IVi-1 r r :i I mr M t R i-q u i rr in ruts
for Oil iiiul (Jri'iisc1
    TREATABILITY OF OIL AND GREASE
     DISCHARGED TO  PUBLICLY OWNED
            TREATMENT WORKS
    U.S. I.NVIRONMI N I Al. PRO I l.( I ION A(;i N( Y
                 APRIL IV75

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            TREATABILITY OF OIL AND GREASE

      DISCHARGED TO PUBLICLY OWNED TREATMENT WORKS
                     Russell Train
                     Administrator
                     James  L. Agee
Assistant Administrator for Water & Hazardous Materials
                       2  JTB  o
                       ussy
                      Allen Cywin
        Director, Effluent Guidelines  Division
                   Raymond C.  Loehr
                    Program Adviser
                     April 1975
                     Prepared for

         Office of Water and Hazardous Materials
              Effluent Guidelines Division
          U.S. Environmental Protection Agency
                Washington, D.C.  20460

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                 TREATABILITY OF OIL AND GREASE




          DISCHARGED TO PUBLICLY OWNED TREATMENT WORKS
    The  Effluent  Guidelines  Division   recommends   that   the



following  pretreatment  requirements be established for existing



point sources discharging into publicly owned treatment works for



the listed categories of oil and grease:







         animal and vegetable origin        no limitation



         petroleum or mineral origin        100 mg/1







Introduction








    The need for pretreatment cf any industrial waste is  related



to  the  ability  of  a  publicly owned treatment works to remove



pollutant parameters in the waste.  The Federal  Water  Pollution



Control  Act Amendments of 1972 (the Act)  contains sections which



required EPA to take specific actions regarding  pretreatment  of



industrial   waste   introduced   into  municipal  systems.   The



pretreatment  sections  of  the  Act  were  intended  to  prevent



intoduction  of  pollutants  into  publicly owned treatment works



which interfere with, pass through, or are otherwise incompatible



with such works.

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    Oil and grease  is  a  pollutant  parameter  which  has  been
considered  to  interfere  with the performance of publicly owned
treatment  works.   Factors  affecting   the   establishment   of
pretreatment  requirements  include  the  constituents  and their
biodegradability in a publicly owned treatment works.

Method of Analysis

    Unlike some pollutant parameters, such as  distinct  chemical
elements,  oils  and  greases  are defined by the method used for
their  determination.   An  absolute  quantity  of   a   specific
substance  is  not  measured.   Ratherr groups of substances with
similar physical characteristics are  determined  quantitatively,
based  on  their mutual solubility in the solvent used,,  The term
oil and grease will include  fatty  acids,  soaps,  fats,  waxes,
petroleum  products  and any other material which is extracted by
the solvent and which is not volatilized  during  evaporation  of
the  solvent.   Both  hexane and freon (trichlorotrifluoroethane)
are the recommended solvents (1, 2, 3) .  A method using activated
alumina is available to separate  polar   (primarily  hydrocarbon)
and  non-polar  (fatty  acids and esters) constituents of oil and
grease (1) .  This method provides information on  the  proportion
of  oil and grease composed primarily of  fatty matter from animal
and vegetable sources and of hydrocarbons from  mineral  oil  and
petroleum sources.

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Constituents







    Oil  and grease in waste waters or natural waters result from



the introduction of animal and vegetable fats and oils  and  from



petroleum  products.   Animal  and  vegetable  fats  and oils are



present in significant concentrations in household sewage.   They



are  also  present in the waste waters from the refining of these



materials for preparation of shortening,  soap,  and  from  other



industries such as meat packing,, slaughterhouse, leather tanning,



and food processing operations.







    Petroleum  products  in  waste  water  result  from losses of



petroleum oils during refining or other processing in  refineries



and petrochemical  plants.  Oil also may be lost during cleanup of



metal  machining   and  metal working operations, from lubricating



operations, and in the case  of  service  stations   some  may  be



deliberately  disposed  of   to  the  sewer   system.   Oil,  though



basically insoluble in water, may become emulsified  or  dispersed



in  waste waters through pumping and other agitation.  Emulsified



oils may also be discharged  from certain industrial  operations.







    The majority of greases  or oils in  food  or animal  fat   exist



as  glycerides.    Glycerides may  bo   hydrolyzed  in waste water



collection  and  treatment   systems  to  yield  glycerol   and the



alkalyzed   salts   of   the  fatty acid.   These compounds constitute

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the major faction of  grease  in  normal  domestic  sewage.   The



principle  constituents  of  these  glycerides  and soaps are the



long-chain saturated fatty acids—lauric, myristic, palmitic, and



stearic acids—and the long-chain unsaturated fatty  acids—oleic



and  linoleic  acids.   Palmitic, stearic and oleic acids usually



constitute over 80% of the fatty acids in  most  municipal  waste



waters.   Vegetable  oils  discharged to sewerage systems will be



absorbed onto other suspended material in sewage and are unlikely



to be in liquid form entering waste water treatment facilities.







    Oil and greases of  petroleum  origin  consist  primarily  of



long-chain,  saturated  hydrocarbons  that  are  relatively  non-



reactive.  These compounds can be  degraded  to  various  degrees



especially  if  the  microorganisms  are  acclimated  to  use the



compounds as a substrate.



Removal by Waste Treatment Processes







    Waste treatment processes are utilized, among  other  reasons



to  reduce  the oxygen demand of waste waters prior to discharge.



The total oxygen demand and the rate of the demand of a  compound



is  related  to  the  ability of microorganisms to metabolize the



compound.  Long chain, saturated, reduced organic compounds, such



as hydrocarbons, generally are oxidized more slowly  but  require



more  oxygen  per  unit  weight  than  short  chain, unsaturated,



oxidized compounds such as organic acids.

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    Grease in waste water can be  in  three  forms  a)   free,   b)



attached to other solids, and c) semi-colloidal.  Free grease  can



float  and  be  skimmed from primary sedimentation tanks.  Grease



attached to other particles can settle with  these  particles   or



remain  in  suspension  if  the resultant specific gravity is  not



greatly different  from  that  of  water.   Much  of  the  grease



attached  to other solids and that in the semi-colloidal state is



not removed in a  primary  sedimentation  tank  and  flows  to  a



secondary  treatment  unit, such as an activated sludge unit or a



trickling filter.  The microorganisms in the secondary biological



treatment unit will metabolize the entering greases.  The  energy



from  such  metabolism  is used for both maintenance of organisms



and for synthesis of additional organisms.  It  can  be  expected



that  biological  waste  treatment  will  not  only  decrease the



quantity of grease in waste  waters  but  will  also  change  the



relative   proportion   of   grease   components  as  the  easily



metabolized greases are  removed,  the  less  easily  metabolized



greases   remain,   and  microbial  oil  and  grease  extractable



compounds are synthesized.  Such  material  forms  a  significant



fraction of microorganisms.







    All greases  are not metabolized at the same rate in  microbial



systems.   Fatty  acids,  glycerides,  and methyl esters are more



readily oxidized than hydrocarbons.   The less easily  metabolized



greases  and  the  greases  in  microorganisms  discharged in  the

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effluent  represent  the  major  part  of  the   organic   matter
discharged from secondary treatment facilities„

    Investigations  of  oil  and greases in waste water and their
removal in  waste  water  treatment  processes  have  shewn  that
hydrocarbons,  sterol  esters,  glycerides, fatty acids, compound
lipids, and possibly sterols were found in  the  oil  and  grease
extractable  material  from  untreated  waste water and activated
sludge samples.  Oil and grease extractables from influent  waste
water  samples  indicated  that  fatty acids were the predominant
extractable components, followed by hydrocarbons,  triglycerides,
and  compound lipids.  In some samples, hydrocarbons and compound
lipids were the predominant extractable components (4,5).

    The general pattern of hexane soluble  material  in  influent
waste  water  was  shown  to  change  as  the degree of treatment
increased.  Compounds more resistant  to  biological  degradation
remained in the waste water for a longer period of time.  Whereas
fatty  acids  were  a predominant oil and grease component in the
effluent from an activated sludge treatment facility (4, 5).

    A waste water treatment plant receives a  heterogenous  group
of organic compounds, the mix being a function of the commercial,
manufacturing   and   domestic  contribution  of  the  community.
Bacteria will adapt to degradation of each category of  material.

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i.e.,  proteins, carbohydrates, and greases,  since these compounds



are  normally  found  in  waste  water.   No  problems concerning



adaptability or acclimation would be expected  until  a  specific



compound suddenly appeared in abnormally high concentrations.







    Analysis  of  oil and grease at waste water facilities is not



as  routine  as  it  is  for  EOD,  COD,  or  solids.   Available



information  indicates  the  following  total  grease removals at



activated sludge plants:  SUE - Topeka, Kansas; 85.7% - Cleveland



easterly plant; 94% - Madison,  Wisconsin.   The  Cleveland  data



represents  a  yearly  average  with  the average influent grease



concentration  being  80.3  ir.g/1   and   the   average   effluent



concentrations being 11.5 mg/1  (6) .



The  Topeka study was done to investigate grease removal patterns



at a secondary treatment facility (7) .  Grease removal by primary



treatment was  U5%, by secondary treatment 7U%,  and  by  complete



treatment  84%.   The average BOD and suspended solids removal at



this time was  85 and 82* respectively.  Other  results  from  the



study  showed  that there was a reasonable correlation between the



grease and the suspended solids concentrations  in   the  effluent



from treatment plant.







When   the   suspended   solids   concentration   was   low,  the



concentration  of grease was also low.   Grease  in   the  effluent

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from  the  activated  sludge  plant  averaged 22 mg/1 with hourly
samples having concentrations that ranged from 7-68 mg/1.

A summary of one years data, 1968, at  the  three  major  Chicago
sewage  treatment  plants  indicated  that  the  West  Southwest,
Calument, and North Side plants failed to meet  an  effluent  oil
and  grease  concentration  of  15  mg/1  36,  34, and 3% of time
respectively.  During the same period, the three plants failed to
meet a BOD effluent standard of 20 mg/1  and  a  total  suspended
solids  effluent  standard of 25 mg/1 40 and 55*r 60 and 40X, and
20 and 1H% of the time respectively.  The data was based on daily
2«l hour composite samples.  The summary indicates  that  the  oil
and  grease  removals were on the same order Two research studies
have provided additional insight into  the  removal  of  oil  and
grease by biological treatment processes.

One  study  investigated  the  effect that wastes from processing
vegetable and animal fats  and  oils  had  on  treatment  systems
involving  biological degradation and sludge filtration  (8).  The
results indicated that these wastes were readily degraded by  the
activated  sludge process even at temperatures as low as 12.25°C,
that they were  readily  degraded  by  anaerobic  treatment  with
removal  efficiencies  of  from  82  to  92 percent, and that the
presence of the wastes, with one minor exception, had no  adverse
effect on oxygen transfer in the activated sludge process.
                                8

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An  EPA  supported  study  determined the tolerance of biological
treatment  systems  to  various  oily  materials  which  included
crankcase oil, crude oil, refinery waste, vegetable oil, benzene,
and  benzene  derivateive  (9).   The  study  indicated  that the
failure of activated sludge systems  due  to  oily  materials  is
physical   rather  than  biochemical.   The  oily  compounds  are
absorbed in the sludge floe but are only slowly metabolized.  The
result of the oil accumulation is  a  lowering  of  floe  density
which  results  in  a  loss  of  sludge  settling properties.  An
activated  sludge  system  will  perform  satisfactorily  with  a
continuous  loading  of oil and grease of 0.1 pounds per pound of
mixed  liquor   suspended   solids.    For   conventional   plant
operations,  the  influent to the biological system was suggested
to contain less than 75 mg/1 oil and grease and  preferably  less
than  50 mg/1.  None of the compounds studied interfered with the
oxygen transfer in  the system.

The above information indicates that  different  oil  and  grease
components   in   waste   water   have   different   removal  and
biodegradation rates in waste treatment facilities.  Hydrocarbons
and complex greases associated with microbial cells are likely to
be the main components  in secondary  treatment  plant  effluent.
Fats  and  oils  of  vegetable and animal origin are more readily
metabolized.  Although data  is  not  excessive,  grease  removal

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efficiencies  in primary facilities appear to be about 40-5055 and
in secondary treatment facilities about 80-90%.

Grease removal  efficiency  correlates  with  BOD  and  suspended
solids removal efficiency.  Grease concentrations in an activated
sludge  effluent  appears to correlate with high suspended solids
in the effluent.  This indicates that one mechanism  to  minimize
oil  and  grease  discharged  to surface waters is to provide for
better suspended  solids  removal  from  the  effluent.   Because
vegetable  and  animal fats and oils can be metabolized by micro-
organisms, they will be removed in secondary biological treatment
facilities and their effect will be observed  in  the  BOD  test.
Control  of  excess  grease  in an effluent, especially that from
vegetable  and  animal  sources,  should   be   accomplished   by
implementation  of BOD and suspended solids effluent standards at
the secondary  treatment  plant.   Additional  constraints  by  a
pretreattnent limitation on these compounds would be redundant.  A
pretreatinent limitation on the less biodegradable compounds, such
as those of petroleum or mineral origin, may be advisable.

Currently Acceptable^Concentrations

Specific  limitations  on  oil and grease discharges to municipal
treatment plants were published in 1949 when  the  Federation  of
Sewage  Works Associations first presented its Manual of Practice
                                10

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on  Municipal  Sewer   Ordinances.    The   recommended   maximum



concentration of oils and greases in the manual was 100 mg/1.  In



the intervening years there has been considerable disagreement on



such  a  rigid  limitation.   The  concern has been with the non-



specificity of the oil and grease components that  may  interfere



with  the  performance  of  a publicly owned treatment works.  As



noted  earlier,  numerous  investigations   have   more   clearly



identified  the  problem  components.   The most recent manual of



practice (10) suggests  the  following  limitations  on  oil  and



grease discharged to municipal treatment systems:







    "Waste  water containing more than 25 milligrams per liter of



    petroleutrt oil,, nonbiodegradable cutting oils, or  product  of



    mineral origin"







    "Waste  water  from  industrial  plants  containing floatable



    oils, fats, or grease."







The  manual  notes  that  oils  .and  grease  of  mineral   origin



 (primarily nonpolar substances) are essentially nen-biodegradable



either  in  aerobic  or  anaerobic  processes  and that animal and



vegetable  oils  and  greases   (polar  substances)  are   readily



degradable  in  these  processes.  It  further  notes that "if oils



and greases are biodegradable and in a physical state  that  does



not  cause  clogging  or  undue maintenance problems in the waste
                                11

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water facilities,  the  discharge  of  these  substances  can  be
accepted  in a wastewater treatment system." Many municipal sewer
ordinances have been based on the material in the editions of the
above Manual of Practice and include a statement  to  the  effect
that  waste water discharges having oil and grease concentrations
in excess of 100 mg/1 are prohibited.  Examples can be  found  in
the sewer ordinances of the metropolitan St. Louis Sewer District
(11) and of Jefferson County, Alabama  (12).

    Oils  and greases are a normal constituent of municipal waste
waters and information on the  concentrations  currently  in  the
untreated waste water of municipalities should provide an idea of
the   concentration   currently   being  accepted,  and  thus  by
inference, able to be  handled  by  municipal  treatment  plants.
Information in the Manual of Practice  (10) indicated that oil and
grease concentrations of 16 to 105 mg/1 were found in waste water
free of industrial wastes.

Summary and Conelusigns

    1.   Available information indicates that oil and  grease  of
animal  and vegetable origin can be metabolized by microorganisms
in  secondary waste treatment facilities and would be  reduced  in
concentration  along with other organics.  The oils and grease in
the effluent from secondary treatment  plants is  related  to  the
                                12

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suspended  solids content of the effluent.  Low concentrations of


oil and grease in the effluent can be obtained by  achieving  low


suspended  solids  concentration  thus, oils and grease of animal

                                         ^
and  vegetable  origin  are  not  expected  to  pass  through  or


interefer  with  a  publicly owned treatment works.  Pretreatment


requirements for these compounds are not needed.




    2.   In the event  that  excessive  quantities  of  oils  and


grease  are  discharged  to a publicly owned treatment works such


that they do cause obstruction to the flow in sewers or interfere


with the operation of such works, or are in such slugs that  they


upset  the  treatment  processes and result in a loss efficiency,


such discharges  are  subject  to  the  general  prohibitions  of


section  128.131  of  the General Pretreatment Regulation (40 CFR


128)   published  on  July  19,  1973.   No   other   pretreatment


requirements are needed to control such discharges.




    3.   Oils and grease of mineral or petroleum origin are  less


biodegradable  in  secondary  treatment plants,  one of the above


studies has noted  that  the  influent  ot  biological  treatment


systems should contain less than 75 mg/1 and preferably less than


50  mg/1  oil and grease.  Varying degree of dilution occur in an


municipal  sewer  system  due   to   household   and   commercial


contributions.  A dilution of a least two occurs, thus a limit of
                                13

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100  mg/l  on  the  discharge  of oils and grease of petroleum or
mineral origin is realistic.

    This concentration is greater than that currently recommended
in the Manual of Practice (10)„ however the available information
justifies a number higher  than  that  noted  in  the  Manual  of
Practice.   Because  of  the dilution the does occur in sewers as
industrial and other waste waters are mixed, it is expected  that
the concentration of petroleum or mineral oils in the influent to
the  publicly owned treatment works will be less than 50 mg/1 and
thus will not interfere with the performance of such works.

    These requirements do not preclude a  municipality  or  other
agency from establishing more stringent pretreatment requirements
where  it can be shown that they are needed for the protection of
the  publicly  owned  treatment  works.   Thus  the   recommended
requirements  for  oils and grease of petroleum or mineral origin
are not  contradictory to the recommendations  in  the  Manual  of
Practice.

References

1.   Standard  Methods for  the Examination of  Water  and; Waste
     Vfatey f          13th    Ed,   (1971) ,   American  Public Health
     Association,  Washington,  D.C.
                                14

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2.  Environmental  Protection  Agency,  "Methods   for   Chemical



    Analysis  of  Water  and Waste—1971", National Environmental



    Research Center, Cincinnati, Ohio.








3.  CFR 38, 199, 10/16/73.







t|.  Loehr, R. C. and Kukar, T. J.  (1965) "Removal  of  Lipids   by



    Conventional  Waste  Treatment",  Intl.  Jour.  Air  and Waste




    Poll,  9,479-485.







5.  Loehr, R. C.  (1969)  "Aerobic Microbial Degradation of Lipids"



    Final  Project Report,   June   1963  -  January   1968,  to   the



    Federal Water Pollution Control Administration.







6.  Ellms, J. W. arid Werts, J. J. (1943)  "Extracts from the  1940



    Report of  Division  of  Sewage Disposal,  Cleveland, Ohio," Sew.



           Journal 15,  100-109.
 7.   Loehr,  R. C.  and the  de Navarra,  C.  T,  (1969)  "Grease Removal



     at  a  Municipal  Treatment Facility,"  JWPCF 41 R 142-154.







 8.   McCarty,  P.  L., Hahn, D. J., McDermott, G. N., and Weaver, P.



     J.   "Treatability of  Oily Waste Water  from  Food  Processing



     and  Soap  Manufacture"  (1972), Presented at the 27th Annual



     Purdue  Industrial Waste Conference,  Lafayette, Indiana.
                                 15

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9.  "Impact of Oily Materials  on  Activated  Sludge   Systems,   "
    (1971)  Environmental  Protection  Agency, Project 12050 DSH,
    March 1971.

10. Water  Pollution   Control  Federation   (1973)  "MOP  No.   3:
    Regulation of  Sewer Use" JWPCF 45 1985-2235.

11. Metropolitan St.  Louis Sewer District,  Ordinance   No.   2289,
    St.  Louis, Missouri.

12. "Rules and Regulations for Discharge of Waste  into  Sanitary
    Sewerage  System,   Jefferson  County,  Alabama,"   Birmingham,
    Alabama.
* U.S. COVERNMENT PRINTING OFFICE: 1975-628-875/590 3-1
                                16

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