined
           above or increase it as necessary while  doubling BOD and
           PCP loadings by halving the aeration tank volume.   Also,
           attempt a 20% reduction in  MLSS concentration.
 Month #6 - Pre-chlorinate as necessary while again  reducing MLSS by
           20%.   After two weeks,  if possible,  reduce  MLSS by  another
           20%.
Month #7 - Pre-chlorinate as necessary while again  reducing MLSS by
           20% with further reductions  if possible.
Month #8 - Operate at  steady state conditions utilizing  the optimum
           pre- and post- chlorination  dosages  determined  during the
           operating period, as  well as the corresponding  optimum
           BOD and penta loading rates.

     Although the package plant  arrived in  Carbondale  in  February 1973,
because of inclement weather it  was not ready for startup  until  July.

                                   49

-------
 Due to the delay,  it was decided  to  initiate operation without pre-
 chlorination  and  thereby determine immediately whether chlorination
 would  be  required.

     On this  basis, plant  startup procedures were initiated on July
 26,  1973.   The  aeration basins were  filled with water from the emergency
 lagoon, Pond  #1,  which had low concentrations of boron, phenols, and
 penta.   Bacterial  inoculation was accomplished by placing horse manure
 into the  aeration  tank and aeration  was begun.  One week later a 23 1pm
 (6  gpm) feed  mixture of emergency lagoon water and concentrated waste
 from Pond  #2  was  begun.  By the middle of August the proportion of the
 mixture consisting of concentrated waste had been increased to 100
 percent.   Normal mechanical problems were encountered during the initial
 startup period.   During the latter part of August, a pin sheared in the
 clarifier  sludge  rake mechanism and  one pump failed.  The sludge rake
 malfunction resulted in low MLSS  concentrations throughout August.  After
 the  shear  pin was replaced, the treatment plant was again placed in
 operation  and startup was continued  through September 1973.

     Because  of the immediate success of the complete mix process with-
 out  pre-chlorination, the entire  operating schedule was modified.
 This revised  schedule is shown in Table 15.  Due to inclement weather
 and  later  mechanical failures, this  schedule could not be adhered to
 exactly; however, all the desired objectives were accomplished during
 the  study  period.

 TESTING SCHEDULE

     The on-site laboratory was equipped with the necessary materials
 to perform basic gravimetric, colorimetric, and titrametric analyses
 including  COD, solids, nutrients, phenols, pentachlorophenol, oil and
 grease, residual chlorine, pH, temperature, and dissolved oxygen.
 BOD  analyses  were performed by an outside laboratory and any special
 analyses required such as gas chromatography or metal analyses were
 performed  elsewhere.

     Samples  were collected daily for analysis.  Batch samples were
 used instead  of composites because of the presence of the large surge
 lagoon  which  minimized fluctuations  and because of the large detention
 time in the treatment plant itself which tended to smooth out variations
 throughout the system.

     Due to the large number of analyses  needed  and  the  limited staff
at Carbondale, a schedule of analyses based  on  the minimum requirements
for experimentation and  the manpower  limitations  had  to  be developed.
The schedule shown in Table 16 was followed  throughout the study  period.
During periods when more  information  was  desired  in one  unit of the
treatment system than another,  more analyses were performed.  For
instance, when the effects  of post-chlorination were  being closely
studied, more chlorine  residual  determinations were required.  BOD,
COD, phenol, solids,  and  oil  and  grease analyses were performed ac-
cording to Standard Methods (13  edition)  (72).  Nutrients were analyzed


                                   50

-------
                  TABLE  15. REVISED OPERATING SCHEDULE
# 2
# 3


# 4


# 5


# 6
i 7
                Objective

        Startup and shakedown
Hydraulic loading
  variation
Organic loading
  variation

Increased organic loading
Increased organic loading
Post-chlorination studies
Pre-chlorination studies
# 8     Optimization
                 Operation

 Inoculate  aeration  tanks with activated
 sludge or other  bacteria source.  Operate
 plant with  increasing proportion of con-
 centrated waste  and  decreasing proportion
 of dilution water.   Shakedown mechanical
 equipment,  repairing and replacing as
 necessary.

 Increase the hydraulic loading to the
 treatment system in  increments up to the
 limit of hydraulic capacity or organic
 loading rate, whichever is reached first.

 Restabilize the  process at 4 to 6 gpm
 using only  one aeration basin.

 Reduce the  mixed liquor suspended solids
 or increase the  flow rate incrementally.

 Continue reducing the MLSS or increasing
 the flow rate incrementally.

 Measure the effects of post-chlorination
 on PCP, phenol,  COD and BOD concentrations
 at various  dosages, increasing the dosage
 incrementally over the month.

 Operate the treatment plant at near constant
 conditions  while increasing the pre-chlori-
 nation dosage incrementally and measuring
 its effect  on the activated sludge process.

 Based on the previous months' experience,
operate the process at those conditions
which gave  the best results including pre-
and post-chlorination as necessary.
                                    51

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TABLE 16.   SCHEDULE OF ANALYSES
Sampling Point and Number of Analyses Per Week
Parameter
BOD
COD
Phenol
Penta
TS
TSS
VSS
TDS
NH4+
P04=
Influent
2
2
2
2
2
2
-
2
1
1
Prechlorination
1
1
1
1
-
-
-
-
-
_
Aeration Basins
2
2
2
2
-
3
3
-
-
_
Clarifier Post Chlorination
1 2
1 2
1 2
1 2
2
2
-
2
1
1
SVI
Oil and grease
Temperature
D.O.
PH
    Residual
                      5
                      5
                      5
    0-5
0-5
                 52

-------
with colorimetric kits.  The determination of penta proved to be
difficult and, in fact, no truly satisfactory method was found.   The
method chosen at the beginning of the study after careful  evaluation
of the two or three methods available was the Safram'n method which
is a distillation and color development technique.
                                  53

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                             SECTION VI

                       RESULTS AND DISCUSSION

      The  experimentation phase of the project was begun in July 1973,
 and  was completed  in May 1974.  The raw data collected during the study
 is contained  in  the Appendix.

 PHASE 1 -  START-UP AND STABILIZATION

      The  start-up of the treatment system was accomplished with rela-
 tively little difficulty.  Without the mechanical start-up problems
 encountered,  the activated sludge process could have been stabilized in
 two  weeks,  but, with the mechanical problems, as previously discussed,
 the  start-up and stabilization phase took about five weeks.  A significant
 amount of  data was not collected during the start-up period; however,
 most of the data obtained is presented in Table 17.  The average influent
 and  effluent concentrations of COD for the five week period were 1540
 mg/1  and 410 mg/1, respectively, which is a reduction efficiency of
 73 percent.  The phenol  reduction efficiency for the same period was
 97 percent.  The influent penta concentration was much less than expected
 but  a  reduction through  the treatment system of 79 percent was obtained.

 PHASE  2 -  STEADY STATE OPERATION

     For a period of about four weeks (August 30 through October 5,
 1973), the treatment plant was operated at constant flow and loading
 to evaluate the performance of the activated sludge process under
 controlled conditions.    During this phase, flowrate was maintained
 at 23  liters per minute  (six gallons per minute), and influent COD
 averaged 178 mg/1, influent phenols averaged 88 mg/1, and influent
 penta averaged 1.7 mg/1.  The average results of this period are pre-
 sented in Table 18 and, as can be seen, the effluent quality varied
 little during the four week period indicating a stable biological
 process.   Effluent COD averaged 404 mg/1  and never varied more than
 10 percent from this value.   Effluent phenols rarely varied from the
 average value of 1 mg/1.  The effluent PCP value never exceeded  0.6
 mg/1  and averaged 0.4 mg/1.   As it turned out,  the loading rate  was
 not constant because of sludge buildup.   However, in general,  it can
 be concluded from this  data  that a conservatively designed activated
 sludge process treating creosote and  pentachlorophenol  wastewater
 should be able to reduce COD by 75 to 80 percent, phenols by 95  to  99
 percent,  and PCP by 75  to 80 percent.

 PHASE 3 - LOADING RATE  VARIATION

     Phase 2,  Steady-State Operation,  was  terminated  after  the first
week in October 1973.   From  that time  until  mid-November,  experimenta-
 tion was  directed primarily  at examining  the effects of  loading rate
 variations on  the activated  sludge process.   Due  to  the conservative
 design of the  treatment system,  a  considerable  degree of  variation  both
 in organic and hydraulic loading rate  was  possible.

                                   54

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TABLE 17.  STARTUP AND STABILIZATION DATA
Date
1973
7-30


7-31


8-1


8-2


8-3



8-4

8-5

8-6



8-8



8-10



Flow, liters per minute
Dilution Concentrated Sampling
Water Waste Point
0 0 #1 Aeration
Dilution
Raw Waste
0 11,350 #1 Aeration
#2 Aeration
Effluent
0 0 #1 Aeration
#2 Aeration
Effluent
0 0 #1 Aeration
#2 Aeration
Effluent
17.0 1.89 Influent
#1 Aeration
#2 Aeration
Effluent
15.1 3.8 Influent
Effluent
13.2 5.7 Influent
Effluent
11.4 7.6 Influent
£1 Aeration
#2 Aeration
Effluent
3.8 15.1 Influent
#1 Aeration
#2 Aeration
Effluent
3.8 15.1 Influent
=1 Aeration
r2 Aeration
Effluent
Parameter
COD Phenols PCP
(mg/1) (mg/1) (mg/1 )
1
- 1
150
16
8
5
1 0.6
1 0.6
1 0.6
0.6
0.6
0.6
1
1
1
1
10
1 -
12
1
15
1
1 -
1
30
1
1
1
65
1.5
1.6
1.4

Sludge
(ml/1)
0
_
-
	
_
-
_
M
-
0.2
0.3
-

0.1
0.05
-
•*
-
.
-
fm
0.1
0.1
-
wm
0.1
0.1
-
_
0.3
0.4
_
                    55

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TABLE 17.  STARTUP AND STABILIZATION DATA
Date
1973
8-16



8-17



8-20
Flow, liters per minute
Dilution
Water
3.8



1.9



0
Concentrated
Waste
15.1



15.1



11.4
(Pump Problems)
8-21



8-23
0



0
7.6



11.4
(Pumps Required)
8-24

8-27



8-28
8-29
8-30



8-31



0

0



Clarifier
Clarifier
0



0



15.1

22.7



paddles found
Sampling COD
Point (mg/1)
Influent
#1 Aeration
#2 Aeration
Effluent
Influent
#1 Aeration
#2 Aeration
Effluent
Influent
Effluent
Influent 1,260
#1 Aeration
#2 Aeration
Effluent 350
Influent
Effluent
Influent
Effluent
Influent
#1 Aeration
#2 Aeration
Effluent
Parameter
Phenols PCP
(mg/1) (mg/1)
70
2
2
2
70
3
2
2
70
1
70 3.4
1.5
1.5
1.5 0.6
70 3.4
1.5 0.3
70 2.6
1 0.3
80
3
2
2

Sludge
(ml/1)

0.7
0.6
-
mm
0.5
0.4
-
w
-
_
0.4
0.4
-
mm
-
_
-
—
2.0
1.7
-
to be not functioning
paddles repaired
22.7



22.7



Influent 1,820
#1 Aeration
$2 Aeration
Effluent 470
Influent
rl Aeration
#2 Aeration
Effluent
85 3.0
3
2
2 0.7
95
3
2
2
—
11.0
7.5
-
—
13.0
9.5
_
                      56

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               TABLE 17.   STARTUP AND  STABILIZATION  DATA
      Flow, liters per minute               	Parameter
Date  Dilution   Concentrated    Sampling    CODPhenols  PCPSludge
1973   Water         Waste       Point      (mg/1)  (mg/1    (mg/1) (ml/1)
AVERAGE OF ALL  STARTUP  PERIOD   Influent     1,540     56      2.9   34
                                #1 Aeration     -        2-30
           DATA                 n Aeration     -        2
                                Effluent       410      2      0.6   43

                                             P04     NH4+
Influent
#1 Aeration
#2 Aeration
Effluent
TABLE 18. EFFECTS OF
Average Values from Steady
Flow Rate
Influent
22.7 1pm
(6 gpm) Effluent
Reduction
Result of Shock
Flow Rate
41.6 1pm
(11 gpm) Influent
Effluent
Reduction
SHOCK
State
COD
1784
404
77%
555 47.5
430 56.7
440 66.0
LOADING
Operation - mg/1
Phenols
88
1
99%



PCP
1.7
0.4
76%
Loading
COD
2650
710
73%
Phenols
90
10
88%
PCP
1.62
1.32
19%
                                    57

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      The  effects of  shock loading were observed during a three day
 period.   The flowrate, which had been maintained at a constant 21 liters
 per minute  (5.5 gpm) for over four weeks, was increased to 42 1pm (11 gpm)
 on October  8 and maintained at this rate for three days.  At this rate,
 the nominal detention time in the aeration tanks was 44 hours, the BOD:
 MLSS  ratio  was about 0.13 kg BOD/kg MLSS, and the COD:MLSS ratio ex-
 ceeded 0.5  kg COD/kg MLSS.  The penta loading was below 1 gm/cu m (0.06
 Ib per 1000 cu ft) of aeration volume.  While this is still far below
 the shock loadings of Thompson (46) — 6.5 gm/cu m (0.4 Ib per 1000
 cu ft), the detention time was less than one-half of the five day
 detention used in his laboratory studies.  The result of this increased
 loading and decreased detention time was a noticeable decrease in treat-
 ment  efficiency as shown in Table 18.  Phenol concentration increased
 rapidly in  both aeration tanks as well as in the effluent.  Phenol
 removal efficiency decreased from 99 percent to about 89 percent and
 was decreasing rapidly with time.  COD removal efficiency was less
 affected  but did show a decrease in efficiency from near 80 percent
 to about 72 percent.  BOD removal was apparently not affected but,  as
 noted previously, the value of the BOD test for this waste is questionable.
 It is noteworthy that penta removal efficiency was apparently affected
 by the shock loading.  At a constant loading, the penta removal  had
 averaged 79 percent but, apparently because of the shock loading, this
 was reduced to virtually zero removal of penta.   Whether the decreased
 removal efficiency was due to a decrease in the rate of oxidation of
 penta  or  to the  decreased hydraulic detention time was not determined.

      In order to determine the effects of increased loading and  decreased
 detention time under more constant conditions, two series of loading var-
 iation were initiated.   The flowrate was increased incrementally from
 20.8 1pm (5.5 gpm) to a maximum of 41.6 1 pm (11  gpm) for the first series
 and to a maximum of 49 1 pm (13 gpm) for the second series.  The first
 series of incremental flow variation was conducted during the last two
 weeks of October and the second series during the first two weeks of
 November.

     The activated sludge process was restabilized for a four day period
 after the shock loading test.   On October 15, the flow rate was  increased
 to 26.5 1pm (7 gpm), then 34 1pm (9 gpm)  on the  16th, and finally to 41.6
 1pm (11 gpm) by the 18th of October.   The flowrate was maintained at 41.6
 1pm (11 gpm) for about one week.   The results of  this phase of experi-
mentation are shown in Table 19.   As the  lo-ading  was  increased,  the  penta
removal efficiency again decreased until  virtually no removal  was obtained.

     The phenol  removal  efficiency decreased  slightly but the effluent
concentration  of phenol  never exceeded 3.0 mg/1.   Apparently,  as  the
loading was increased,  the capacity of the activated  sludge in the first
aeration basin to oxidize phenols  was approached  and  exceeded.  As the
loading was increased the concentration of phenols in the first aeration
tank increased.   This resulted  in an increase in  the  loading  on  the  second
tank and some  increase  in effluent phenol  concentration.   The  increased
loading on the second aeration  tank produced  a rapid  buildup of  suspended
solids which indicated  increased  biological activity.
                                    58

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TABLE 19.  RESULTS OF LOADING RATE VARIATION
Date
1973
(FIRST
10-15



10-16



10-17



10-18



10-19



10-24



(SECOND
11-2



11-6



Flow Sampling
1pm Point
LOADING SERIES)
26.5 Influent
#1 Aeration
#2 Aeration
Effluent
35.1 Influent
#1 Aeration
#2 Aeration
Effluent
35.1 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
LOADING SERIES)
20.8 Influent
#1 Aeration
#2 Aeration
Effluent
20.8 Influent
#1 Aeration
#2 Aeration
Effluent

COD BOD
(mg/1) (mg/1)
_
-
-
-
_ _
-
-
-
2117
-
-
757
_ _
-
-
-
755
-
-
75
2117
-
-
846

1045
-
-
no
2290
-
-
730
Parameter
Phenol PCP
(mg/1) (mg/1)
75 2.15
2
1
1 1.62
75
3
2
1
80
3
2
1
90 2.15
5
3
2 2.15
75 2.28
5
2
1 1.78
70
6
4
3

90 2.3
3
2
1 2.4
90
3
2
1

Sludge
(ml/1)

400
305
-
.
430
330
-
•»
470
340
-
_
500
365
-
mt
500
380
-
—
560
440
-

_
600
425
-
—
680
490
_
                     59

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              TABLE  19.   RESULTS OF LOADING RATE VARIATION
Date
1973
(FIRST
11-7



11-8



11-9



11-12



11-13



11-14



Flow Sampling
1pm Point COD
LOADING SERIES) (mg/1 )
26.5 Influent
#1 Aeration
#2 Aeration
Effluent
36.0 Influent
#1 Aeration
#2 Aeration
Effluent
41.6 Influent
#1 Aeration
#2 Aeration
Effluent
49.2 Influent
#1 Aeration
#2 Aeration
Effluent
49.2 Influent 2650
#1 Aeration
#2 Aeration
Effluent 1040
49.2 Influent
#1 Aeration
#2 Aeration
Effluent
Parameter
BOD Phenol
(mg/1) (mg/1)
90
5
3
2
100
5
2
1
90
7
3
2
80
9
5
2
90
25
15
TO
90
25
20
20

PCP
(mg/1)
2.1
_
-
2.1
_
-
-
-
2.4
-
-
2.2
2.7
-
_
3.2
w
-
_
-
3.1
_
_
2.7

Sludge
(ml/1)
_
700
470
-
—
620
470
-
..
690
480
-
_
_
_
-
_
525
580
-
«•
500
500
-
11-15    0      Effluent                      40
(Flowrate Variation Discontinued)
                                    60

-------
     The COD removal efficiency, which had decreased during the earlier
period of shock loading, continued to decrease during this period also.
By October 24, the COD removal efficiency had decreased to about 60
percent.  During the same period, however, BOD analyses indicated good
BOD removal efficiency.  On October 19, with the flowrate at 41.6 1pm
(11 gpm), the BOD removal was 93 percent.

     The second series of loading variation was begun on November 7,
following a week-long period of stabilization at the design flowrate.
The flowrate was increased to 49 1pm (13 gpm) over a five day period,
the results of which are shown in Table 19.  The results are quite
similar to those obtained in the October series of loading variation.
Virtually no penta removal occurred and the COD removal efficiency was
reduced to about 60 percent.  The buildup of phenol  in both aeration  basins
occurred as before.  However, at 49 1pm (13 gpm) the oxidation of phenols
decreased very rapidly and was accompanied by sludge bulking in the
clarifier.  At this rate, detention time in the aeration tanks was
37 hours, the BODrMLSS ratio was approximately 0.12 kg BOD/day/kg
MLSS and the COD:MLSS ratio equalled 0.36 kg COD/day/kg MLSS.  The
penta loading was nearly 1.8 gm/cu m (0.II lb/1000 cu ft) of aeration
volume and the phenol:MLSS ratio was 0.01 kg phenol/day/kg MLSS.

     Because of the fact that the hydraulic capacity of the treatment
system was probably exceeded at 49 1pm (13 gpm) and because the de-
tention time in the aeration basins was less than 50 percent of the
design aeration time, the above loadings probably do not represent
the maximum organic loading conditions at which the complete mix
activated sludge process could effectively function.  It was there-
fore decided to reduce the aeration volume by about 50 percent by
utilizing only one aeration tank.  By then increasing the flowrate
or decreasing the MLSS, a comparatively large change In loading could
be obtained without hydraulically overloading any unit of the treatment
system.  Before this phase of the experimentation could be commenced,
however, severe winter weather including snow, ice,  and subzero tempera-
tures set in.  At the same time, the immersion heaters which had been
placed in the aeration tanks failed.  The result was a period from
December 8, 1973, through January 17, 1974, during which the treat-
ment plant was inoperative due to frozen and broken valves and pipes.
During this period the aeration tank contents were aerated to maintain
aerobic conditions.  Following a period of a few warm days in mid-
January, the necessary repairs were completed and plant operations
resumed.

     It should be noted that the activated sludge responded immediately
to the reintroduction of feed water and stability was soon apparent.

     As noted above, it had been decided to utilize only one aeration
tank for the purpose of loading variation.  Because of the continuing
cold weather, it was decided to postpone further loading variation
until spring.  The main experimentation efforts for the period from
January 17, 1974, through March 4, 1974, were directed at observing
the effects of post-chlorination of effluent quality.  In order to
maintain continuity, this period will be discussed out of chronological

                                     61

-------
order so that the results of loading variation can  be  concluded.

     Loading variation recommenced  on March 5, 197^,  following
the post-chlorination study.  As mentioned previously, this  portion
of the study was performed using only the first aeration  basin which
had a volume of about 56,400 liters (14,900 gallons).  The initial
flowrate was 15 1pm (4 gpm) and the detention time  in  the aeration
tank was 62 hours.  The BOD:MLSS ratio  was approximately 0.10 kg
BOD/day/kg MLSS, the CODrMLSS ratio  was 0.27 kg COD/day/kg  MLSS, the
ratio of phenol to MLSS equalled 0.007 phenol/day/kg MLSS, and the
penta loading reached 3.2 gm/cu m (0.2 lb/1000 cu ft)  of  aeration volume.
Using this configuration of treatment units at 15 1pm  (4  gpm), a COD
reduction of 70 percent,  a BOD reduction of 85 percent, and  a phenol
reduction of 99 percent were obtained.

     From March 4 through the end of April the flowrate was  increased
in increments from 15 1pm to 30 1pm (4gpm to 8 gpm). At first, it
appeared that a flowrate of 19 to 23 1pm (5 to 6 gpm)  was the maximum
rate which could be handled without upsetting the biological process.
As can be seen in Figure 15, on three different occasions as this
flowrate was reached, the phenolic reduction decreased rapidly.  The
sludge settling characteristics also changed at this loading with the
sludge volume index (SVI) increasing from about 100  to  over 200.  On
the third occasion the flowrate was increased beyond this loading range
to a maximum of 30 1pm (8 gpm). At this loading, the activated sludge
appeared to restabilize considerably and the SVI decreased to approxi-
mately 100.  The phenol reduction efficiency again  returned  to 99 percent
removal  and BOD was removed at about 90 percent efficiency.  COD re-
moval had decreased markedly at this loading, however, to about 57
percent.  Also, the plant operator reported that after about five days
at 30 1pm (8 gpm), sludge was beginning to rise in  the clarifier.  At
this point loading variation was suspended.  Thus,  the maximum loadings
achieved with a 31 hour detention time were a CODrMLSS ratio of 0.50
kg COD/day/kg MLSS, a BODrMLSS ratio of 0.18 kg BOD/day/kg MLSS, a
phenol:MLSS ratio of 0.013 kg phenol/day/kg MLSS, and  a penta loading
of 7.3 gm/cu m (0.45 Ib penta/1000 cu ft) of aeration  volume.  As can  be
seen, these are relatively high loading rates.  The detention time of
31 hours is much less than that reported for penta  removal and the penta
loading exceeds the maximum loading attempted in previous laboratory
studies.

PHASE 4 - POST-CHLORINATION STUDIES

     Post-chlorination studies were begun on February  6,  1974, with
the primary objective of determining the effects of chlorine on
effluent quality.  During this period of the study, the activated
sludge process was operated with one aeration basin.   The influent
flowrate was maintained at 15 1pm (4 gpm) and the MLSS concentration
was held constant at about 3500 mg/1 by wasting sludge as necessary.
All other operating parameters were maintained constant to minimize
as many variables as possible during the post-chlorination phase of
the study.
                                   62

-------
CO
  70-



  63-




  60-




  83-




  30-




  45-


<

Z 40-


a"   _,
O 33-
~Z.
LU


°- 30-




   28-
          20
          15-




          10-




          3-
                        INFLUENT PHENOL  CONCENTRATION
                      EFFLUENT PHENOL CONCENTRATION,
                                                                                                                                 10
                                                                                                                                   a.
                                                                                                                                   o
                                                                                                                          -3




                                                                                                                           4




                                                                                                                          -3
            I  2 3 4 5 6 7 8 9 10 II 12 13 14 B 16 17 18 19 2021 22 232423 2627 28 2930 I  2  3 4 5 6 7 8 9 10 II 12 13 14 18 16 17 IB 19 20 21 22232425 262728 293031


                               MARCH, 1974                                               APRIL.I974


                                                               FIGURE  15.

                                            Influent and  Effluent Phenol  Concentration

-------
      Prior  to initiating  full-scale post-chlorination, some labora-
 tory scale  studies were performed on the clarified effluent to determine
 the range of post-chlorination which would be most effective.  For
 this purpose,  sodium  hypochlorite (clorox) was used at dosages ranging
 from 15  mg/1  to  500 mg/1  as HOC1.  As  illustrated in Figure 16, the
 residual  chlorine stabilized within thirty minutes for all dosages and
 then decreased slowly, if at all.  The effect of increasing dosage
 on  COD,  penta, and phenol is shown in  Table 20.  Minimal reduction in
 COD occurred  at  even  the  500 mg/1 chlorine dosage.  The effluent
 phenol was  already below  1 mg/1  and the reduction due to chlorine was
 not significant.  As  can  be seen in Figure 17, the effect of chlorine
 on  penta  was  quite significant,  producing  a  maximum apparent reduction
 of  77 percent  at a chlorine dosage of  250 mg/1.  The normally brown
 wastewater  was considerably lightened  in color with increasing chlorine
 dose.

 TABLE 20.   LABORATORY POST-CHLORINATION STUDIES
C19 Dosage
*(mg/l)
15
30
45
250
500
Time
(min)
40
40
40
60
60
Penta Phenol
(percent reduction)
16
31
38
77
75
—
--
--
25
33
COD
--
—
—
7
12
     In spite of the lack of beneficial   results from the laboratory
study, full-scale post-chlorination studies were conducted to  confirm
the laboratory results and to further study the effects  of chlorine
on penta.  Chlorine was injected into the post-chlorination tank at
concentrations varying from 7 mg/1  to 155 mg/1  as HOC1.   The detention
time in the post-chlorination tank  at 15 1pm 14 gpm)  was about 10
hours.   The MLSS concentration was maintained  between 3500 and 4000
mg/1.  The immersion heaters in the aeration tank limited temperature
variations while pH was held constant by lime additions.   The  dissolved
oxygen concentration was maintained at 2 mg/1.

     As shown in Table 21, there was no reduction in  COD even  at the
highest chlorine dosage.  Phenol concentrations in the effluent were
reduced by about 50 percent at chlorine residuals exceeding 11.1  mg/1.
There were apparent reductions in BOD ranging up to 64 percent.   How-
ever, the validity of this reduction is questionable  considering the
retardance of the BOD test and the  fact that no COD reduction  occurred.
The effect of chlorine on penta was either a reduction of penta or  a
reduction of the concentration of substances which interfered  with  the
analysis for penta.

                                  64

-------
     500-
   ^400-

   o>
   E


   "5
   £300-
    e
    c
in
     200
      100
                    i
                    15
30
45
60
                                                      Time (min)
90
105
120
135
                                                 FIGURE 16.

                                         Chlorine Residuals with Time

-------
 5.0i
 4.0-
o»
E
  3.0-

  2.0
  1.0-
                15
                          IS mg/| Chlorine
30         45
60
 i
75
90
K)5
                                             Time (min)
120
                                          FIGURE  17.

      Effects of  Chlorine on Pentachlorophenol  Concentrations  as  Measured bv Safranin Method
 i
135

-------
CD
                                                    TABLE 21.

                                       EFFECTS OF FULL SCALE POST CHLORINATION
Date
2/11/74
2/14/74
2/18/74
2/21/74
2/25/74
2/28/74
3/4/74
Chlorine
Feed
Ob/day)
0.75
0.75
1.0
3.0
5.0
7.0
10
Chlorine
Residual
(mg/1)
2
0
3
11
24
32
35
.0
.5
.3
.1
.4
.0
.7
Phenol ,
, 0)
0.6
0.5
0.4
0.9
1.2
0.8
1.1
mg/1
J2I
0.6
0.5
0.4
0.9
0.6
0.4
0.6
Penta,
Jll_
8.4
7.6
8.1
9.2
9.6
8.2
9.4
mg/1
J21
4.4
5.3
5.2
4.3
3.2
1.4
5.2
COD,
HI
595
645
755
700
855
835
805
mg/1
Jii
595
670
760
735
835
860
800
BOD,
HI
125
80
95
110
265
100
125
mg/1
Jil
95
75
80
85
95
80
65
           (1)  Before Chiorination
           (2)  After Chiorination

-------
      It should be noted that the nutrient levels during this period,
as throughout the entire study, were quite elevated due to the previous
use of a fire retardant which contained ammonia and phosphorus com-
pounds.  The presence of large concentrations of ammonium ions in the
wastestream may have caused the high residuals of chlorine and con-
tributed to the poor reaction of chlorine with the organics in the
treated effluent.

PHASE 5- PRE-CHLORINATION

     As has been previously discussed, the primary purpose of pre-
chlorination was to reduce penta concentrations to a level that would
allow satisfactory biological activity in the activated sludge process.
It had been demonstrated during the previous phases of the project
that pre-chlorination was not required in order to treat the wastes
biologically.  The need for pre-chlorination was therefore considered
limited.  However, before abandoning the concept entirely, it was
decided to experiment on a laboratory scale with chlori nation of the
raw waste to determine if any measurable benefical effects occurred.

      Initially, laboratory tests were conducted to determine chlorine
persistence.  This was considered important due to the high dosages
which were expected to be required and because only small chlorine
residuals could be allowed to enter the aeration units without damage
to the activated sludge.  Chlorine doses of approximately 600, 1200,
3400, and 6900 mg/1 were prepared in the laboratory using sodium
hypochlorite.  Chlorine residual was measured with time over a period
of at least 10 hours for each sample.  The resulting chlorine residual
curves are shown in Figure 18.   It can be seen that the primary
reaction of chlorine with the raw wastewater occurred within two to
four hours and that the decrease in total residual occurred at a much
slower rate after this initial  period.  After 19 hours of reaction
time the sample initially treated with 600 mg/1. of chlorine still
contained a residual of over 200 mg/1.  High initial doses resulted
in correspondingly higher total residuals.  The 6900 mg/1 initial
doses, for instance, produced a residual  after 10 hours of over
2600 mg/1.  Obviously, if large chlorine doses were required, high
chlorine residuals would result and a substantial degree of dechlorina-
tion would be required before biological  treatment would be possible.

    .Subsequent laboratory studies were conducted to determine the
effects of chlorine on the raw waste at concentrations of chlorine
of 500 mg/1 and 1000 mg/1.   As  illustrated in Figure 19, oxidation of
phenols occurred rapidly and completely at chlorine levels of 500
mg/1  and 1000 mg/1.  The reaction at pH 8 was somewhat more complete
after one hour than the reaction at pH 2.  Figure 20 shows penta
removal  with chlorine doses of  500 mg/1  and 1000 mg/1.   The efficiency
of removal of penta was 40 percent using  500 mg/1 of chlorine at pH
8, 81 percent using 500 mg/1  of chlorine  at pH 2 and about 80 percent
using 1000 mg/1  of chlorine at  pH 8.
                                   68

-------
     1400-1
CT>
VO
                                               1200 rag/1  chlorine dosage


                                                           A
                                                600 mg/1  chlorine dosage
           0
                       16
18
20
                                        Time After  Initial Dose
                                                 FIGURE 18  (a).
                                            Chlorine Persistence
(hrs)

-------
7000
                          6900 mg/1 chlorine dosage
2000-
                      3400 mg/1 chlorine dosage
1000-
     0
     6         8        10        12
   Time after Initial Dose (hrs)
FIGURE  18  (b).    Chlorine Persistence
14
16
18
20

-------
  60H


   55


   50


   45-


  40-


   35


   30-
x

f  25-


£  20-


    15-


   10


    5-
                                       25Omg/l Clodded
                     500 mg/l
                     CMpH=8
                                        1.0
                                      1.5
2J5
3.0
                                              Tim* (hrs)

Figure 19. Effect of Chlorination on Phenolic Concentration of Raw Wastewater with Activated Carbon

-------
ro
                                                                       pH=8
                                                                                   mg/1 C12, pH=8
                                                                                            3.0
                                                          TIME  (hrs)

                                                           FIGURE 20.
                              Effect of Chiorination  on  Penta Concentration of Raw Wastewater
                                                     with Activated  Carbon

-------
      Also shown in Figures 19 and 20 is the effect of adding powdered
 activated carbon to the raw wastewater.  As this was not part of the
 project objectives, the use of activated carbon was not studied exten-
 sively.  However, the few tests performed indicated that activated
 carbon at a concentration of 0.5 grams/liter can reduce phenol  concen-
 tration in the raw waste by 84 percent and penta by about 25 percent
 At a concentration of 2.0 grams/liter,  powdered activated carbon removed
 about 61  percent of the phenols and 98 percent of the penta       rem°ved

 ** H-iU wa? thought that the  adsorbed  phenol and penta  might be more
 readily oxidized either chemically or  biologically  while attached  to
 the carbon than when  in solution.   Therefore,  Figures  19 and 20 also
 show the  results of a  few  experiments  in which chlorine was  added  to a
 solution  of powdered activated  carbon and  raw  wastewater.  The  effert
 of the  chlorine was apparently  to  attack the carbon preferentially
 resulting  in  the desorption of  the phenol  and  penta molecules!

     Based on the above results, it was intended that a full-scale
 pre-chlorination study be performed.  A schedule of chlorine doses
 and dechlorinating agent requirements was prepared and pre-chlorination
 was begun on May 7, 1974.  Due to the high chlorine residuals expected
 it was decided  to initiate pre-chlorination at 50 mg/1 and gradually
 increase the dosage to a maximum of 500 mg/1.  Dechlorination was to
 be accomplished by the addition of sodium sulfite.

     Pre-chlorination was continued for one month.  Unfortunately, due
 to several problems, the chlorine dosage never exceeded about 75 mg/1
 and no significant reductions in phenol, penta, or COD were obtained.
 Problems related to pre-chlorination were largely operational.  De-
 chlorination has not been anticipated to be a major problem in the
 initial  design and, consequently, no alternatives other than air
 stripping were  included in the treatment plant.  Therefore, control
 of chlorine residual was accomplished during the study by gravity
 fed sodium sulfite, and the reliability of this system was poor.
 Consequently, either due to the chlorine or to excess sodium sulfite
 entering the aeration basin, the activated sludge process appeared
 to be suffering rather than benefiting from pre-chlorination.  As
 can be seen by examination of the data  contained in the Appendix,
on May 28, 1974, phenol reduction efficiency appeared to be decreasing
rapidly.  Therefore, pre-chlorination was suspended on May 29.

 DISCUSSION OF RESULTS

     Based on the data developed during the study, the optimum
design and operating parameters for the treatment of the specific wood
preserving wastewater studied  can be presented.  As  the characteristics
of the waste are dependent upon the wood preserving process from  which
 it comes,  the design parameters for this waste may differ significantly
from those at any other plant.  However, the results and conclusions
should allow generalizations for similar wood preserving plants.
                                 73

-------
      It was determined early in the study that the wastewater inhibited
 the BOD test.  While this fact precludes the use of the BOD test as a
 precise method of analysis, it does not eliminate its usefulness as an
 indicator.  The average BOD/COD ratio of 0.35 was found to be rather
 constant for the raw waste.

      The result of loading the activated sludge at various rates is
 summarized for COD in Figure 21.  The percent reductions of COD when
 plotted against the nominal hydraulic detention time produce a linear
 relation as indicated.  Increasing organic loading resulted in a
 linear decrease in treatment efficiency up to a loading of about 0.35
 kg COD/day/dg MLSS, while the decrease in removal efficiency became
 much  less rapid above the loading.

      BOD and phenol concentration were readily reduced at practically
 every loading level tested.  A BOD reduction of 90 percent and a phenol
 reduction of 99 percent were obtained.

      The primary measurable effects of post-chlorination were to marked-
 ly improve the color of the wastewater and to reduce the penta concen-
 tration of the wastewater and/or the concentration of substances being
measured as penta.   Slight reduction of phenol  and no reductions of
 organics were indicated under these operating conditions.   At the
 conclusion of the EPA sponsored program,  Koppers Company conducted a
 further investigation of post-chlorination.   Preliminary results
 indicated that at a pH of 7 to 8 and a flow of 5.5 gpm, penta was
 reduced from about 5 mg/1  to less than 0.10 mg/1.

      Pre-chlorination was  found to be effective for reducing penta and
phenols in the raw waste.   The ratio of chlorine to penta  required to
produce an 80 percent reduction in penta  concentration was found to be
 in excess of 300:1  on a molar basis.  In  addition, the residual  chlorine
was found to be high following pre-chlorination,. a condition which was
possibly aggravated by the presence of ammonia.  The high  residual
chlorine caused operational  problems which were not overcome.   Con-
sequently, whether pre-chlorination could be beneficial to the activated
sludge process was  not clearly established.

     Based on the results  of this study,  the following are design para-
meters for this particular waste:

     Average COD loading =0.3 kg/day/kg  MLSS
     Maximum COD loading = 0.4 to 0.5 kg/day/kg MLSS
     Average BOD loading = 0.1  kg/day/kg  MLSS
     Maximum BOD loading = 0.2 kg/day/kg  MLSS
     Average phenol  loading =0.01  kg/day/kg MLSS
     Average penta  loading =1.62 gm/day/cu  m (0.1 lb/day/1000 cu ft)
     Maximum penta  loading =6.5 gm/day/cu m (0.4  lb/day/1000 cu ft)
     Average hydraulic detention time = 60 hours
     Minimum hydraulic detention time = 40 hours
                                   74

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                                          Hydraulic Detention  Time (hrs.)


                           10     20     30     40      50     60     70     80     90     100
en
                 80 .
              >


              O)
              o
              O
              O
                 70 .
                 60 -
                 50
0
I                0.3                0.4

    COD LOADING  RATE,  Ibs  COD/day/1b  MLSS

                  FIGURE 21,
COD Removal  In  The  Activated Sludge  Process
                                                                                        0.5

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     At the Carbondale wood preserving facility, the pretreatment system
was adequate for recovering pentachlorophenol  from the process waste
stream prior to biological treatment.   A properly designed and operated
preservation recovery system in conjunction with equalization is impor-
tant for successful  operation at the loadings  listed above.

     An activated sludge process designed on the basis of the above
should result in the following reduction efficiencies:

     COD removal efficiency = 70 to 80 percent
     BOD removal efficiency = 90 percent
     Phenol  removal  efficiency = 99 percent
     Penta removal  efficiency = 99 percent
                                  76

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                               SECTION VII

                               REFERENCES
 1.  American Petroleum Institute.  Manual on Disposal of Refinery
     Wastes, Vol. I.  Waste Water Containing Oil (6th Edition).(1959).

 2.  Industrial Waste Profiles, No. 5 - Petroleum Refining.  U.S. Depart-
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 3.  Wallace, A. T., G. A. Rohlich, and J. R. Villemonte.  The Effect of
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 4.  Mississippi Forest Products Laboratory.  Unpublished data.
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 5.  Middlebrooks, E. J. and E. A. Pearson.  Wastes from the Preservation
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     Thompson, Editor).Mississippi  Forest Products Laboratory,
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 8.  Simonsen, R.  N.   Oil  Removal by A1r Flotation at SOHIO Refineries.
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10.  Middlebrooks,  E. J.  Wastes From the Preservation of Wood, Journal.
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11.  Gaskln, P.  C.   A Wastewater Treating Plant for  the Wood Preserving
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     State College,  Mississippi.  (1971).


                                   77

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 12.   Jones,  R.  H.   Toxicity  in  Biological  Waste  Treatment Processes.
      In:   Proceedings,  Conference  on  Pollution Abatement and  Control
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      22:4. (1950).

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 17.   Chamber!in, N.  S.  and R. V. Day.  Technology of Chrome Reduction
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 18.   Dodge, B.   F.  and D. C. Reams, Jr.  Disposing of Plating  Room
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      and Technical  Development Committees.  Proceedings.  Washington,
      D. C.  (1958).

 20.   Eckenfelder,  W. W.  Industrial Water Pollution Control, McGraw-Hill,
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      44.  (1948).	

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     Wastes..  Vol.  I_v  Waste Water Containing Oil  (6th Edition).   (1969).

24.   Ingols,  R.  S., and G.  M. Ridenour.   The Elimination of Phenolic
     Tastes by  Chloro-Oxidation.  Water and Sewage Works.  (1948).

 25.  Ettinger,  M.  B. and C.  C.  Ruchhoft.  Effect of Stepwise Chlorination
     on Taste-and-Odor-Producing Intensity of Some Phenolic  Compounds.
     Journal  American Water Works Association.   43:  (1951).
                                    78

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 26.   Burttschell,  R.  G.  Chlorine Derivatives  of Phenol Causing Taste
      and Odor.   Journal American Water Works Association.  51:2.   1959.

 27.   Lee, C.  F.  Kinetics of Reactions Between Chlorine and Phenolic
      Compounds.  Proc. Fourth Rudolfs Research Conf.  Rutgers U.,
      New Brunswick, N. J. (1967).

 28.   Weil,  I., and J. C. Morris.  J. Am. Chem. Soc.  71.   (1949).

 29.   Vaughn,  J.  C.  Problems in Water Treatment.  Journal American
      Water  Works Association 56:5.   (1964).

 30.   Woodward, E. R.  Chlorine Dioxide for Water Purification.  Journal
      Pennsylvania Water Works Operators Association  2£k33_.  (1956). .

 31.   Glabisz, 0.  Chlorine Dioxide Action on Phenol  Wastes.  Przem.
      Chem.  45:211.   Chem. Abs.  65:10310. (1966).

 32.   American Petroleum Institute.  Manual on Disposal of Refinery Wastes.
      Volume on Liquid Wastes,  p. 11-3. (1969).

 33.   Dust,  J.  Pollution Abatement and Control in the Wood Preserving
      Industry.  Proceedings, Conference on Wood Preserving.  Mississippi
      State  College. (November 1970).

 34.   Cooke, R. and,P.  W. Graham.  The Biological Purification of the
      Effluent from a Lurgi Plant Gasifying Biuminous Coals.  International
      Journal of Air and Water Pollution.  9(3):97. (1965).

 35.   Badger, E. H.  M.  and M. I. Jackman.  Loadings and Efficiencies in
      the Biological Oxidation of Spent Gas Liquor.   Journal and Proceedings
      of the Institute of Sewage Purification.  Vol.  (2):159. (1961).

 36.   Preussner, R.  D.  and J. Mancini.  Extended Aeration Activated Sludge
      Treatment of Petrochemical Waste at the Houston Plant of Petro-Tex
      Chemical Corporation.  Proceedings, 21st Purdue Industrial Waste
      Conference,  pp.  591-599.  (1967JT

 37    Coe, R. H.  Bench-Scale Method for Treating Waste by Activated
      Sludge!  Petroleum Processing.   7:1128-1132.  (1952).

 38    Ludberg, J, E. and G. D. Nicks.  Phenols and Thiocyanate Removed
      from Coke Plant Effluent.   Ind. Wastes.   Vol: 10-13. (November 1969).

39.  American Wood Preservers'  Association.  Report of Wastewater
     Disposal Committee.   Proceedings. American Wood Preservers'
     Association.  56:201-204.  (1960).

40.  Nakashio, M.  Phenolic Waste Treatment by an Activated-Sludge
      Process.  Hajcko Kosaku. Zassjri. 47:389 and Chem. Abs..  71(8):236.  (1969).
                                   -79-

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41.  Reid, G. W. and R. J. Janson.  Pilot Plant Studies on Phenolic
     Wastes at Tinker Air Force Base.  Proceedings, 10th Purdue Industrial
     l-Jaste Conference,  p. 28. (1955).

42.  Putilina, N. T.  Removal of Phenol from Coke Works Waste Waters.
     Hygiene and Sanitation, Moscow.  Vol. (12):8. (1952), and Water Pol-
     lution Abs. 28:428.  (1955).

43.  Meissner, B.  Investigations of the Disposal of Phenol -Containing
     Wastes by Biological Procedures.  Wasserwerke-Wass Technology
     5:82 and Chem. Abs.  49:14237. (19557:

44.  Shukov, A. I.  The Treatment of Phenolic Waste Waters.  Hygiene
     and Sanitation, Moscow.  22(5):69.  1957. and Water Pollution Abs.
     32:424. (1959T:

45.  Kostenbader, P. 0. and J. W. Flacksteiner.  Biological Oxidation
     of Coke Plant Weak Ammonia Liquor.  J. WPCF.  41(2):199. (1969).

46.  Thompson, W. S. and J.  V. Dust.  Pollution Control in the Wood
     Preserving Industry, Part 2.  In-Plant Process Changes and Sanita-
     tion.  Forest Products Journal.  .22(7).  (1972).

47.  Kirsh, E. J. and J. E.  Etzel.  Microbial Decomposition of Penta-
     chlorophenol.  Personal correspondence from E. J.  Kirsh
     to Warren S. Thompson,  1972 and submitted for publication to J. WPCF.

48.  Cooper, R. L. and J. R. Catchpole.  The  Biological Treatment of
     Coke Oven Effluents.  Yearbook, Coke Oven Managers Association.
     (1967) and Water Pollution Abs. 42T562":   (1969).

49.  Hsu, C. P., W. F. Yang, and C. N. Weng.   Phenolic Industrial
     Wastes Treatment by a Trickling Filter.   K'uo Li Taiwan Ta Hsueh
     King Cheng Hsueh Kan.  Vol. (10):162.  19661  and Chemical Abs.
     67:8845. (
50.  Francingues, N. R.  Evaluation of a Pilot Study on a Creosote
     Waste from the Wood Preserving Industry.  Proceedings of Mississippi
     State University short course on Pollution Abatement and Control
     in the Wood Preserving Industry,  p. 165. (1970).

51.  Sweets, W. H. , M. K. Hamdy, and H. H.  Weiser.  Microbiological
     Studies on the Treatment of Petroleum Refinery Phenolic Wastes.
     Sewage Ind. Wastes.  26:826-868. (1954).

52.  Reid, G. W. and R. W. Libjjy.  Phenolic Waste Treatment Studies.
     Proceedings, 12th Purdue Industrial Waste Conference,  pp. 250-258.
     (1957).

53.  Ross, W. K. , and A. A. Sheppard.  Biological Oxidation of Petroleum
     Phenolic Wastewater.  Proceedings, 10th Purdue Industrial Waste
     Conference,  pp. 106-119.  (1955).
                                    80

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 54.  Reid, G. W., R. Wortman and R. Walker.  Removal of Phenol with
      Biological Slimes.  In:  Proceedings, 11th Purdue Industrial Waste
      Conference,  pp. 354-357.  (1956).

 55.  Harlowe, H. W., E. S.  Shannon and C.  L.  Sercu.  A Retro-Chemical
      Waste Treatment System.  In:   Proceedings, 16th Purdue Industrial
      Waste Conference,   pp.   156-166.   (1961).

 56.  Montes, G. E.,  D.  L.  Allen and E. B.  Showell.   Petro-Chemical
      Waste Treatment Problems.   Sewage Ind. Wastes  28:507-512.  (1956).

 57.  Dickerson, B. W. and  W. T. Laffey.   Pilot  Plant Studies of Phenolic
      Wastes from Petro-Chemical Operations.  In:   Proceedings. 13th
      Purdue Industrial  Waste Conference,   pp.  780-79T(1958).

 58.  Davies, R. W.,  J.  A.  Biehl and R. M.  Smith.   Pollution Control and
      Waste Treatment at an  Inland  Refinery.  In:   Proceedings. 21st
      Purdue Industrial  Waste Conference,   pp. 126-T31T(1967).

 59.  Austin, R.  H.,  W.  F. Meehan and J.  D.  Stockham.   Biological
      Oxidation  of Oil-Containing Wastewaters.   jnd.  Eng.  Chem. 46:316-318
      (1954).                            .               	

 60.   Prather, B. V.  and A. F. Gaudy, Jr.   Combined  Chemical, Physical,
      and  Biological  Processes in Refinery  Wastewater  Purification.   In-
      Proceedings. American Petroleum Institute  44fIII):1Q5-112.  (1964).

 61.   American Petroleum Institute.   Manual  on Disposal  of Refinery Wastes,
      Vol.  I.  Waste Water Containing'Oil (6th Edition).   Q960).  	

 62.   Montes, G.  E., D.  L. Allen and  E. B.  Showell.  Petro-Chemical  Waste
      Treatment  Problems.  Sewage Ind.  Wastes 28:507-512.   (1956).

 63.   Biczyski,  J. and J. Suschka.   Investigations on  Phenolic  Wastes
      Treatment  in an Oxidation  Ditch.  In:  Advances  in Water  Pollution
      Research 2:285-289.  Pergamon Press, New York.(1967).

 64.   Skogen, D. B.  Treat HPI Wastes With Bugs.  Hydrocarbon Processing
      46(7):105.  (1967).

 65.   Crane, L.  E.  An Operational Pollution Control System for Pressure
     Treating Plant Waste.    In:   Proceedings, Conference on Pollution
     Abatement and Control  in the Wood Preserving Industry.(W. S.
     Thompson, Editor).  Mississippi Forest Products Laboratory,
     Mississippi State University, State College, Mississippi.
     pp. 261-270.  (1971).

66.  Gaudy, A. F., Jr., R.  Scudder, M.  M. Neeley and J. J. Perot.  Studies
     on the Treatment of Wood Preserving Wastes.  Paper presented at 55th
     National Meeting, Amer.  Insti. Chem. Eng.,  Houston, Texas.  (1965).
                                    81

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67.  Gaudy, A. F., Jr.  The Role of Oxidation Ponds in a Wood Treating
     Plant Waste Abatement Program.  In:  Proceedings, Conference on Pollu-
     tion Abatement and Control jiji the Wood Preserving Industry.  (W. S.
     Thompson, Editor).Mississippi Forest Products Laboratory, Mississippi
     State Univ., State College, Mississippi,  pp. 150-164.  (1971).

68.  Fisher, C. W.   Koppers1 Experience Regarding Irrigation of Indus-
     trial Effluent Waters and Especially Wood Treating Plant Effluents.
     In:  Proceedings, Conference on Pollution Abatement and Control in the
     Wood Preserving Industry.(W. S.  Thompson, Editor).Mississippi
     Forest Products Laboratory, Mississippi State University, State
     College, Mississippi,  pp. 232-248.  (1971).

69.  Gloyna, E. F.  and J.  F. Malina, Jr.  Petrochemical Waste Effects
     on Water, Part 2.  Physiological Characteristics.  Industrial Water
     and Wastes.   (November-December, 1962).

70.  Gould, M.  and  J.  Taylor.   Temporary Water Clarification System.
     Chem. Eng. Progress 65(12).  (1969).

71.  Kirsch, Edwin  J.  and J. E. Etzel.   Microbial Decomposition of PCP.
     JWPCF 45(2).  (February 1973).

72.  American Public Health Association Standard Methods.  American
     Public Health  Assoc., Inc., New York, New York.
                                    82

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                            SECTION VIII

                              GLOSSARY
Activated Sludge - Sludge floe produced in raw or settled wastewater
by the growth of zoogleal bacteria and other organisms in the presence
of dissolved oxygen and accumulated in sufficient concentration by re-
turning floe previously formed.

Aerated Lagoon - A natural or artificial wastewater treatment pond in
which mechanical or diffused-air aeration is used to supplement the
oxygen supply.

Alum - A common name in the water and wastewater treatment field for-
commercial -grade aluminum sulfate.

Bentonite - An absorptive and colloidal clay used especially as a filler
(as in paper) or carrier (as of drugs).

BOD - Biological Oxygen Demand is a measure of biological decomposition
oTbrganic matter in a water sample.  It is determined by measuring the
oxygen required by microorganisms to oxidize the organic contaminants
of a water sample under standard laboratory conditions.  The standard
conditions include incubation for five days at 20°C.

COD - Chemical Oxygen Demand.  Its determination provides a measure of
thT oxygen demand equivalent to that portion of matter in a sample which
is susceptible to oxidation by a strong chemical oxidant.

Creosote - A complex mixture of organic materials obtained as a by-product
from coking and petroleum refining operations that is used as a wood pre-
servative.

Cresol - Any of three poisonous colorless crystalline or liquid isomeric
phenols
Emulsion - A heterogeneous liquid mixture of two or more liquids not
normally dissolved in one another, but held in suspension one in the
other by forceful agitation or by emulsifiers which modify the surface
tension of the droplets to prevent coalescence.

Flocculation - In water and wastewater treatment, the agglomeration of
colloidal and finely divided suspended matter after coagulation by gentle
stirring by either mechanical or hydraulic means.  In biological wastewater
treatment where coagulation is not used, agglomeration may be accomplished
biologically.

Lime - Any of a family of chemicals consisting essentially of calcium
fiydroxide made from limestone (calcite) which is composed almost wholly
of calcium carbonate or a mixture of calcium and magnesium carbonate.
                                    83

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Mixed Liquor - A mixture of activated sludge and organic matter under
going activated sludge treatment in the aeration tank.

Pentachlorophenol - A crystalline compound CgClgOH used as a wood
preservative, fungicide and disinfectant.

Phenol - The simplest aromatic alcohol.

Polyelectrolyte - A nonmetallic electric conductor of high molecular
weight in which current is carried by the movement of ions.

Quinone - Either of two isomeric  cyclic crystalline compounds
that are di-keto derivatives of dihydro-benzene.

Sludge Volume Index (SVI) -  It is the volume in milliliters occupied
by 1 gm of activated sludge after settling  of the aerated liquid for
thirty minutes.

Thiocyanate - A salt or ester of thiocyahic acid, a colorless unstable
liquid acid (HSCN) of strong odor.

Trickling Filter - A filter consisting of an artificial  bed  of  coarse
material, such as broken stone, clinkers,  slate, slats,  brush,  or plastic
materials, over which wastewater is distributed or applied in drops,
films, or spray from troughs, drippers, moving distributors, of fixed
nozzles,  and through which it trickles to the underdrains, giving oppor-
tunity for the formation of zoogleal  slimes which clarify and oxidize
the wastewater.
                                  84

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                            SECTION IX

                             APPENDIX
OPERATIONS LOG

     The treatment facilities at Carbondale were placed in operation
on July 26, 1973 and the testing program was terminated on May 31,
1974.  Table A presents a summary of key data collected during the
study.  Following is a condensation of the daily log maintained by
the treatment plant operators:

August 1973

     The activated sludge plant was installed and filled with water
from the emergency lagoon.   Horse manure was used as a seed and
aeration began on July 26.   The reason for using water from the emergency
lagoon initially was that it had relatively low concentrations of
phenol, penta, and boron and its pH was near neutrality.  Subsequently,
wastewater from Lagoon No.  1 was gradually added.  Three thousand
gallons of water from Lagoon No. 1 were added on July 31.  Until
August 20 the influent to the activated sludge system consisted of  a
mixture of waters from the emergency lagoon and Lagoon No. 1, but
on that date the emergency lagoon pump broke down and problems de-
veloped with the pump on Lagoon No. 1.  Although both pumps were
repaired on August 23, it was decided to continue use of only water
from Lagoon No. 1, and to increase the flow by one gallon per minute
each day until a flow of 6 gpm was obtained.

     It was observed that almost no suspended solids were building  up
in the aeration tanks.  On August 13 floating sludge was observed in
the clarifier.  Although sludge was returned to aeration at maximum
capacity, the problem continued.  On August 28 it was discovered
that a pin had sheared in the clarifier paddle assembly preventing
aeration of the paddles.  The clarifier was emptied into the aeration
tank and repairs were made.

     Considerable amounts of protozoa were observed from initial  start-
up until August 21 when the numbers began to drop drastically.  Small
amounts of lime were added to Aeration Tank No. 1 to increase the
pH, and the protozoa count increased.

     Due to lack of power at the on-site laboratory, penta analyses
were not begun until August 21.

September 1973

     The month of September was intended as a sludge build-up period.
Settleable solids increased from 35 ml/1  at the beginning of September
to 180 ml/1 at the end of the month.  By the end of the month the
MLSS was about 2000 mg/1.

                                   85

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      The  water  level  in  Lagoon  No.  1 was getting low enough  that  the pump
 began to  pick up  debris  from  the bottom, so water was added  to Lagoon
 No.  1  from  Lagoon No.  3.   This  temporarily lowered  the concentration
 of  penta  and phenol  entering  the activated sludge system, but as  raw
 wastes continued  to  be added  to Lagoon No. 1,  these concentrations
 began to  rise.

 October 1973

      On October 8, by  which time the MLSS of both aeration tanks
 averaged  about  2500  mg/1 and  settleable solids about 270 ml/1, the
 feed  rate was set at 11  gpm and maintained at  that  rate through October
 10.   From October 11 through  October 14 the feed was reduced to 5.5
 gpm while the aeration tanks  were being sprayed with an insulation
 material  and painted.

      As indicated in Table A, the flow rate of 11 gpm resulted in a
 reduced efficiency as  phenol  removal.  So on October 15, when both
 aeration  tanks were  back in operation it was decided to raise the feed
 rate  gradually while allowing the system to adjust  and reduce phenol
 levels prior to each increase.  It  took four days to again achieve a
 flow  of 11  gpm.   The rate of  11 gpm was maintained  from October 18
 through October 25 with only  a slight loss in phenol removal efficiency.
 On October  26 the flow was reduced  to 5.5 gpm to allow stabilization
 in preparation for tripling the feed rate.

      As can be seen  in Table A, the pH of the influent to the activated
 sludge system was consistently below 5.0.  Prior to the feed increase
 on October  8, only periodic additions of small amounts of lime were
 necessary to maintain  a pH in the aeration tank at above 6.0.  How-
 ever,  after the flow was increased on October 8, considerably larger
 lime  dosages were necessary nearly every day.

November 1973

     On November 7 the feed rate was increased from  5.5  to  7  gpm  and
then gradually increased to 13 gpm  by November 12.   This  rate was
maintained for three days,  at  which time  drastically reduced  phenol
removal necessitated a feed reduction.   Six  gallons  per minute were
fed until  the holiday weekend  of November 22  during  which time the
flow was cut off and the air supply decreased.

     The reason for shutting off the flow was  that many wood  preserving
plants do  not have the lagoon  capacity  that  the Carbondale  facility
does and no flow on a long  weekend  would  be  normal.   Also,  in an
effort to  conserve electricity (the winter of  1973 found  the  United
States  in  an "Energy Crisis"), the  metabolism  of the sludge was
reduced by timing the air pumps to  run  for one hour  and  be  off for
five hours.

     Large quantities of lime  were  necessary  to maintain  the  pH in
the aeration basins near neutrality. This was especially true during
the period of high feed rate.

-------
      Protozoa were easily visible until the system upset of November.
 15.   On November 16 horse manure was added to replace protozoa.

 December  1973

      The  stabilization period of the last week in November was maintain-
 ed into December.  On December 3 heaters were installed in the aeration
 tanks and these were expected to maintain a water temperature of at
 least 20°C.

     On December 3 the water temperature was 15°C.  By the next day the
 heaters had increased it to 17°C; however, the temperature then dropped
 until by  December 7 it was at 11°C.

     During the weekend of December 8 and 9 the flow was cut off and the
 air pumps were operated for one hour of each six hours.  This did not
 allow adequate water circulation over the immersion heaters; they'
 developed a sludge layer and burned out.  The lack of circulation also
 led to freezing of several lines and both pumps in Lagoon No. 1.  There
was a thin layer of ice on all tanks.

     By December 13 the system had thawed enough that repairs could be
 begun.
     More cold weather appeared on December 19 and from that date until
 December  25 there was at least a four inch layer of ice on all tanks.
 All operations were suspended.

     The  plant was back in operation on December 26.   Then, on December
 29, a line became clogged with ice and the system became frozen again.

 January 1974

     It was decided that for the remainder of the study only Aeration
 Tank No. 1 would be used in order to allow better operational control.
 On January 8 new heaters were installed in the aeration tank by chopping
 through five inches of ice.   By January 10 the aeration tank had thawed,
 but the external valves and lines were still  frozen.   On January 17 the
 system was placed in operation with a flow of 1.5 gpm.  Also on January
 17, heaters were installed in the pre-chlorination unit.  The temperature
 in the aeration basin gradually increased but did not rise above 20°C
until January 21.

     The flow was gradually increased until  it reached 4 gpm on January
28 (it would be maintained at this rate until  March 11).

     On January 23 a program of wasting small  amounts of sludge to  the
digester was initiated.   The MLSS at this time was 4650 mg/1, and it was
 intended to eventually reduce it to 3500 mg/1.

February 1974

     By the beginning of February the activated sludge system was
operated as designed and as  soon as the ,MLSS  became stationary it was
                                -87-

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 planned  to begin post-chlorination.

     By  February 7 the MLSS was below 3800 mg/1 and post-chlorination
 was initiated at 7 pounds of chlorine per day.  This resulted in a
 chlorine residual of 35 mg/1.

     It  was decided to determine what chlorine feed rate would yield a
 residual of near 1 mg/1.  February 10 through 14 results on Table B
 show a feed of 0.75 ppd would achieve a residual of about 1 mg/1.

     It  was also intended to increase the chlorine feed gradually to
 a maximum of 10 ppd to determine effects of BOD, COD, penta, and
 phenols.  This was done from February 15 through March 4.  From February
 22 through March 4 the pH of the post-chlorinated water began to drop
 drastically as the chlorine feed approached 10 ppd.

 March and April 1974

     The objective during March and April was to determine the effects
 of increased flow rates while maintaining other factors constant.
 Throughout the two-month period it was necessary to add large amounts
 of lime  (12 to 16 pounds every second or third day) in order to control
 pH in the aeration basin.

     On  March 7 the line between the aeration basin and the clarifier
 became clogged.  This caused the aeration basin to overflow and lose
 solids.

     Beginning March 9 flow rates were increased until March 17.  On
 March 16 the sludge return line became clogged and large amounts of
 sludge had to be wasted in order to unclog the line.  Horse manure was
 added to the aeration basin on March 13 to increase the protozoa count.

     Beginning on March 19 the flow rate was again increased until it
 reached  6.5 gpm on March 22.  At this point the phenol concentration
 in the effluent had risen to such a high level that the flow was
 reduced  to 3 gpm to allow system stabilization.

     Sludge had to be wasted almost daily in order to maintain a MLSS
 of approximately 3500 mg/1.   On March 21 phenols and penta concentrations
were observed to be low in the digester.  It was decided to incorporate
 a sludge contact chamber.  On March 26 all  return sludge was pumped to
 the digester for two hours detention before being returned to the aeration
 basin.   Using the contact tank, the flow was gradually increased until
April  8 when the submersible pumps went out.  The system was immediately
 converted back to straight activated sludge.

     The feed rate  was continually increased, despite increased phenol
 concentrations in the effluent, until  April  29 when sludge began to
 float in the clarifier.

     On April  11  the penta oil  separation system malfunctioned and penta
was spilled into Lagoon No.  1.   On April 15 the spill  began to appear
 in the treatment system.
                                    88

-------
May 1974

     The primary objective during May was to determine the effects and
operating parameters of pre-chlorination.  The flow rate was set at
6 gprru  It was intended to maintain a MLSS of 3500 mg/1, but, as shown
in Table A, the MLSS varied from 2790 to 4320 mg/1.

     Pre-chlorination began at 50 mg/1 and was scheduled to be increased
to 500 mg/1 during the month.  Sodium sulfite was used for de-chlorination
prior to aeration.  Sodium hydroxide was used to maintain a pH of 7 to
8 in the aeration basin.

     Pre-chlorination was initiated on May 7 at 50 mg/1.  No residual
resulted.  On May 9 the chlorine feed rate was increased to 75 mg/1 and
a residual of 1 to 2 mg/1 resulted.

     Due to the fact that extreme difficulties were encountered in
controlling the sodium sulfite addition by the gravity feed system, 'it
was decided to install  a feed pump.  The pre-chlorination feed rate
was maintained at 75 mg/1 until the pump could be installed.

     The feed pump was received on May 22 and prepared for installation.
However, on May 28 it became apparent from increasing phenol levels in
the effluent that the activated sludge system was breaking down.  The
pre-chlorination schedule was discontinued.
                                    89

-------
                                                                                TABLE A.
10
O
                                                                           DAILY LOG SUMMARY

                                                                                                                                      DO in
                                                     Phenol       Penta       BOD         COD        PO*          NH4         SS      Aeration   MLSS
                                 Flow                (mg/1)       (mg/1)    (mg/1)       (mg/1)     (mg/1)       (mg/1)     (mg/1)     (mg/1)     (mg/1)
pH
7/26/73
7/31/73
8/2/73
8/31/73
8/4/73
8/5/73
8/6/73
8/7/73
8/8/73
a/9/73
8/10/73
8/13/73
8/14/73
8/15/73
8/16/73
8/17/73
8/21/73
8/22/73
8/23/73
8/24/73
8/25/73
8/26/73
8/27/73
8/28/73


8/30/73
8/31/73
9/4/73
9/5/73
9/6/73
9/7/73
Aeration Basin
Wastewater
Added








Rising Sludge



Pump Problems
Pumps
Corrected
Lime Added



Clarifier
Paddles
Corrected



Lime Added
AHfl-Lf 	
5
5
5
5
5
5
5
5
5
5
5
5
4.5
2
2
3
4
5
5
6


6
6
6
6
6
6
6


5.9

5.8
5.8
5.8
5.5
5.4
5.5
5.5
5.4
5.5
5.5
5.4
5.5
5.5
5.4
-
-
5.2


5.3
5.0
5.1
5.0
4.9
3.9
5.0


6.1

6.4
6.3
6.4
6.4
6.5
6.5
6.5
6.5
6.5
6.5
6.2
6.1
6.2
6.2
6.2
6.2
6.5


6.3
6.6
6.6
6.5
6.7
6.6
6.4


0.4
12
15
27
30
65
65
65
75
65
70
70
70
70
70
70
-
-
80



85
95
90
90
95
95


0.6
<1
<1
<1
<1
1
1.4
1.6
1.5
1.5
2.0
2.0
1.5 3.4 0.6
1,5 3.4 0.3
2.0 2.3 0.86
1.0 2.6 0.3
2.0
3.0
2.0



2.0
2.0
1
2 2.2 0.6
1 2.7 0.5
2








40




1 260 350
- 440 - 67







1820 470

1960 440
- 380 - 67


-------
DATE
REMARKS
                                                TABLE A.

                                           DAILY LOG SUMMARY

                                                                                                      DO in
           pH        Phenol        Penta        BOD          COD        P04          NH4         SS      Aeration   MLSS
 How                (mg/1)        (mg/1)     (mg/1)        (mg/1)      (mg/l)        (mg/1)     {mg/1)     (mg/1)    (mg/1)
(gpm)  Inf.  Eff.   Inf.   Eff.   Inf.   Eff.   Inf.  Eff.   Inf.  Eff.   Inf.  Eff.   Inf.  Eff.  Inf.  Eff.  #1  #2   #1   #2
9/10/73
9/12/73
9/13/73
9/14/73
9/17/73
9/18/73
9/19/73
9/20/73
9/21/73
9/24/73
9/25/73
9/27/73
9/28/73
10/1/73
10/2/73
10/3/73
10/4/73
10/5/73
10/8/73
10/9/73
10/10/73
10/11/73

10/12/73
10/15/73
10/16/73
10/17/73
10/18/73
10/19/73



















Added Lime
Added Line

Tank
Maintenance

Added Lime

Added Lime

Added Lime
(10/19-10/22)
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
11
11
11

5.5
5.5
7
9
9
11

11
5.2
5.5
5.1
5.0
5.0
5.0
5.0
4.9
4.9
4.9
4.9
4.9
4.8
4.7
4.7
4.7
4.7
4.5
4.7
4.7
4.6

4.7
4.7
4.8
4.8
4.8
4.8

4.7
6.6
6.5
6.5
6.5
6.5
6.6
6.4
6.4
6.3
6.2
6.4
6.2
6.1
6.0
6.2
6.2
6.2
6.2
6.0
6.1
6.3

6.2
6.3
6.2
6.4
6.2
6.1

6.2
70
70
70
95
90
90
90
90
90
90
90
100
100
100
110
100
100
100
110
no
120

90
100
75
75
80
90

75
<1
<1
1
1
<1
1
1



<


2
2
1
1
1
1
3
9

10
7
1
1
1
2

1
1

1

1

1

1
1


1
1

1

1
1

1


2
2


2

2
.7

.8

.6

.5

.5
.2


.7
.53

.73

.82
.35

.62


.36
.15


.15

.28
0.

0.

0.

0.

0.
0.


0.
0.

0.

0.
0.

1.


1.
1.


2.

1.
6
1550 400
3 - 430 - 57

1
1700 400 - 400 - 67
3

2
3
1925 375

5 - 360 - 55
64 - 106
2272 612
64 - 350 - 50

97
57
2647 708
32 415 40


62
62

2117 757
15

78 755 75 - 340














2426 1751





4050 3690








3650 2640

-------
                                                                            TABLE A.


                                                                       DAILY LOG SUWARY
10
ro
DATE
10/23/73
10/24/73
1 0/25/73
10/26/73
10/29/73
10/30/73
10/31/73
11/1/73
11/2/73
11/5/73
11/6/73
11/7/73
11/8/73
11/9/73
11/12/73
11/13/73
11/14/73
11/18/73

11/19/73
11/20/73
11/21/73
11/26/73
11/27/73
11/28/73
11/29/73
REMARKS

Added Lime

Added Lime
Added Lime


Began Regular
Lime Addition


Poor Sludge
Separation

No Feed
(11/15,11/16)

No Feed
(11/22-11/25)
Flow
(gpm)
11
11
11

5.5
5.
5.
5.
5.
5.
5.
5.
7
9.
11
13
13
13

6
6
6
6

6
6
6
6
5
5
5
5
5
5
5
5









pH
Inf. Eff.
4.8
4.8
4.8
4.9
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.8
4.9
4.7
4.7
4.8
4.7

-
4.7
4.7
4.7

4.8
4.8
4.8
6.4
6.3
6.4
6.4
6.4
6.4
6.7
6.7
6.7
6.6
6.6
6.6
6.6
6.6
6.6
6.8
6.7

6.9
6.9
6.7
6.8

6.8
6.9
6.8
Phenol
("9/1 )
Inf. Eff.
75
70
70
70
90
80
90
80
90
90
90
90
100
90
80
90
90

-
90
90
90

70
3
3
2
3
2
1
1
1
1
1
1
2
1
2
2
10
20-

4
4
2
1

2
Penta BOD COD P04 NH4
(mg/1) (mg/1) (mg/1) (mg/1) (mg/l)
Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff.
1.68
2.22
1.93
2
2
2
2

2
2

3


4
4

4
.30
.3
.1
.1

.4
.7

.1


.4
.4

.6
2.02
2117 846
- 460 - 45
2.56 860 63
2.15
3.13
2217 803
- 320 - 55
2.4 1045 110
2.3
2290 730
2.1
- 300 - 52
2.2
3.3
2650 1040
2.7


3.8
2910 1090
3.5 - 260 - 40

- 260 - 45
4.3 2240 1030
DO in
SS Aeration MLSS
(mg/1) (mg/1) (mg/1)
Inf. Eff. #1 #2 #1 #2



4280 3500
2.5 7.8

3.0 9.5
4940 3800
2C A C
.5 4.5

1115
1 . O 1 . J
5250 '4930

5340 4970
1.0 3.5

120 270 1.5 1.5
2.0 6.0 5110 4660
2.3 7.5

-------
                                                                                 TABLE A



                                                                             DAILY  LOG SUMMARY
U3
DATE REMARKS
11/30/73
12/3/73 Heaters
Installed
12/4/73
12/5/73
12/6/73
12/7/73
12/10/73 Lagoon Pump
Frozen
12/12/73
12/13/73
12/14/73 #1 Tank
Repair Begun
12/17/73
12/18/73
12/19/73
12/26/73
12/27/73
12/28/73 Both Tanks
in Operation
1/15/74 No Row
1/18/74 Flow Into
#1 Only
1/21/74
1/22/74 Increased Air
1/23/74
1/24/74
1/25/74
1/28/74 Air Pump
Break Down
1/29/74
Flow
(gpm)
6

6
6
6
6
6

0
6
6

3
3
3
3
3
3

1.5
0

1.5
2.5
3
3
3
3

4
4
pH
Inf. Eff.
4.8

4.7
4.7
4.9
4.8
4.8


4.8
4.8

4.7
4.8
4.7
4.8
4.8
4.9

4.8


4.8
4.8
4.9
4.8
4.9
4.8

4.8
4.9
6.9

6.9
7.0
7.1
6.9
6.9


7.2
7.0

6.9
6.7
6.9
6.9
7.0


7.1


6.9
7.4
7.1
7.2
7.0
7.1

6.7
6.6
Phenol
(mg/l )
Inf. Eff.


54

55

56


54


55
55

56
35


44


42
38

43

43

44



0.7

0.5

0.4


0.9


0.7
5.1

13
1.5


0.7


0.4
0.1

0.2

0.1

0.4

Penta
(mg/l)
Inf. Eff.


4.1

4.5

4.1


3.8


4.9
4.2

4.1
3.7


3.4


4.0
4.2

3.0

3.6

3.0



4.1

4.9

4.0


4.3


5.9
4.8

5.2
4.5


.4.9


4.6
5.0

4.3

4.2

3.8

BOD COD P04
(mg/l) (mg/l) (mg/l)
Inf. Eff. Inf. Eff. Inf. Eff.
780 100

2100

2110

985 103 2040


2150


1065 125 2180
2170

821 - 2110



1620


540 85 1610
1730

1730

695 100 1730

790 135 1640



1000
220 200
940
200 200
820


360
300 260

880
910
240 240
1060



990


690
690
200 200
690
200 200
610

710
260 200
DO in
NH4 SS Aeration MLSS
(mg/l) (mg/l) (rag/1) (mg/l)
Inf. Eff. Inf. Eff. #1 #2 #1 12
110 200 2.2

2.0
60 40 90 200 1.5
2.2
60 42 100 160 2.9
2.8

3.2

60 35 60 120 5.0

_
.
65 55 100 160







3.0
2.0
55 55 80 110 0.5
2.2
60 45 100 150 1.6
2.0

0.5
55 45 130 170 0.5
9.0 5180

8.5
6.5 5000
7.5
5.5 5040
7.8

5.0

7.5 5190

5.8
7.5
9.5 3570


4900


3810

_
j,
- 4650

- 4620


4610

4090


3940

4420




4540



4860


4080


4880



_

—





-------
     TABLE A.



DAILY LOG SUMMARY
DATE REMARKS
1/30/74
1/31/74
2/1/74
2/4/74
2/6/74
2/8/74
2/11/74
2/12/74
2/13/74
2/14/74
2/15/74
2/18/74
2/19/74
2/20/74
2/21/74
2/22/74
2/25/74
2/26/74
2/27/74
2/28/74
3/1/74
3/4/74
3/5/74
3/6/74
3/7/74
3/8/74
3/11/74
3/12/74
3/13/74 Added Horse
Manure
3/14/74
Flow
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5

5
5
Inf.
4.8
4.8
4.8
4.8

-
4.9
4.8
4.8
4.8
4.8
4.8
4.9
4.8
4.9
4.9
4.9
5.3
5.0
5.0
5.1
5.0
5.1
5.1

5.0
4.7
4.9

4.7
4.7
PH
Eff.
6.5
6.8
6.7
6.8

5.8
6.4
6.8
6.6
6.6
6.5
6.6
6.0
5.7
6.2
5.6
4.2
4.7
3.7
4.6
3.3
3.0
6.9
6.9

6.9
6.5
6.7

6.8
6.7
Phenol
(mg/1)
Inf. Eff.

52 0.2

56 0.4


62 0.6


59 0.5

58 0.4


62 0.9

64 0.6


63 0.4
,
70 0.6



66 0.2
60 0.6




Inf

3.5

4.0


5.1


3.9

5.2


7.4

Penta
(mg/1)
. Eff.

4.9

5.7


4.4


5.3

5.2


4.3

6.0 3.2


3.2

5.4



7.8
8.6



7.5


1.4

5.2



7.4
8.6



8.1
BOD COD P0a
(mg/1) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. Inf. Eff.

515

1040

520
465


565

630


730

1070


740

920



860
770



1015

85 1830 570

220 2110 605

55
95 2340 595
220 180

75 2450 570

80 2390 760
200 160

85 2420 735

95 2500 835
220 180

80 2630 860

65 2800 800
200 200


85 2965 722
95 2620 855
180 180


135 2715 985
DO In
NHd SS Aeration
(mg/1) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. #1 #2


90




55 30 115


no

60 40 175


160

70 50 140


160

65 40 850




60 25 175



1.0
1.0
100 1.0 -
1.0 -
2.5 -
2.4 -
3.0
100 2.1 -
2.0 -
1.5 -
90 1.5
0.5 -
110 1.9 -
2.5 -
0.4 -
115 0.5 -
3.5 -
110 2.5 -
1.5 -
2.2 -
135 0.5 -
0.5 -
700 1.7 -
2.2 -
1.0 -
2.0 -
1.5 -
165 1.7 -

1.2 -
1.2 -
MLSS
(mg/D
#1 #2
4340 -

4125 -
3375 -
3860 -
3620 -
3880 -

3780 -

3660 -
3760 -

3390 -

3610 -
3765 -



3585 -
4155 -

3930 -
2750 -
3445 -
4290 -


4395 -
3775 -

-------
                                                                                 TABLE A.

                                                                            DAILY LOG SUfWARY
in
        DATE
REMARKS
                                                                                                     DO in
           pH        Phenol       Penta       BOD         COD        P04          NH4         SS      Aeration   MLSS
 Flow               (mg/1)       (rag/1)    (mg/1)       (mg/1)     (mg/1)       (mg/1)      (mg/1)     (mg/1)    (mg/1)
(gpro)  Inf.  Eff.   Inf.  Eff.  Inf.  Eff.  Inf.  Eff.  Inf.  Eff.  Inf.  Eff.  Inf.   Eff.   Inf.   Eff.  11  K   11  #2
3/15/74
3/16/74
3/17/74
3/18/74
3/19/74
3/20/74
3/21/74
3/22/74
3/25/74
3/26/74


3/27/74

3/28/74

3/29/74
4/1/74
4/2/74
4/3/74
4/4/74
4/5/74
4/8/74

4/9/74
4/10/74
4/11/74
4/12/74
4/15/74
Sludge Return
Line Clogged







Started
Returning
Sludge
To Contact
Tank For 2 hr
Then to 11
Tank






Stop Use of
Contact Tank





5
5.5
5.5
4
5
5.5
6
6.5
4


4

4

4
4
4
5
5
5
5.5

5.5
5.5
6
6
6
6
4.7

4.7
.8
.7
.8
.8
.8




4.9

4.8
4.8
4.8
4.9
4.8
4.8
4.8

4.8
4.7
4.7
4.7
4.7
4.7
6.9

6.9
6.9
6.9
6.7
6.9
6.8




6.7

6.8
6.8
6.8
6.8
6.8
6.8
6.8

6.6
6.8
6.7
6.7
6.6
6.8


65


59
60







63

60


64


60


58

59


0.5


1.2
5.0







0.3

0.2


0.2


0.2


9.5

0.3


7.2


8.1
7.4







6.6

6.1


6.4


6.7


7.1

8.6


9.1


9.9
7.0







6.2

6.5


6.8


6.4


7.2

10.4


830


910








875

750


865


945


995

845


100


115








95

120


100


115


135

120


2245


2455








2400

2365


2375


2285


2580

2640


700

160 160
725








720

710

160 140
.


650
125 125

790

1070
180 65


160 100
50 35

80 120








145 145

140 135
60 40

105 155


65 60 110 135


320 155

1.0
2.7
3.0
1.4
3.0
3.5
3.0
4.0




4.0

2.8
2.2
3.5
2.5
2.5
3.0
3.5

4.0
4.0
2.7

2.0
3.0
- 3805
- 1645
- 3530
_
- 3605
-
- 3350
-


3785

- 2920

_
- 3315
- 3040
-
- 3320
- 2910
- 3355

- 3780
- 4220
- 3980

- 4385
- 4880
-
_


.

_



_

_


_
_

-
_
-

_
.
_

_
-

-------
                                                                         TABLE A.
                                                                    DAILY LOG SUWARY
10
DATE
4/16/74
4/17/74
4/22/74
4/23/74
4/24/74
4/25/74
4/26/74
4/29/74-
4/30/74
5/1/74
5/2/74
5/3/74
5/6/74
5/7/74

5/8/74

5/9/74

5/10/74
5/11/74
5/12/74
5/13/74
5/15/74
5/16/74
5/17/74
5/20/74
5/21/74
5/22/74
5/23/74
5/24/74
5/28/74
5/29/74

5/30/74
5/31/74
REMARKS




Rising Sludge





Started Pre-
Chlori nation
Excessive
Foam
Began NaOH for
pH Control













Stop Free
Chi ori nation


Flow
(gpm)
6.5
6.5
7.5
7.5
8
8
8
8
6
6
6
6
6

6

6

6
6
6
6
6
6
6
6
6
6
6
5
6
6

6
0
0
pH
Inf. Eff.
4.9
4.7
4.7
4.8
4.7
4.7
4.7
4.8
4.7




4.8





4.7
4.7
4.9
4.7
4.7
4.7

4.7

4.7




6.6
6.7
6.9
6.6
6.8
6.7
6.8
7.0
6.8




6.8





7.2
7.0
7.2
7.2
7.2
6.9

7.0

6.8




Phenol
(mg/1)
Inf. Eff.
56

65

64


68





70





72

80

74


82

74




2.3

0.5

0.4


0.4





0.4





0.5

0.5

0.2


0.2

8




DO in
Penta BOD COD P04 NH. SS Aeration MLSS
(mg/1) (mg/1) (rng/1) (mg/1) (mg/1) (mg/1 ) (mg/1) (mg/1)
Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. Inf. Eff. #1 #2 #1 #2
15.8

11.2

7.6


8.9





8.9





8.0

9.2

2.8


6.6

5.4




17.2

22.4

15.2


19.2





14.5





7.2

12.0

9.6


6.2

5.0






885 100 2595

935 95 2465


2565





835 102 2465





680 90 2580

740 85 2320

660 85 2225


720 90 2070

695 85 2105





120 120
1155

1100
120 120

930





780





895

970

685


740

655




225 210 3.5
5.0
3.5
60 40 1.2
1.3
180 90 0.5
3.0
70 40 150 280 1.0
1.5
0.7
130 110 2.0
2.0



1.8

130 140
1.0


1.0
135 210 1.0
1.7
2.1
3.0
1.5
1.5
1.5
3.0
0.8

0.6


- 5070 -
- 3710 -
4225 -
- 4050 -
-
- 4260 -
- 3285 -
-
- 3515 -
- 3715 -
- 3865 -
-



- 4150


- 4180 -


- 4320 -
- 3725 -
-
- 3495
3410
2790
2940

3470
3670

3630

3040

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                  TABLE B,

              POST-CHLORINATION
 Date

2/7/74
2/8/74
2/9/74
2/10/74
2/11/74
2/12/74
2/13/74
2/14/74
2/15/74
2/18/74
2/19/74
2/20/74
2/21/74
2/22/74
2/25/74
2/26/74
2/27/74
2/28/74
3/1/74
3/4/74
cr
OJ
? Feed
3/day)

 7
 0.5
 1.5
 1
 0.75
 0.75
 0.75
 0.75
 1
 1
 3
 3
 3
 5
 5
 7
 7
 7
 10
 10
    7
    1
g Residual
(mg/1)
                         35
                          0
                          4.4
                          6.6
                          2.0
                          1
                          1
                          0.5
                          3.3
                          2.4
                         11.6
                         13.9
                         11.1
                         22.4
                         24.4
                         33.4
                         35.2
                         32.0
                         47,4
                         35.7
                        97

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/2-76-231
                                                            3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE
     Treating Wood Preserving Plant Wastewater by
     Chemical and Biological Methods
                                                            5. REPORT DATE
                                                            September 1976 (Issue Date)
              6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
     John T.  White, T. A. Bursztynsky,  John D,
     and  Richard H. Jones	
                                                           8. PERFORMING ORGANIZATION REPORT NO,
   Crane
9. PERFORMING ORGANIZATION NAME AND ADDRESS

     Koppers Company
     Forest  Products Division
              10. PROGRAM ELEMENT NO.

               1BB610	
              11. CONTRACT/GRANT NO.
                                                            12100 HIG
 12. SPONSORING AGENCY NAME AND ADDRESS
 Industrial Environmental Research Laboratory - Cin., OH
 Office of Research and Development
 U.S. Environmental Protection Agency
 Cincinnati, Ohio   45268
              13. TYPE OF REPORT AND PERIOD COVERED
                Final
              14. SPONSORING AGENCY CODE

                EPA/600/12
 15. SUPPLEMENTARY NOTES
   Performed  for the Koppers Company  by ENVIRONMENTAL SCIENCE AND ENGINEERING,  INC,
   P. 0. Box  13454,  University Station, Gainesville, Florida   32604
16. ABSTRACT
          A completely mixed activated  sludge system was designed for a wood pre-
     serving plant with an average daily wastewater flow of  27,000 I/day
     (7,150 gal/day),  a BOD concentration of 1,100 mg/1, and a phenol concen-
     tration of  120 mg/1.  Included  in  the design were capabilities for pre- and
     post-chlorination.  The activated  sludge system alone was capable of re-
     moving 90 percent BOD, 75 percent  COD, 99 percent phenol, and 76 percent
     pentachlorophenol.  Post chlorination dosages of over 50 mg/1 resulted in
     50 and 52 percent reductions of phenol and pentachlorophenol, respectively.
     Laboratory  pre-chlorination studies showed removal of phenol and penta-
     chlorophenol at chlorine dosages in excess of 250 mg/1.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS  C.  COSATI Field/Group
     *Wood preservatives, *Activated
     sludge, *0xidation,  Phenol, Creosote
^Completely mixed,
*Chlorination,  pentachloro
 phenol.
13/B
 8. DISTRIBUTION STATEMENT
                                              19. SECURITY CLASS (ThisReport)
                                                UNCLASSIFIED
                           21. NO. OF PAGES

                                108
                                              20. SECURITY CLASS (Thispage)
                                                UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                             98
                 ftUSGPO: 1977 - 757-056/5479 Region 5-11

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