United States       Office of Water ft      sw-758

            Environmental Protection    Waste Management     May 1979

            Agency         Washington D.C. 20460

            Solid Waste
vvEPA    Demonstrating Leachate
           Treatment Report
           on a Full-Scale
           Operating Plant

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          DEMONSTRATING  LEACHATE  TREATMENT

       REPORT ON A FULL-SCALE  OPERATING PLANT
          This report  (SW-758)  was  written
by R. L. Steiner, J. D.  Keenan, and A.  A.  Fungaroli,
   and is reproduced as  received from the  grantee.
        U.S. ENVIRONMENTAL PROTECTION AGENCY
                        1979
                        U.S. Environr-or:*-:! Protection Agency
                        Rcg;on V,  UN--/
                        230 South [;--:,.>;•...-:•' i':..cot

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        This project was conducted at the GROWS (Geological  Reclamation
   Operations and Waste Systems,  Inc.)  landfill in Falls Township,
   Pennsylvania,  with partial  funding from the U.S.  Environmental
   Protection Agency, demonstration grant No.  S-803926.

        Publication does not signify that the  contents necessarily reflect
   the views and  policies of the  U.S. Environmental  Protection Agency, nor
   does mention of commercial  products  constitute endorsement by the U.S.
   Government.

        An environmental protection publication (SW-758) in  the solid
   waste management series.
U.S.

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                                                           CONTENTS
                                                               Page




     Summary and  Conclusions	     1




 I.   INTRODUCTION	-			-	     8




II.   OVERVIEW OF  LEACHATE TREATMENT OPTIONS	    12




     Leachate Composition	    12




     Leachate Treatment	    22




     Summary	    31




11.   LEACHATE TREATMENT SYSTEM		    33




     Design  Overview	    36




          Design  Flow	    36




          Design  Leachate Characteristics	    38




          Design  Concept	    40




          Leachate  Collection System	    ^0




     Chemical/Physical  Section	    k2




          Chemical  Precipitation	    k2




          Air Stripping of Ammonia	    k3




          Neutralization and Nutrient  Supplementation	    A*t

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                                              CONTENTS (Continued)

                                                              Page

     Biologtcal  Treatment Section                                44

IV.   MATERIALS  AND METHODS	    47

     Experimental  Systems	    47

          System 1  -  Chemical/Physical  followed by
                     Biological  Treatment	    47

          System 2 -  Chemical/Physical  Treatment	    47

          System 3 -  Biological  followed  by Chemical/
                     Physical  Treatment	    49

          System 4 -  Biological  Treatment	    49

          System 5 -  Bench-Scale Testing	    49

     Process  Monitoring	    50

     Statistical  Tests	-		    52

     Presentation  of  Results	    54

 V.   RESULTS  AND DISCUSSION	--    55

     Preliminary Results	    55

          Raw Leachate  Quality	    55

          Lime  Dosage	    59

          Sulfuric Acid Dosage	    60

          Phosphoric  Acid Dosage	    60

     System 1  -  Physical/Chemical Plus  Activated Sludge	    61

          Operational Comments	    69

          Cost  Data	    72

     Nitrification	    75

          Summary	•	•—r	'	    90

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                                                CONTENTS (Continued)




                                                                Page




     System 2 - Chemical/Physical Treatment	   90




          Operational Comments	   95




          Cost Data	   95




     Factors Influencing Lime Treatment Performance	   95




     Systems 3 and k - Biological Treatment of Raw Leachate	  104




     System 5 - Laboratory Studies	  107




          Activated Carbon	  107




          Additional  Laboratory-Scale Studies	  115




          Leachate Treatment Plant Startup	  125




VI .   CONCLUSIONS		-	  132




VII. REFERENCES		-	-	-  136

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                           LIST OF TABLES

                                                                Page

 1  - Summary of System 1  Operation Data	    6

 2  - The Strength of Raw Leachates	   13

 3  - Effect of Solid Waste Disposal  on Groundwater Quality	   17

 4  - Effect of Landfill  Depth on Leachate Composition and
     Pollutant Removal at the University of West Virginia
     - 1965	-	-		   18

 5  - Theoretical  Removal  of Heavy Metals During Lime
     Precipitation	   27

 6  - Leachate Treatability as Hypothesized by Chian and Dewalle   30

 7  - Precipitation and Average Monthly Temperature Data
     Trenton, New Jersey	   35

 8  - Summary of Effluent Criteria for GROWS Sanitary Landfill
     Leachate Treatment Facility	   37

 9  - Design Leachate Characteristics	   39

10  - Periods of Operation of Leachate Treatment Systems	   48

11  - Routine Laboratory Chemical Analysis	   51

12  - Landfill Leachate Characteristics		   57

13  - Effect of Equalization Pond on  Raw Leachate Variability	   58

14  - System 1 Treatment Performance  after Acclimation of
     Activated Sludge (August 1, 1976 - May 1, 1977 and
     July 1, 1978 - August 31, 1978)		—		   63

15  - Summary of System 1  Operation
     (8/1/76 to 4/30/77 and A/1/78 to 8/31/78)		   68

16  - Warm Weather Operation of System 1	   70

17  - Comparison of Series and Parallel Operation of Activated
     Sludge Units-	-		   71

18  - Operation and Maintenance Costs Incurred During the
     Operation of System 1 following Acclimation of Activated
     Sludge  (8/1/76 to 5/1/77 and 7/1/78 to 8/31/78)	   73

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                     LIST OF TABLES (Continued)

                                                                Page

19 - Ammonia Removal In Activated Sludge Units--—----—•—"-»-   78

20 - Summary of System 2 Results	   91

21 - Summary of Effects of Chemical/Physical Treatment	—   93

22 - Summary of Operation and Maintenance Costs During
     Evaluation of System 2 (11/15/75-5/1/77 and 11/1/77-
     8/31/78)	   96

23 - Summary of Operational Data for Lime Treatment and
     Clarification	   97

2k - Results of Batch Draw-and-FI11 Activated Sludge
     Experiments to Determine the Extent of Phosphorus
     Limitation			—  106

25 - System 3 Operation	  108

26 - System 4 Operation	  109

27 - Summary of System 3 Operation Data (5/1/77-8/31/77)	—  110

28 - Summary of Results of Carbon Adsorption Treatment of Raw
     Leachate	  112

29 - Treatment of Final Effluent with Bench-Scale Activated
     Carbon Columns	  113

30 - Pilot-Scale Carbon Treatment of Final Effluent	  114

31 - Results of Alkaline Chlorination Studies	  118

32 - Experimental  Protocol and Preliminary Results in
     Evaluation of Lime Treatment Additives	  120

33 - Results of Additive Evaluation		—-	-	-  121

34 - Preliminary Filtration Results	  124

35 - Process Loading Rates and Concentrations Observed During
     the Period April  1, 1978 through June 30, 1978	  129

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                          LIST OF FIGURES

                                                                Page

 1  - Reduction in COD During Aerobic Treatment	   24

 2  - Changes in Total  Dissolved Solids  (TDS)  During Aerobic
     Treatment Studies	   25

 3  - Location of Leachate Treatment Plant	   3^

 k  - Schematic Flow System 1 with Ammonia Stripping Lagoon	   k]

 5  - Schematic of Pilot Leachate Treatment Plant
     (Scaled Version of System 1)	   53

 6  - Raw Leachate Chemical  Oxygen Demand	   56

 7  - Flow Chart for Activated Sludge in Series	   67

 8  - Effect of Temperature on Specific  Oxidation Rate	   82

 9  - Substrate Inhibition of Nitrification	   85

10  - Effect of Low Concentrations of Substrate on Specific
     Oxidation Rate (R-)	   87

11  - Effect of pH on Clarifier Effluent Nickel Concentration—  101

12  - Effect of pH on Clarifier Effluent Mercury Concentration--  102

13  - Effect of Leachate Temperature on  Clarifier Effluent
     Nickel Concentration	  103

]k  - Carbon Breakthrough Curve	  116

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                   DEMONSTRATING LEACHATE TREATMENT
                Report on a Full-Scale Operating Plant
              R.L. Steiner, Ph.D., P.E., J.D. Keenan, Ph.D.,
                       A.A. Fungaroli, Ph.D., P.E.
                        Summary and Conclusions


     The results of 3 years of operation of a full-scale sanitary

landfill leachate treatment plant are reported.  The plant  is designed

to provide a variety of chemical/physical and biological treatment

sequence options.  The chemical/physical units include equalization,

lime precipitation, sedimentation, air stripping, neutralization and

nutrient supplementation.  These treatment processes are designed to

remove heavy metals, ammonia and organic materials, and to encourage

subsequent biological treatment by reducing the pH and adding the

nutrient phosphorus.  The biological treatment process is activated

sludge designed to provide both organic 5-day biochemical oxygen

demand (BOD_) degradation and nitrification.  The demonstration

leachate treatment plant is designed to provide operational flexibility

in that the flow can be directed through the various unit processes and

operations in any sequence.

     The purpose of this project was to demonstrate the efficiency of a

number of treatment sequences.  Specifically, five modes of operation

were defined and have been investigated.  System 1  consists of chemical/

physical  treatment followed by activated sludge;  System 2,  chemical/

                                  -1-

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physical treatment only; System 3, biological treatment followed by

chemical/physical; System 4, biological treatment only; and, System 5,

bench-scale studies, including activated carbon adsorption treatment.

     Data have been collected which can be used to characterize the

quality of raw leachate generated in an operating sanitary landfill.

These data show that the leachate from this sanitary landfill source

is high in organic matter (average chemical oxygen demand (COD)/liter

of 18,553 mg, average BOD^/liter of 10,907 mg) and nitrogen (average

NH^-N/liter of 1,001 mg).  At the end of the first 2 years of operation

these figures were 11,210 and 17,562; 4,460 and 10,773; and 1,503 and

1,047, respectively.  Thus, although influent nitrogen values have

fallen, the increase in organic strength has been extremely large.  The

raw leachate heavy metal  concentrations are somewhat lower than

expected, possibly reflecting the relatively high pH of the leachate.

(Note that all data have been collected with nonfiltered samples.)

     High concentrations of ammonia in the raw leachate exceed the

plant's effluent criterion and are sufficient to inhibit the growth of

the activated sludge microorganisms.  For this reason the original

plant design was augmented with an ammonia stripping lagoon.

     System 5 studies have been conducted for a number of purposes.

Bench-scale tests have provided optimal operating data for chemical/

physical units.  In particular, System 5 has provided data for the
                            f
development of lime, sulfuric acid, and phosphoric acid dosages.

     Activated carbon adsorption has been evaluated as a treatment

method for raw leachate.  For raw leachate, carbon adsorption did not

prove to be an effective treatment procedure.  The inability to use


                                  -2-

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carbon adsorption is the result of high suspended solids loading causing



pore plugging and the wide range of flow variability.



     Pilot scale data have been collected for System 5, carbon



adsorption of System 1 effluent.  In this mode, the carbon column would



serve as a tertiary, or advanced waste, treatment process.  The results



indicate that the carbon can remove much of the remaining COD and heavy



metals.  The results have been analyzed in terms of Langmuir adsorption



isotherms and carbon breakthrough curves.  This way of handling the data



provides preliminary full-scale design information.



     Systems 3 and k, those in which raw leachate is influent to the



biological units, have received considerable operating attention.  The



results indicate that the raw leachate is not directly treatable by



biological means.  Systems 3 and k yield an effluent which is high in



organic matter.  The mean effluent BOD from System 3 was 763 mg per



liter.  The performance of Systems 3 and A has not been satisfactory



for the treatment of this leachate.



     Systems 1 and 2 are those in which the raw leachate is treated



first by chemical and physical means.  The results of these systems



are most promising.   During the third year, these systems were preceded



by equalization.  Lime precipitation followed by sedimentation has been



successful in removing the heavy metals and a portion of the organic



matter.  Specifically, this sequence (System 2) has removed about one-



quarter of the nitrogen; one-third of the dissolved solids; one-half




of the organic matter; three-quarters of the suspended solids; and



ninety percent of the phosphates.  The sequence has been successful in




                                  -3-

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removing  the  heavy metals including one-half of the cadmium and




mercury; two-thirds of the lead, chromium, and nickel; three-quarters




of the copper; over ninety percent of the iron and zinc.




     The performance of System 2 has been studied carefully in order to




determine the treatment unit's response to a number of operational




parameters.  It was found that temperature and pH both exert an effect




on the concentration of heavy metals in the lime treatment effluent.




However, the response is not identical  for all heavy metals.  It may be




possible to use the differences in these responses in an  operational




control strategy to achieve optimal removal  efficiences of selected




contaminants.




     An ammonia stripping lagoon is included in the chemical/physical




treatment sequence because of the excessive ammonia levels in the raw




leachate.  During the lime precipitation/clarification/ammonia stripping




mode of operation, the following removal efficiencies have been achieved:




66 and 50 percent of the BOD and COD, respectively; approximately 60




percent of the ammonia-N and total  Kjeldahl-N; approximately 75 percent




of the suspended solids; 25 percent of  copper; 50 to 60 percent of




cadmium and nickel; 6k to 68 percent of lead; approximately 96 percent




of zinc; 98 percent of iron.




     The ammonia lagoon has a detention time of 1.7^ days, thereby




providing an equalizing effect.  That is, the effect of the lagoon  is




to dampen the peaks and to minimize shock loadings on subsequent




treatment units.  For example, during the period in which the lagoon




was included in the treatment sequence, the mean ammonia  concentration




                                  -k-

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 in the raw leachate was 1001 mg per liter with a standard deviation




 slightly larger, indicating tremendous variability.  During the same




 period, the t] standard deviation interval for the ammonia lagoon




 effluent was 203 to 6^1 mg per  liter. Thus, the equalization effect  is




 significantly beneficial  in terms of lessening shock loadings.




      During the third year, an equalization pond was used to further




 dampen the fluctuations in leachate quality and quantity.  This was




 done to provide a more even flow to the lime treatment unit.   The




 effect of the equalization was to reduce influent variability for many




 parameters, as measured by the coefficient of variation; and to enable




 more uniform dosing of raw leachate with lime.




      System 1  provided the best degree of treatment.  This sequence




 consists of equalization,  lime precipitation/clarification/ammonia




 stripping/neutralization/phosphorus addition/activated sludge.  In this




 operational configuration,  excellent removal  efficiencies have been




 observed, following the adaptation of the activated sludge to the waste




 (Table 1).   Except for NH.-N,  BOD,.,  and lead, the effluent concentrations




 comply with the criteria  developed by the Pennsylvania Department of




 Environmental  Resources and the Delaware River Basin Commission for




 discharge to the Delaware  River.   The standards for these parameters




 were not met because  of the unusually severe  temperatures of  the winter




 of 1976-77, and secondarily because of the great increase in  raw




 leachate strength which began  during the second year of this  project.




(The treatment  performance  of System  1  met all  standards during periods




 with relatively warm  weather.   During  the period up to January 1977




                                   -5-

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                              TABLE 1




                 SUMMARY OF SYSTEM 1 OPERATION DATA

Parameter
Ammon ia-N
BOD
Cadmium
Chromium
COD
Copper
1 ron
Lead
Mercury
Nickel
Zinc
8/1/76
Raw
Leachate
mc/1 iter
758
11886
0.08
0.26
18*490
0.1*0
333
0.7^
0.006
1.76
19.5
to 5/1/77 and 4/1/78 to 8/31/78
Final Discharge
Effluent Percent Standard
mq/liter Removal mq/Uter
75
153
0.017
0.07
9^5
0.11
2.7
0.12
0.00*»
0.75
0.53
90.1
98.7
78.2
73-1
9^.9
72.5
99.2
83.8
27.4
57.^
97-3
35
100
0.02
0.1
5V
0.2
7.0
0.1
0.01
a.
0.6

No discharge standard for this parameter.
                                  -6-

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System 1 consistently met the effluent criteria.  Likewise, during



the third project year, the summertime performance of System 1 was



excel lent.)



     The System 1 operating data have been examined closely in order to



characterize the ammonia removal mechanisms.   In the lagoon this occurs



as the result of volatilization of the free ammonia predominant at high



pH levels.  In the activated sludge units, the principal mechanism for



ammonia removal is biological nitrification to nitrate.  The rate of



nitrification, expressed as the specific oxidation rate, is a function



of temperature which follows the van't-Hoff Arrhenius relationship.



The results show that the activation energy is approximately 12350 cal.


                                                         9     ~1
per mole, and the Arrhenius frequency factor is 2.18 x 10  day



The data indicate that substrate inhibition due to ammonium ion



concentration occurs in this system.  This relationship has been fitted



to the Haldane inhibition model.  The maximum specific oxidation rate



is 3.5 g N oxidized per g biomass/day.  The saturation constant is A



mg per liter,  and the inhibition constant is 36 mg per liter.
                                 -7-

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                   DEMONSTRATING LEACHATE TREATMENT
                Report on a Full-Scale Operating Plant
             R.L. Steiner, J.D. Keenan, and A.A. Fungaroli


                           I.  INTRODUCTION

     The potential for water pollution from sanitary landfill  sites has

become recognized in recent years.  A number of studies have documented

the great pollutional strength of landfill  leachates.       The quality

of this material varies with landfill age,  nature and  moisture content

of the wastes disposed at the site, and hydrologic and soil  factors.

In spite of this variability, it can be stated that, especially for

young landfills, the values of the critical sanitary parameters of

leachate are at least an order of magnitude greater than for domestic

sewage.  The deleterious consequences following contamination of ground

and/or surface waters by leachate may be severe, and it is  for this

reason that leachate treatment is receiving attention.

     Solid waste consists of matter which can be decomposed  by bacterial

or microbial action, as well  as of materials which are inert to

microbiological activity.  Some of the compounds, cellulose  in

particular, are resistant to biological breakdown, but with  sufficient

time decomposition will occur.  Because of this resistivity  and

necessity to acclimate the biological system, the chemical  characteristics

of leachate are time-dependent.  To complicate treatment, as the paper

                                  -8-

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decomposes, some of the Inorganic ions which are bound to the organic




matrix are released and can be removed by water percolating through




the landfill.  The actual mechanism of removal varies with the component




but includes solution as well as colloidal transport.




     The generation of leachate in landfills is complicated and cannot




be generalized simply as surface water percolating through the sanitary




landfill.  When refuse is placed in the landfill, decomposition begins




to occur.  Some decomposition products may be water soluble whereas the




parent products might not have been.  This is especially true of




cellulose.  In addition, the inorganic constituents also must be




considered since they vary with the state of decomposition.  The amount




of water percolating through a sanitary landfill is the primary control




of leachate quality, but the chemical  characteristics of the leachate




are dependent on other parameters, including temperature, water




composition, moisture content, time, mode of decomposition (aerobic,




etc.)  and the amount of infiltration of rainfall at the landfill.




     Recent studies have shown that leachate is produced in a sanitary




landfill when the precipitation exceeds the net evapotranspiration of




the region.  Remson, Fungaroli and Lawrence developed a model for




predicting the movement of leachate through a sanitary landfill.




Further results using this model  have substantiated the validity of the




approach and prediction of leachate generation patterns is reasonably




accurate.  Dass et al.  have also used  a water budget method for




predicting leachate generation.




     Ground and surface waters can be  protected if the landfill  is




underlain with an impervious membrane.  With proper design, leachate




                                  -9-

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is then directed toward collection points.  A waste such as this, which



is properly considered an industrial waste, must be treated prior to



surface discharge.  The leachate treatment state-of-the-art is still



embryonic, although a few small scale studies have been conducted.



These have demonstrated that neither conventional chemical treatment



nor biological treatment can achieve the high degree of treatment



efficiency expected today.  Consequently, although we know that the




pollution potential of sanitary landfill leachate can be avoided by



interception using impervious liners, we are not yet able to define



the optimum sequence of unit operations and processes required for



adequate wastewater renovation.



     The U.S. Environmental  Protection Agency, Office of Solid Waste,



awarded a demonstration grant (S-803926) to investigate the



effectiveness of alternative treatment sequences as employed at the



full-scale facility in Falls Township, Pennsylvania.  A 380 liter



per minute (0.144 mgpd)  plant had  been constructed to treat leachate



from the GROWS (Geological Reclamation Operations and Waste Systems,



Inc.) landfill.  This project had  as its primary goal the evaluation



of the technical feasibility, operational efficiency, and cost



effectiveness of four alternative  treatment sequences.  These are:



(1) chemical/physical followed by  biological; (2) chemical/physical




alone; (3) biological followed by  chemical/physical; and  (4) biological



alone.  The chemical/physical processing includes precipitation of



heavy metals by lime addition, sedimentation, air stripping of ammonia,



and neutralization using sulfuric  and/or phosphoric acids.  Equalization



                                -10-

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of raw leachate was initiated during the third year of the project.




Biological treatment consists of conventional activated sludge.



Additional objectives of the study were the bench-scale evaluation of



carbon adsorption on both raw leachate and unit process effluents; and



bench-scale testing to determine chemical  dosage, sludge return rates,



aeration rates, and other plant operation criteria (System 5).  The



purpose of this document is to present and discuss the results of the



3 years of operation of this facility.
                                  -11-

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               II.   OVERVIEW OF LEACHATE TREATMENT OPTIONS


       The purpose  of this chapter Is to review the literature regarding


  the composition of sanitary landfill  leachates and their  treatment.   In


  brief,  the character and variability of the leachate dictates the types


  of treatment systems which will  be effective.   The contaminants  of


  greatest concern  fall  into several  groups.   The first group is the


  organic chamicals, important primarily because they exert an oxygen


  demand  on receiving waters which may result in a depletion of dissolved


  oxygen  deleterious to aquatic life.  The second major group of


  contaminants found in sanitary landfill  leachates is comprised of the


  heavy metals.   As a group, these elements are of concern  because they


  are toxic at sufficiently high concentrations.  It is conventional


  practice to chemically characterize wastewaters such as  leachate in  terms


  of a number of other parameters.  These are used for a variety of


  purposes including design, operation control,  and evaluation of  pollution


  potential.


                           Leachate Composition


       In 1932,  one of the first studies indicating that the disposal  of


.  solid waste could cause environmental pollution was reported by  Calvert


  who investigated  the liquid waste from a garbage reduction plant in

               2
  Indianapolis.    In this process the garbage was cooked and the grease


  removed to produce fertilizer and animal feed, and the liquid waste  was


  discharged into an impounding pit or lagoon.  An analysis of this liquid


  is presented in Table 2, Column 1.   Calvert analyzed the  groundwater


  from existing  wells surrounding the lagoon and found that wells  up to


                                   -12-

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        s=
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500 feet downstream of the site showed a marked increase in magnesium,



calcium, total dissolved solids and carbon dioxide.




     Carpenter and Setter, working at New York University in 1940,


                                                                       19
conducted one of the earliest studies concerned with landfill leachate.



Auger holes were drilled through an existing landfill  of undetermined



age into the subsoil.   Twenty-eight samples of leachate which were



collected in the bore holes were analyzed chemically.   The range of



concentrations is presented in Table 2, Column 2.   These results showed



a wide variation of concentration over the site, thus  indicating the



difference of filled materials at various locations, or the differences



in the age of the refuse at different points.  Analysis of groundwater



in the area was not performed; therefore, the effect on the subsurface



environment was undefined.



     The first comprehensive research study of sanitary landfills under



controlled conditions was conducted at the University  of Southern



California.   Test bins, simulating landfill conditions, were constructed.



Water was added to simulate the infiltration of 1.12 m and leachate was



collected and analyzed.  Table 2 gives the minimum and maximum (Column




3) values of the initial (first 45.9 liters of leachate per cu m of



compacted refuse) leachate.  The most rapid removal (the highest



concentrations) occurred with the first 232 liters per cu m of refuse.



Thus, it was postulated that removal would continue for many years  but




at a very slow rate, and it was considered unlikely that all the




constituents would ever be removed.

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     The same study also examined a field site consisting of 2.k m of




refuse and 0.61 m of cover material.  The refuse was in Intermittent




contact with the groundwater, analysis of which showed increases in all




organic ions and a maximum biochemical oxygen demand of 125 mg/liter.




One conclusion of the study was that the dissolved inorganic ions




entering the groundwater through intermittent contact would decrease In




concentration as a result of dilution and adsorption and travel in the




direction of the groundwater movement.




     The other conclusions reached in this study are summarized as




follows:  (1) A landfill, if located so that it is in intermittent or




continuous contact with ground water, will cause the ground water in the




immediate vicinity of the landfill  to become grossly polluted and unfit




for domestic or irrigational use; (2) dissolved mineral  matter, entering




ground water as a result of intermittent and partial  contact of a




landfill with the underlying ground water will  have its greatest travel




in the direction of flow, undergo a vertical diffusion to  a limited




extent, and be subject to dilution, the result of which will be a




minimizing of the effect of the entering pollutant ions;  (3) a landfill,




if located so that no portion of it intercepts the ground water, will




not cause impairment of the ground  water for either domestic or




irrigational  use;  (4) rainfall  alone (in the area of this study) will




not penetrate a 2.3 m thick landfill  sufficiently to cause entry of




leachate Into the underlying ground water.




     Longwel1 stated in 1957 that an appreciable proportion of refuse




could be extracted by water to produce a leachate rich in organic



                                 -15-

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                                             21
matter, Inorganic salts (ions), and bacteria.    The analysis of a



surface leachate obtained from an unnamed landfill is given in Table



2 (Column *f).



     In 1961 the British Ministry of Housing and Local  Government



conducted extensive research on the placement of landfills above the



groundwater table (which they called "dry tipping"), and the placement



of landfills below the groundwater table (which they called "wet


          22
tipping").  In the "wet tipped" experiment the refuse was completely



submerged and the horizontal groundwater flow rate was equivalent to



138 liters per sq m per day.  The leachate quality is included in Table



2 (Column 5).  Analyses of the groundwater before and after contact with



the refuse are given in Table 3-  These results show the considerable



extent of groundwater quality degradation due to pollution by leachate.



     In 1965, Qasim studied the seepage waters from simulated landfills


                                   23
at the University of West Virginia.   Three concrete cylinders 0.9 m in



diameter  and 1.2, 2.A and 3.7 m in height were filled with municipal



refuse.  Approximately 102 cm of precipitation were artificially added



to the cylinders over a period of 6 months and leachate samples were



collected.  The maximum concentrations of certain organic and inorganic



components in the leachate from the three cylinders are presented in



Table k.  Table k also presents the total weight removed per cubic



meter from each depth of fill by 102 cm of simulated infiltration.



     A summary of results presented by Qasim demonstrates the effect of



depth on leachates generated by landfills.  Concentrations of various



pollutants were higher in leachates obtained from deeper fills.



Concentrations of various pollutants per unit depth of fill decrease



                                 -16-

-------
                    TABLE 3

EFFECT OF SOLID WASTE DISPOSAL ON GROUNDWATER QUALITY-
  GROUNDWATER QUALITY BEFORE AND AFTER INTRODUCTION
            OF "WET TIPPED" LANDFILL - 196126

Concentration (mg/liter)
Measured Quantity
Total Solids (Residue)
Chloride
Alkal inity, as CaCO,
Sulfate
Biochemical Oxygen Demand (BODc)
Organic Nitrogen
upstream or
Landfill
1*50
30
180
120
0
0
Downstream ot
Landfill
5,000
500
800
1,300
2,500
70
                    -17-

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-18-

-------
with increasing depths of refuse.  For an equal amount of influent,



shallower fills showed greater extraction rate per unit volume of fill



than deeper fills.  The bulk of the pollution was attributed to initial



leaching.



     Anderson and Dornbush conducted an extensive investigation of the


                                                                  27
groundwater leaving a landfill in Brookings, South Dakota in 1967.



An abandoned gravel pit of 160 acres with its base well below the



water table was filled with municipal solid waste.  The purpose of the



investigation was to determine which chemical parameters were the most



reliable indicators of the influence of landfills on the groundwater.



Groundwater samples from 22 wells located over the site were analyzed



for chloride, total hardness, alkalinity, sodium, pH, potassium, iron,



nitrate, and specific conductance.  A considerable increase in all



constituents measured was observed in three wells immediately downstream



of the fill area.  Although the authors did not evaluate the potential



pollution of municipal refuse, they did report an increase of up to



50 times the chloride content of native waters in the groundwater



affected by the leachate.  The major conclusion of this investigation



was that two of the most important indicators of pollution from



landfills are chlorides and specific conductance or total dissolved



solids.   Chloride ions are easily detectable, not readily absorbed by



soils,  not affected by biological processes, and apparently an abundant



product  of leachates.



     Disposal sites in northern Illinois were investigated in 1970 by

             28
Hughes  et_ aj_.   Leachate samples from three landfills of varying age



                                 -19-

-------
were obtained as near to the base of the refuse layer as possible.  The
results of these analyses are presented in Table 2 (Columns 6-8).
Although no Information is given in the study as to the composition of
the solid waste in each fill, and the analyses were performed on only one
sample, the results do show a decreasing trend with time.  However, It
was noted that refuse more than 15 years of age can still have a high
total dissolved solids content—indicating that the stabilization of
landfills is a long process.
     The laboratory simulated landfill  or lysimeter study conducted at
Drexel University from 196? to 1972 is the only study reported that was
conducted under completely controlled laboratory conditions.  It was
also the only study reported in which the environmental conditions
completely simulate the existing climatic conditions of a region, In
this case, southeastern Pennsylvania.  The refuse was placed at as
received moisture content and allowed to reach field capacity naturally
through the addition of amounts of distilled water equal to the
precipitation of the area nrnus the evapotranspiration.  This
infiltration was added on a weekly basis and varied from a rate of 8.9
cm per month during the wet periods to zero during the dry or summer
periods.  Approximately one year was required for the refuse to reach
field capacity, but small quantities of leachate were generated before
field capacity was reached.  The maximum concentrations obtained in the
first year are given in Table 2, Column 9.
      It was concluded that this initial leachate production came from
the following sources:  (l) From the refuse.  Most of the initially
generated leachate is squeezed from the organic components of the refuse
                                 -20-

-------
by the compaction and placement procedure.   (2) From channeling.  Some



of the water added at the top of the lysimeter may find a direct route



through the refuse to the collection trough, due to any inhomogeneities



in the refuse.  (3)  From an advanced wetting front.  The wetting front



in the refuse probably moves as a broad band rather than as a single



line interface.  As a result, substantial increases in leachate will



occur before the entire system is at field capacity,  (k)  From the main



wetting front.  This is the leachate which is produced when the system



reaches field capacity.  At this time, the input water and the output


leachate quantities become approximately equal.



     Other studies have mentioned the leachate problem of refuse


disposal  in papers dealing with other aspects of the solid waste problem.



Leo Weaver has stated that municipal refuse can generate leachates high



in organic pollutants.     Data from this study are included in Table



2 (column 10).



     Engineering Science in a study conducted in 1967 in southern


California concluded that groundwater pollution, which may arise from


refuse leachate reaching a water source, will be shown largely as an

                                                            32
increase in total  dissolved solids and specific conductance.


     Walker in 1969 found that a sand and gravel aquifer in Illinois



was -ineffective in removing dissolved chemical  ions generated by a



landfill.    He did report that travel  of leachate through a short



distance (3 to 5 m) of  this aquifer will remove organic pollutants


generated by landfills  in Illinois and concluded by stating that



inorganic pollutants constitute the greatest source of concern.


                                 -21-

-------
Roessler noted an increase in inorganic pollutants in an industrial



water supply 2i miles downstream from a refuse dump 10 years after the


                           34

dump had started operation.




     Table 2 (columns 11 to 13)  presents a summary of values of raw



leachate composition as compiled by Chian and DeWalle.^5  The ranges



represent leachates examined by a number of investigators (Range 1 —



Column II) and a variety of leachates studied at the University of



Illinois (Range 2—Column  12).  These data are the results of a recently



completed literature review.   Another recent report summarizes the



state-of-the-art with respect to ground water monitoring for leachate



contamination.   This paper should be consulted before initiating a



monitoring program.



     The conclusion to be drawn from this review of landfill leachate



quality (as summarized in Table 2) is that its composition is highly



variable from site to site.  In addition, the data show that even at



a given landfill, considerable variation is encountered with respect



to both space and age.  That is, variability is a factor within a



landfill and also over the history of the site.  Consequently, it  is



concluded that landfill leachate quality cannot be predicted a priori;



and that this quality is even variable at a given site.



                          Leachate Treatment



     Leachate treatment system? have been evaluated on a laboratory



scale at Drexel University.  In one study, the purpose was to



characterize the biodegradation of organic matter both with and without


                                        37
the supplementary addition of chemicals.    The system consisted of



                                 -22-

-------
five aerobic units which were treated in the following manner:



(1) control-no treatment; (2) addition of sodium hydroxide to pH 9;



(3) addition of sodium hydroxide to pH 11;  (4) addition of lime;




(5) addition of lime plus sodium carbonate.  Otherwise, all units were



handled in the same manner.  This procedure included preparation of an



activated sludge culture by aerating leachate.  Each experimental unit



was seeded with this culture and was aerated at a rate of 3k liters of




air per gram chemical oxygen demand (COD) (1500 cu ft per Ib COD).



During the testing, all settled solids were recycled to the aeration



tank with no sludge wastage.  The aeration treatment systems were



operated on a continuous basis with a hydraulic residence time of



five days.



     The COD values decrease quite rapidly during the first six days



and thereafter approach a limit (Figure l).  The results indicate that




there are components of leachate which are not amenable to treatment



in an aerobic system.  The time of adaptation of microorganisms for



treatment of the organic fraction of leachate may be considerably longer



than normal sewage.  Volatile solids concentrations in these tests were



low when compared to normal  activated sludge systems.  This may be one



reason for the long time required for stabilization.



     A high variation in the concentration of total  dissolved solids




in the treated effluent was noted (Figure 2).   The cyclic variation of



several  systems is of interest,  but not all  of the systems show this



phenomenon.  Since the withdrawal  and addition of leachate was constant,



there was no reason for the cyclic effect.   Only pretreatment with lime



                                 -23-

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gave any type of stability and COD reduction.

     Thus, neither biological waste treatment nor chemical-physical

treatment separately is able to reduce the biochemical oxygen demand

(BOD)more than eighty percent.  In fact, the efficiency of the

chemical-physical process is considerably below this level.  It is

hypothesized that two reasons exist for the poor removal efficiency of

each individual system: l) the large percentage of high molecular weight

organic materials, and 2) the biological inhibition caused by heavy

metal presence.  The physical-chemical treatment is needed to remove

the metals and also to hydrolyze some of the organics, and biological

treatment to stabilize the degradable organic matter.

     In addition, biological treatment alone does not remove significant

amounts of the heavy metals.  In fact, biological units may be inhibited

due to the toxic effects of the metals.  Consequently, chemical and/or

physical processing is needed for the removal of substantial amounts of

these'materials.  Lime treatment is particularly effective in that it

creates the alkaline conditions under which the metals become insoluble.

     The removal of heavy metals during lime precipitation depends upon

the formation of insoluble metal compounds, primarily hydroxides, at

alkaline pH.  The optimum set of conditions is not identical for all

metals, and the result is that it is impossible to achieve the maximum

theoretical removals for each metal within a single tank.  In general,
                                                           oQ
the optimum pH levels are in the range of 7-10.3 (Table 5).

Hexavalent chromium is not removed by lime addition unless it has

previously been reduced to trivalent chromium.

                                 -26-

-------
                                   TABLE 5

       THEORETICAL REMOVAL OF HEAVY METALS DURING LIME PRECIPITATION^1
                                                       Theoretical Effluent
                                    Optimum pH Range  Concentration mg/liter

Cadmium                                    10                 i.0

Hexavalent chromium

Trivalent chromium                      8.5~9-5                <1

Copper                                  9.0-10.3              0.01

Soluble Iron                                7

Lead                                       --                
-------
     These studies demonstrated that the aerobic treatment of sanitary



landfill leachate is feasible and that pretreatment may be required.



Lime precipitation appears to be the most favorable pretreatment. method.



The organic fraction of leachate was found to contain substances not



readily assimilated by the microorganisms, and it was hypothesized that



chemical treatment is needed to remove these organics.


                                                                     39
     Chian and DeWalle have treated lysimeter leachate  anaerobically.



They used a completely mixed anaerobic filter with recirculatiori of



effluent.  The unit responded well  to shock loads, produced low sludge



yields and operated without nutrient supplementation in spite of a COD:



N:P ratio as high as ^360:112:1.  Heavy metal toxicity  was minimized by



the addition of sodium sulflde.



     Chian and DeWalle have recently completed an extensive review of


                              AO
leachate treatment techniques.    Their conclusion was  that leachate



collected from recently leaching landfills is best treated biologically.



This is because the organic fraction of such leachate is composed



predominantly of free volatile fatty acids which are readily



biodegradable by either aerobic or anaerobic means.  On the other hand,



leachate from older landfills is more efficiently handled by



chemical-physical processes, because these organics are more resistant



to biodegradation.  They also concluded that activated  carbon and reverse



osmosis were the most efficient chemical-physical methods in terms of the




removal of organics.



     A more recent study by Chian has been devoted to a detailed analysis



of the constituents of the organic fraction of grossly polluted



groundwater and of leachate collected from wells or underdrains near




                                  -28-

-------
                           42

solid waste disposal sites.    The techniques used for concentrating,




separating, and characterizing the soluble organics were membrane




ultrafi1tration, gel permeation chromatography and analysis for functional




groups and specific organics.  The free volatile fatty acids constituted




the largest fraction and this fraction became relatively smaller as the




age of the landfill increased.  Increasing stability with increasing




landfill age was noted for other groups of organics.  These results tend




to confirm the concept that biological treatment is best suited for




treating leachate from a young landfill, and that physical-chemical




processes are more appropriate for older landfills.




     The compilation of data presented by Chian and Dewalle indicate




the following range of COD removal efficiencies for various treatment




methods: 0 to 98 percent for aerobic biological; 87 to 99 percent for




anaerobic biological; 17 to 40 percent for aerobic/anaerobic biological;




0 to 40 percent for chemical precipitation with alum, ferric chloride,




ferrosulfate or lime; 34 to 94 percent for activated carbon and ion




exchange; 0 to 48 percent for chemical oxidation; 56-98 percent for



                43
reverse osmosis.



     As a means to bring order to the wide disagreement found in the




literature, Chian and DeWalle postulated that the age of the landfill




affected the character of the leachate, and that this character is best




measured in terms of the ratios of chemical oxygen demand to total




organic carbon (COD/TOC) or of biochemical oxygen demand to chemical




oxygen demand (BOD/COD)  (Table 6).^




     A recent laboratory scale study by Uloth and Mavinic is closely



                              45
related to the present effort.    They studied aerobic biological




                                  -29-

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                                             -30-

-------
treatment of very strong leachates.  They were able to develop kinetic
constants fitting the Lawrence-McCarty model.     Successful operation was
attained at mixed liquor volatile suspended solids concentrations of
8000 to 16000 ppm at sludge ages in excess of ten days.
                                 Summary
     The state-of-the-art concerning the composition and treatment of
sanitary landfill leachates has been assessed.  The most obvious
characteristics of leachate are Its strength and its variability.
Leachate is generally of much greater strength than domestic sewage.
This is especially true in terms of organic materials and the potentially
toxic heavy metals.  As important a characteristic as strength is the
variability of leachate composition.  Leachate quality not only
fluctuates from landfill site to site, but also from time to time at
one landfill.  Changes over time result from differences in seasonal
hydrology and microbiological activity.  Rainy weather may dilute the
leachate, but, at the same time, may flush out large quantities of
pollutional material.  The typical  pattern observed over many years is
that the pollution potential  of leachate is greatest during the first
five years or so after placement, but that leachate strength remains
significant for as long as ten to twenty years.   This sequence Is
encountered because the microbiological processes responsible for the
decomposition of the solid wastes are relatively slow acting and are
first directed at the most readily biodegradable components of the
waste.
     Considerable differences are encountered  In leachate quality when
comparing landfills.   In addition to the seasonal,  hydrologlc and age
                                 -31-

-------
of landfill factors mentioned above, there are several  other reasons



for this observation.  The chemical nature of the wastes accepted at



the landfill has a marked effect on the composition of  the leachate.



The land disposal of industrial  liquid and solid wastes is critical  in



this light.



     The variability and the strength of leachate have  important waste



treatment implications.  First,  the sheer magnitude of  the measures of




pollution potential dictate the use of thorough waste treatment.  Second,



the changes encountered from landfill to landfill are such that waste



treatment techniques applicable at one site are not necessarily directly



transferable to other locations.  That is, it may be mandatory that each



instance be separately engineered to achieve adequate treatment.  Third,



the fluctuations in leachate quality which occur over both short and



long term intervals must be accounted for in the treatment design.  Not




only must processes be designed to treat efficiently the waste flow from



minute to minute, but the design must also reconcile the possibility



that treatment techniques which work well for a young leachate may



become wholly inadequate as landfill age increases.



     It is apparent today that most landfill leachate cannot be treated



adequately by just conventional  chemical/physical treatment or




conventional biological treatment.  Rather, what is needed is a



combination of the two approaches with perhaps a supplementary form of




advanced wastewater treatment.  The purpose of this project is to



investigate, at both the full and bench-scale levels of operation, the



efficiency of treatment afforded by these processes.




                                  -32-

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                     III.  LEACHATE TREATMENT SYSTEM




     The leachate treatment facility used  In this study  is located at




the GROWS landfill in Tullytown, Falls Township, Bucks County,




Pennsylvania  (see Figure 3).  The plant  is designed to provide maximum




operational flexibility  in order to permit full-scale testing of a




variety of treatment sequences.  Plant design and treatment modes are




considered in subsequent paragraphs.




     The sanitary landfill has a surface area of 50 acres.  The landfill




will be filled with about 1,^00,000 cu m of refuse over  the next several




years.  The time required to fill the landfill depends upon many unknown




factors, but  it is estimated that it will probably be between 5 and 10




years.  The receipt of refuse is about 800 tons per day.  Eighty-five




percent of the refuse is from municipal sources.  The remainder is




industrial and commercial.  The landfill is also permitted to accept




sewage sludge and selected industrial liquid wastes.




     The landfill  is located in the semi-humid northeastern part of the




United States.  The thirty year monthly average precipitation and




temperature data are given in Table 7.   In this region there is a net




positive infiltration of rainfall into the landfill.  As long as there




is a net positive infiltration, leachate will  eventually begin to be




produced by the landfill.




     Because of these meteorological conditions and the  site hydrologic




situation, groundwater pollution potential  existed.  To alleviate this




pollution potential  the Pennsylvania Department of Environmental Resources




required the landfill to be underlain by an impervious asphaltic membrane.




This membrane system was  designed to collect and transport the leachate




                                  -33-

-------
^i
                                                                              '«
FIGURE 3.   LOCATION  OF LEACHATE TREATMENT. PLANT
           WL
              PKNNSBtlRY M ANORM
                    STATE PAKKl
                                                                         74°45'
     PENNSYLVAMIA
            .MIA /
                                             ROAD CLASSIFICATION
                                Heavy-duty     __^___   Light-duty      = — ====
                                Medium-duty   — =^^=_   Unimproved dir1 == = = = = -_-
                                       Q U S Route       (]) State Route
                                                  Interstate Route
   QUADRANGLE LOCATION
                                  TRENTON WEST, PA.— N. J.
                                     NE/4 BURLINGTON 15' QUADRANGLE
                                          N4007.5— W744B/7.5
                                  -3k-

-------
                                  TABLE 7

             PRECIPITATION  AND  AVERAGE MONTHLY TEMPERATURE DATA
                             TRENTON,  NEW JERSEY2*8

Month

January
February
March
April
May
June
July
August
September
October
November
December
Rainfall
cm
8.87
6.58
9-75
8.15
9.19
9.14
10.62
12.12
8.89
7.21
8.03
7.29
in.
3.10
2.59
3.o4
3.21
3.62
3.60
4.18
4.77
3.50
2.84
3.16
2.87
Temperature

0.8C
1.0
5.1
11.1
16.9
21.7
24.2
23.3
19.6
13-5
12.7
1.7

33.4 F
33.8
41.3
52.1
62.7
71.4
76.0
74.3
67.6
56.5
45.1
35.1
Total
104.85    41.28
                                 -35-

-------
to the leachate treatment plant.
     The treated effluent is discharged to the Delaware Estuary.  The
river zone is tidal and flow figures are not available.  At the nearest
gage (Trenton) the drainage area  is 6/00 square miles and the projected
low flow is 33,000 liters per second.  The discharge of treated effluent
directly to the Delaware River occurs only during the months of December
through April.  During the remainder of the year, the effluent is
returned to the landfill.  During the latter portion of the third year,
a program of land disposal was initiated.  The landfill has ample storage
capacity in the pore space so that storage for 6 months does not create
any difficulties.  The effluent is spread on the landfill using aeration
nozzles.
     The treatment plant operates under permits from the Commonwealth of
Pennsylvania Department of Environmental Resources Water Quality Section
and the Delaware River Basin Commission.  The effluent criteria for the
facility are summarized in Table  8.
                             Design Overview
     The purpose of this section  Is to summarize briefly the design
criteria and to discuss the design of the treatment facility.  The
effluent limits have been mentioned above and presented in Table 8.
The following paragraphs are devoted to a discussion of the leachate
quantity and quality as estimated for design purposes.
     Design Flow.  The source of  liquid waste is the leachate which
results from the degradation of refuse and percolation of rain water
through the landfill.  In addition, as the treated effluent is recycled
to the landfill during the summer months, and to the Delaware River
                                  -36-

-------
                     TABLE 8

         SUMMARY OF EFFLUENT CRITERIA^*9 FOR
GROWS SANITARY LANDFILL LEACHATE TREATMENT FACILITY
Parameter
5
Ammonia -Nitrogen
Phosphate
Oil and grease
1 ron
Zinc
Copper
Cadmium
Lead
Mercury
Chromium
Maximum Concentration
mg/I iter
100.0
35.0
20.0
10.0
7.0
0.6
0.2
0.02
0.1
0.01
0.1
                          -37-

-------
during the winter, the raw leachate volume includes this recycled
effluent.  The quantity of waste which is generated is dependent upon
many individual factors of the landfill.   The maximum generation of
waste (including the recycled volume) for design purposes was estimated
to be about 20 liters per sq m-week at this site.  However, the production
of leachate is dependent upon the time cycle, both as to placement and to
the season of the year.  Leachate itself occurs as the result of the
excess of infiltration over evapotransp!ration and the soil moisture
deficit.  Thus, the actual generation of leachate depends upon
precipitation patterns, landfill moisture and effluent recycling.
     Since the generation of leachate is also a function of the age of
the fill, not all the expected leachate will  be produced simultaneously.
There is an initial period of operation when  the landfill comes to field
capacity, followed by an extended period of leaching of contaminants,
after which there exists a period when the leachate is no longer of a
polluting nature.  It is possible that some portions of the landfill
will be in this latter state when the final parts of the landfill are
being completed.  Hence, the maximum flow of  20 liters per sq m-week is
a value which may never be attained for extremely strong leachate.  This
maximum flow rate was determined using the site meteorological data
presented in Table 7 and the procedure developed by Remson, Fungaroli
and Lawrence.
     Design Leachate Characteristics.  The leachate strength parameters
used for design purposes are presented in Table 9.  These were obtained
through a modest sampling program conducted during the very early stages
                                  -38-

-------
             TABLE 9


 DESIGN LEACHATE CHARACTERISTICS
 Constituents	Raw Leachate'"
8005
Suspended Sol ids
Total Solids
Percent Volati le
pH, pH units
Chlorine
Iron, total
Zinc
Chloride
Organic Nitrogen
Nitrate
Sulfate
Copper
Hardness
Alkal ini ty
Color, standard units
Flow, mod
Temperature, F
1500
1500
3000
55
5.5
200
600
10
800
100
20
300
1
800
1100
50
.144
80
'•All  units are mg/liter except pH,  color,
 flow,  and temperature.
                  -39-

-------
of the landfill.  However, as discussed In Chapter II, the exact




character of waste is difficult to predict for a number of reasons,




including the fact that it is subject to dilution when the infiltration




is high.  In addition, because of the on-slte variability, it is




possible that single samples do not accurately reflect the character




of the waste.




     Design Concept.   As discussed in Chapter II, a combination of




chemical/physical treatment plus biological  treatment is often required




for leachate treatment.  The principle is that the chemical/physical




units can be used for the removal of refractory organics and for




pretreatment prior to the biological  process.  In the latter case, the




chemical/physical processes are used for the removal  of potentially




inhibitory materials such as heavy metals and ammonia-nitrogen.  The




function of the biological units is the stabilization of organic matter




and the oxidation of ammonia nitrogen.  As a result of the findings




discussed in Chapter II and the design leachate quality, this treatment




plant was designed to consist of lime treatment and sedimentation




followed by activated sludge and chlorination.  Equalization, air




stripping of ammonia and nutrient addition have subsequently been added




into the chemical/physical section.  A schematic of the leachate treatment




plant appears as Figure 4.




     Leachate Collection System.  The raw leachate is contained within




the lined landfill which was designed to allow for the collection by




gravity of leachate at three locations.  These locations are outfitted




with manholes from which the leachate is pumped and transported via




pressure lines to the treatment facility.  The leachate entered the plant




                                 -40-

-------
o
                            -k]-

-------
via a one thousand gallon holding tank In which little mixing occurred



because the flow from the individual  manholes is highly variable, and




pumped sequentially.  Following start-up of the equalization pond in



the third year, the holding tank was by-passed.




                         Chemical/Physical Section



     The chemical/physical portion of the plant consists of the



following: equalization, chemical precipitation and coagulation,



sedimentation of precipitate, air stripping at elevated pH for ammonia



removal, neutralization and nutrient supplementation.  Each of these are



discussed in the following paragraphs.



     An equalization pond was put on-line during the final project year.



The volume is 950 cu m, and so the design detention time is ].7k days.



This pond is aerated to maintain aerobiosis and prevent solids deposition.



A chlorinated polyethylene liner is used as the inner wall of the pond.




     Chemical Precipitation.   In the chemical treatment phase, the major



design goal  was the removal of inorganic materials.  In particular, metals



that may interfere with the subsequent biological treatment process are



removed; also, the metals are removed to achieve discharge standards



(Table 8).  As part of the chemical treatment, the biochemical oxygen



demand will  also be reduced, and the design percentage of reduction was



30 to 50 percent, on the basis of the experience with municipal




wastewater and with leachate as discussed in Chapter II.




     The chemical treatment step consists of flash mixing followed by



quiescent conditions favorable for coagulation as well as sedimentation



of the chemical sludge.  Lime has been the only chemical utilized  in




                                 -42-

-------
this chemical precipitation step.  However, additional feeders and points



of injection have been provided for the use of other chemicals if



necessary.  Other chemicals which might be used include alum, ferric



chloride, synthetic polymers, and powdered activated carbon.




     This unit Is an upflow solids contact reactor clarifier.  Lime



slurry Is added to cause coagulation and precipitation of the waste



materials.  The lime is pumped at a rate commensurate with the rate of



leachate production.  The lime slurry Is flash mixed with the incoming




waste, and mixing, flocculatjon and upflow clarification occur within



a single unit.  Solids contact may be optimized by variable sludge



recycle.   The chemical  treatment facility Is a 3.66 m diameter,  3.66 m



deep cylinder with a hydraulic retention time of 1.7 hours at 380



liter/min flow rate.



     Sludge is drawn off the bottom of the reactor clarifier and placed



in a common sludge holding tank with the waste activated sludge.  Sludge



return pumps are available to recirculate the sludge and mix It  with the



incoming waste water to reduce the amount of chemicals that are  needed



for precipitation.  (However, the practice to date has been to use fresh



lime and to not recirculate the sludge.).  The amount of sludge  that



is produced in this step depends upon the composition of the leachate.



The design projection was that approximately 5 percent of the flow will



be produced as sludge at 1  percent solids concentration.




     Air Stripping of Ammonia.  As a means of controlling excessive



levels of ammonia in the lime treated stream and in the final effluent,



a lagoon incorporating  air stripping of ammonia is included in the



chemical/precipitation-clarification unit In order to take advantage of



                                 -43-

-------
the high pH of the .upflow solids contact reactor clariffer effluent and



to minimize the solids loading on the lagoon.  On occasion, sodium



hydroxide has been added to the lagoon to further elevate the pH and



force off additional ammonia.  This has been done during cold weather



periods.



     The volume of the ammonia lagoon is 950 cu m, thus providing a



detention time of approximately 1.7^ days at design flow.  The primary



function of the lagoon Is to encourage air stripping of ammonia by an



elevated influent pH of 10, aeration and high internal recycle.  The



lagoon is lined with chlorinated polyethylene.  In addition to ammonia



removal, the-lagoon provides equalization in terms of both flow and



sanitary parameters.



     Neutralization and Nutrient Supplementation.  Sulfuric and



phosphoric acids are added to reduce the pH of the leachate prior to




entering the biological waste treatment portion of the process.



Phosphoric acid replenishes the supply of o-phosphate, a necessary



biological nutrient, which is precipitated and removed following the



addition of 1ime.



                       Biological Treatment Section



     The biological treatment units consist of two aeration tanks and two



secondary clarifiers.  The units may be operated  in series or parallel.




The capacity of each tank  is 75,710 liter, which corresponds to a 6.6



hour detention time at the maximum flow rate of 380 liter/min.  The



aeration chambers are provided with diffused aerators, each driven by




a 14.2 cu m per min blower.



                                 -kk-

-------
     Depending on the actual hydraulic residence time  in the aeration



tanks, the activated sludge units were designed to operate  in either the



conventional or extended aeration modes.   In order to  achieve this, the



mixed liquor volatile suspended solids (MLVSS) would be maintained  in



the range of 3000 to 8000 mg/liter.  Because of the high organfcs loadings



experienced during the last 2 years, the MLVSS was in  the 8000 to 16,000



mg per liter range.  This level is high relative to that normally



maintained in units handling municipal wastewater.  However, it  is



necessary because of the high BOD loading, and because of the requirement



to remove about 90 percent of the BOD remaining after  chemical/physical



treatment.  The MLVSS is maintained by return sludge pumps capable of



delivering a return sludge flow equal to 200 percent of the influent



flow.



     The waste sludge from the activated sludge units  and from the



chemical treatment process is stored in the sludge holding tank.  The



capacity of this tank is 21 cu m, and sludge Is removed as required



and conveyed back to the landfill via tank truck.



     Separation of treated wastewater from the MLVSS is achieved by



gravity sedimentation in the secondary clarifiers.  The total clarlfier



volume is ^7,313 liters, in two parallel independently  operable units.



Sludge return is provided with air lifts Installed in  the final settling



tanks.  A skimming device is located in the settling basin in front of




the scum baffle to remove floating material which is returned to the




aeration compartment.  The maximum surface overflow rate is 20.^ cu m



per day per sq m (500 gpd/sq ft) based on the peak flow of 380 liter/



min.

-------
     Final effluent is directed to the chlorine contact tank after



secondary clarification.   The chlorine contact tank provides a retention



time of 20 minutes at the 380 liter/mln flow rate.   The effluent after



chlorination is discharged to the Delaware River or to the land disposal



site depending upon the season of the year.  The effluent is not



chlorinated when it is recycled to the landfill.  The chlorine contact



tank is a simple baffled  tank to assure mixing of the chlorine which is




provided by hypochlorination.

-------
                         IV.  MATERIALS AND METHODS



                           Experimental Systems



     The  leachate treatment plant, although designed for chemical/physical




treatment followed by biological treatment, was equipped with  sufficient



flexibility to provide for operational evaluation of a variety of  treatment



sequences.  These sequences are each defined  in the following  paragraphs



with reference to Figure 4.  Note  that the final effluent  is disinfected



with sodium hypochlorite prior to  discharqe during the winter  months.



The periods of operation of each system is summarized  in Table 10.  The



principal analysis was conducted during the first two years.   Additional



trials were conducted during the third year.  The flow rate and  raw



leachate quality was sufficiently  different In the third year  to



oftentimes prevent direct comparisons.



     System 1 - Chemical/Physical  followed by Biological Treatment.



System 1  is the basic treatment sequence with lime treatment for metals



removal followed by ammonia stripping and conventional activated sludge.



System la refers to the use of System 1 when the air stripping was not



used, whereas System Ib signifies  that the lagoon was  included in  the



'flow sequence.  System la was tested in the late winter of 1975-76,



and System Ib in the summer of 1976, the winter of 1976-77, the  early




spring of 1977, and the spring and summer of 1978.  During the 1978 test



period, the raw leachate entered the plant via the equalization  pond.




     System 2 - Chemical/Physical  Treatment.  Two subsystems have  been



evaluated.  These, Systems 2a and  2b, consist of lime treatment  either



without or with subsequent removal of ammonia by air stripping.  The




                                 -k7-

-------
                                  TABLE  10


             PERIODS OF OPERATION  OF  LEACHATE TREATMENT SYSTEMS





System                     Period  of  Operation of Full-Scale Units


  la'                       November  15,  1975 through January 12, 1976


  lb+                      June  14,  1976 through April 30, 1977


  lb+                      January 1,  1978  through August 31,  1978

    *
  2a                       November  15,  1975 through January 12, 1976


  2b+                      June  14,  1976 through April 30, 1977


  2bt                      January 1,  1978  through August 31,  1978


  3"                       January 12, 1976 through April 2, 1976


  3+                       May 1,  1977 through August 31, 1977


  4'                        January 12, 1976 through April 2, 1976


  4+                       May 1,  1977 through August 31, 1977
 Neither ammonia lagoon  nor  equalization  pond used.



 Ammonia lagoon used.



 Both ammonia lagoon and equalization  pond  used.
                                 -48-

-------
system without ammonia stripping (System 2a) was evaluated In the winter




of 1975-1976; and System 2b in the summer of 1976, the winter of



1976-1977, early spring of 1977, and the spring and summer of 1978.



The equalization pond was included In this treatment sequence during



the most recent period.



     System 3 - Biological followed by Chemical/Physical Treatment.



This is the reversal of System 1.  This system was studied during the



winter of 1976.  The results  indicated poor treatment efficiency, most




likely due to heavy metal and ammonia toxiclty.  However, it might have



been argued that a sufficient amount of activated sludge had not



developed.  Therefore, System 3 was reevaluated in order to test this



latter hypothesis.  This took place during the late spring and early




summer of 1977.



     System k - Biological Treatment.  This system has been tested, the



results showing poor treatment efficiency.  However, as indicated above,



the performance might have improved if a previously acclimated activated



sludge were available.  Consequently, System 4 was operated and tested



simultaneously with System 3 during the spring and early summer of 1977.



     System 5 - Bench-Scale Testing.   As a supplement to the full-scale



treatment processing, some smaller scale work has been undertaken.  This



effort serves two purposes.   First, it allows the operator to readily



develop operational  guidelines.  For  example, jar tests have been used



to determine proper chemical  dosages.




     The second purpose is to provide an opportunity for evaluating



additional  treatment techniques.   Specifically, bench-scale testing has



been used to evaluate activated carbon treatment  of raw leachate,



                                 -49-

-------
Granular activated carbon has been used |n column studies to obtain



performance characteristics.  The results are discussed in Chapter IV.



                              P roce s s MpnI toring



     An analytical laboratory was established in a trailer located



immediately adjacent to the treatment plant.  The trailer Is outfitted



with the apparatus to perform the analyses Indicated below and Is



environmentally controlled with a heating/air conditioning system.



The need for extensive bench-scale testing and the large number of



analyses needed for process control and monitoring made the on-slte



laboratory mandatory.  The laboratory Is operated by the chemist-operator



employed specifically for this project.



     The chemical analyses performed routinely are presented In Table 11.



These have been selected on the basis of four criteria:  they represent



the most common chemical parameters used in the literature to characterize



landfill leachate; they provide sufficient data to completely evaluate the



unit operations in terms of process and total system efficiency; they are



needed for process control; and they are required to specifically define



the leachate.



     All analyses are performed in accordance with the 13th edition



of Standard Methods, ASTM Standards pt-23, and the 1974 edition


               51-54
of EPA Methods.       The analyses are performed on total samples as



opposed to filtrate samples.  Some preparation of the raw leachate is



required for heavy metals determinations.



     Electrometric techniques are used in the determination of ammonla-N,



dissolved oxygen  (with periodic checks using the Azide Modification of



                                  -50-

-------
                                 TABLE 11



                  ROUTINE LABORATORY CHEMICAL  ANALYSIS

Dally


Item
PH
Chemical oxygen demand
Dissolved oxygen
Mixed liquor suspended solids
Mixed liquor settleable solids
Dissolved solids
Volatile suspended solids
Total residue

Alkal ini ty
Biochemical oxygen demand
Total hardness
Kjeldahl nitrogen
Ammonia nitrogen

Phosphate
Sulfate
Chloride
Total iron
Chromium
Copper
Cadmium
Lead
Mercury
Zinc
Nickel
Ca 1 c I urn
Magnesium
Sod i urn
Potassium



Method

Dlchromate reflux
Electrode
Gooch crucible
Imhoff cbne
Potent fometric
Gooch crucible
Drying crucible
Weekly
Titrimetric (pH k.5)
Probe method
Titrimetric
Titrimetric
Distillation &
Potent iometric
Persulfate digestion
Gravimetric
Titrimetric
AA*
AA
AA
AA
AA
Mercury analyzer
AA
AA
AA
AA
AA
AA
Aperiodic
EPA
Storet
No.

003l»9
00299
70300
50086
00536
00529
00520

001(10
00310
00900
00625

00610
00665
009^5
00940
..
—
--
—
--
—
--
—
--
--
—
—

Detec-
tion
Limit

—
—
--
--
—
—
—

„
—
-.
—

—
—
--
—
0.02
0.02
0.01
0.002
0.05
0.0002
0.005
0.005
0.003
0.005
0.002
0.005

Oil & Grease
Freon extraction
*Atomic Absorption  Spectroscopy
                             -51-

-------
the Winkler lodometric procedure), pH, and dissolved solids.  Atomic



absorption spectroscopy is used for iron, chromium, copper, nickel, zinc,



sodium, cadmium, lead, and potassium.



     A number of sampling points are used in the analysis program.



Routinely, samples are collected of (l) the raw leachate; (2) chemical/



physical sedimentation tank effluent;  (3) ammonia lagoon effluent;



(4) final effluent.   In addition, samples are collected on an irregular



basis from the three  landfill manholes and directly from the individual



treatment units.   In all cases, every effort is made to ensure that a



representative sample is obtained.



     A pilot-scale treatment plant was constructed in order to facilitate



the smaller scale studies.  This pilot plant was built durinq the spring



of 1977.  The basis of its design was to simulate System 1 operation as



it was apparent that this was the most efficient treatment sequence for



this leachate.  Thus, the pilot plant would generate final effluent which



could be used in the bench-scale experiments using granular activated



carbon.  A schematic of the pilot plant is presented in Figure 5.



                          Statistical  Tests



     The following notation is used throughout: n, number of data points;



x, arithmetic mean; and s, standard deviation.  The mean is calculated as


                                   1 N^
                               X = — >  X.
                                   n *-•   i



and the standard deviation as
                               e -     (x - xj)
                                        n-1
where the x. are the n data points,



and the coefficient of variation is



                                  -52-

-------
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                                        -53-

-------
                                 cv-2.
                                      X

The value of the coefficient of variation decreases with decreasing

variabi1ity.

                         Presentation of Results

     A note of caution is placed here for the reader.   As would be

expected in a three year study of this magnitude, a vast array of data

has been collected.  It is not appropriate to present  the entire data

set in this report.  Consequently, many of the tables  presented represent

averages taken over certain specified time periods.  Thus, values given

in different tables are not necessarily comparable.  This is especially

true if the time periods are not identical,   The reader is asked to pay

particular attention to the time periods and to avoid  making comparisons

when these periods differ.
                                 -54-

-------
                        V.  RESULTS AND DISCUSSION



                            P re1i m t nary Resu11s



     Raw Leachate Quality.  A summary of actual leachate quality is shown



in Table 12.  These data are a summary of the entire set of results.  As




is evident from a comparison of Tables 9 and 12, there are significant



differences between the two.  These changes toward increased leachate



strength are seen mainly between the design and actual raw leachate




organic matter, dissolved solids, pH and ammonia.  The biodegradable



organics concentration is three times the design level.  Dissolved



solids are an order of magnitude greater, caused by increased hardness,



organic matter and chloride.  The ammonia concentrations actually



observed have been extremely high and have been a source of operating



problems especially in the biological units.  The factors influencing



this difference between the projected and observed leachate quality




have been discussed in Chapter II.



     Considerable variability In the raw leachate quality has been noted




on a day-to-day basis.  The influent COD data are presented In Figure 6



to show this variability.  (An additional indication is provided by the



coefficient of variation data provided in Table 13, columns 1 and 2.)



It was felt that the raw leachate variability had an adverse Impact on



the efficiency of the subsequent treatment units.  This was because it



was impossible to fine tune the operational  controls as quickly as the



influent quality changed.  This was especially true for the lime dosage



in the heavy metals removal  step.   For this reason, the equalization



pond was constructed.   The effect of the pond  on dampening of the




                                 -55-

-------
                   FIGURE 6.  RAW LEACHATE CHEMICAL OXYGEN  DEMAND

                              (Note change in scale on ordinate)
  !_

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 a
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  25




  20.




  15.




  10-




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     50-
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         DEC.  JAN.  FEB. MAR. APR.  MAY JUNE JULY AUG.SEPT.OCT.NOV.

           1976
         i    I     I    T    I     <    i     r    r    i     I    I

         DEC. JAN. FEB. MAR. APR.  MAY JUNE JULY  AUG.SEPT.OCT.NOV.

           1977
                                -56-

-------
























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-57-

-------
                       TABLE 13




EFFECT OF EQUALIZATION POND ON RAW LEACHATE VARIABILITY

Coefficients of Variation

Unequal ized
Raw Leachate
Equal ized
Raw Leachate
Project Year

Alkalinity, as CaCO_
Ammonia-N
BOD
Cadmi urn
Calcium
Chloride
Chromium
COD
Copper
Di ssol ved Sol ids
Hardness, as CaCO,
1 ron
Kjeldahl-N
Lead
Magnes ium
Mercury
Nickel
PH
Phosphates
Potassium
Sod i urn
Sylfate
Suspended Sol ids
Zinc
First Second
0.23 0.21
1.14 0.21
0.60 0.72
0.39 0.80
0.31 0.57
0.58 0.16
0.56 0.32
0.40 0.66
0.81 1.00
0.24 0.58
1.02 0.48
0.65 0.77
1.23 0.19
0.60 0.68
0.47 0.32
0.90 1.04
0.33 0.97
0.64 2.33
0.63 0.74
0.32 0.21
0.32 0.31
0.90 2.10
0.65 1.32
0.65 0.62
Third
0.26
0.33
0.50
0.73
0.57
0.30
0.49
0.25
0.67
0.16
0.41
0.33
0.39
0.53
0.29
1.73
0.52
--
0.84
0.19
0.16
0.71
0.64
0.68
                      -58-

-------
influent quality is impossible to ascertain because raw leachate samples

were not collected after pond startup.  Rather, the influent samples were

taken from the pond.  As an approximate indicator of the degree of

attained equalization, Table 13 was constructed.  This compares the

coefficients of variation for each parameter during the three project

years.  As shown in Table 13, the variability decreased for one-half

of the parameters and was approximately the same for several others.

This is taken as indirect evidence of the efficiency of equalization.

     Lime Dosage.  Jar tests were carried out }n the laboratory in order

to determine proper dosages for the lime treatment unit.  In the first

series of tests, three types of 1iipe were monitored for their ability

to raise the pH of raw leachate to 10,0,  The limes used were high

magnesium lime, high calcium quick 1Jme and high calcium hydrated lime.

The results may be summarized as:

                                                   Dosage
                                            Ib/1000 gal   kg/cu m

          High Magnesium Lime                    125        15
          High Calcium Quick Lime                 52         6.2
          High Calcium Hydrated Lime              50         6.0

It is economically impractical  to use the high magnesium because its

properties are such that to raise the pH to 10.5 requires 30 kg per

cu m (250 Ib per 1000 gal).

     Required dosages to obtain pH 10.0 are nearly identical for both

types of high calcium lime.   For pH greater than 10.0,  the high calcium

quick lime becomes more efficient  and hence Is desirable economically.

However, the slaking characteristics of the quick lime  have caused

problems with pumping the resultant slurry so that this lime cannot be

                                  -59-

-------
used with the available lime feed system.  On the other hand, the hydrated



lime does not offer such problems, and consequently, the high calcium



hydrated lime is being used.




     Sulfuric Acid Dosage.   The amount of sulfuric acid required to lower



the clarifier effluent pH to 6.5 has been determined.  To do this,



approximately 0.6 ml  of concentrated sulfuric acid per liter leachate




(0.6 gal/1000 gal) is required.  The actual  dosages used are presented




later in this chapter as part of treatment costs.



     Phosphoric Acid  Dosage.  The need for a phosphoric acid supplement



became apparent from  three lines of evidence:  (a) very low phosphate



levels in the chemical/physical effluent; (b) unrealistically low values



obtained in the biochemical  oxygen demand test; and (c) poor biological



treatment performance following the chemical/physical process.   These



points all  indicated  that the chemical/physical treatment effluent is



phosphorus deficient, and that, if biological treatment is to follow,  it



must be supplemented  with phosphorus.  Additional evidence was collected



by performing a series of BOD_ tests in which a variable amount of



phosphorus supplement was added to the bottles.   It was observed that



the BOD increased with the amount of phosphorus.  In addition, bench



scale tests Indicated greater activated sludge production when o-phosphate




was added.   Thus, it  has been concluded that orthophosphate, as



phosphoric acid, should be added to form a nutrient supplement.




     Additional experiments were performed to address the phosphate



issue.  These were conducted using the pilot scale unit shown In Figure



5.  The unit was operated with and without an addition of phosphorus.



                                 -60-

-------
Raw leachate COD was 4528 mg per  liter during the no addition run, and




4823 and 21406 mg per liter during the two runs receiving a phosphate




supplement.  The lime clarifier effluent COD values for these runs were




3926, 4062 and 18121, respectively, and the average fractions of COD




removed during biological treatment were 0.711, 0.811, and 0.762,




respectively.  These results indicate that the removal efficiency of




acclimated activated sludge can be improved by the addition of phosphorus,




and that the removals were acceptable when the effluent phosphate




concentration is 1 to 2 mg per liter as P.




     The preliminary calculation of phosphoric acid dosage has been made




on the basis of providing a ratio of BQD:N;P of 100:5:1.  This is




approximately 4-6 liter  (1-1.5 gal) phosphoric acid per day.  More




recently, however, the criterion  is to add phosphoric acid so that




there is measurable o-phosphate in the bio-unit effluent.  This amounts




to about 3.8 liter (1 gal) of phosphoric acid per day.




           System 1  - Physical/Chemical  Plus Activated Sludge




     System 1 consists of chemical/physical treatment followed by




activated sludge.  The early attempts (winter and spring 1976) to develop



an activated sludge culture were not successful.   As discussed In




connection with Systems 3 and 4, phosphorus limitation and ammonia




toxicity inhibited these efforts.   These two difficulties were overcome




by the addition of phosphoric acid as a  neutralizing agent for the lime




treatment effluent and by the use of air stripping of ammonia.  System




1   was successful only after the implementation of these measures and,




as a result, this discussion is limited  to the time period after




implementation.



                                  -61-

-------
       The  BOD,  COD, and  ammonia-N data  showed a dramatic  improvement  in




  treatment efficiency during and after  August, 1976.  Approximately four



  weeks had been needed  to  develop the activated sludge microorganisms to



  the  point where they were capable of rapid growth at the expense of  the



  leachate  substrate.  A  similar time sequence was observed  in  1978



  during a  re-test of System 1.  Table lA  shows the results  following  the



  successful  adaptations  of the activated  sludge.  The starting dates  for



  analysis  of these data  were chosen at  the points at which  the activated



  sludge had become fully acclimated in  terms of ammonia-N,  BOD and COD



  removals.   The time periods are August 1, 1976 to May 1, 1977 and July



  1, 1978 to August 31,  1978,



       The  results presented in Table 14 demonstrate the high level of



  treatment efficiency attainable with System 1.  This treatment system



  achieved  removals during  the  1976-77 trial of approximately eighty-nine



  percent or more for ammonia,  BOD, COD, suspended solids, and  iron; and



  greater than two-thirds for alkalinity,  hardness, kjeldahl nitrogen,



  copper, chromium, magnesium,  cadmium,  lead, and zinc.  Relatively poor



  removals  of mercury were  achieved with System #1.  The fairly low removals



•  of nickel  may  be related  to the relatively low hydrogen  ion concentrations,



  Based on  theoretical considerations of the solubility of nickel hydroxide,



  the  nickel  concentration  in the effluent should be on the  order of 0,01



  mg/1   , as opposed to observed average of 0,75 mg/1,  This observation



  is perhaps also due to  the formation of  nickel complexes with unknown



  chelating agents within the landfill.  Thus, we are able to see removals



  as a  function  of clarlfier pH, and this  opens the possibility that the



                                  -62-

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-63-

-------
operator can control pH as a method of differentially affecting




effluent heavy metals concentration.



     The results observed with phosphates and sulfates should be noted.



The concentration of phosphates and sulfates increase during the course




of treatment because of the addition of sulfuric and phosphoric acids



as neutralizing agents.  Initially, both acids were used In excess in



order to encourage the growth of the activated sludge microorganisms.




That is, the goal was to provide a very favorable environment in terms



of both pH and the nutrient phosphorus.  However, following the



successful acclimation of the activated sludge, the addition of sulfuric



acid practically stopped while that of the phosphoric acid was




drastically cut back.  Neutralization was not needed because of the



recarbonation effect of aeration in the lagoon.  The final  criterion




for phosphoric acid addition was to provide just enough to satisfy



the microorganisms' demand as indicated by an effluent concentration of



about 1 mg/liter.  That is, the criterion was to add enough H,PO,  so



that there is residual phosphorus (1 mg/liter)  in the effluent.   This



level is one to two orders of magnitude greater than the amount In



the lime clarifier effluent.



     The difficulties in obtaining a healthy culture of activated sludge



were overcome.  The operating experience indicated that the earlier



problems were in fact due to ammonia toxiclty and phosphorus limitation.



The ammonia stripping lagoon maintained the concentration of this



inhibitor below toxic levels.  The mean and standard deviation of the



lagoon effluent ammonia concentration were such that 95 percent of the



                                 -6k-

-------
time, the feed to the activated sludge unit was less than k23 mg




NH,-N/liter.  The corresponding raw leachate concentration was 1072




mg NH,-N/liter.  (Similar results were obtained during the other test




period.  Pooling all the data, the t]  standard deviation interval for




the lagoon effluent was 203 to 6^1 mg per liter, whereas, for the raw




leachate, the mean was 1,001 mg NH,-N per liter and the standard




deviation, 10^9 mg per liter.)   Thus, the lagoon functioned to minimize




the shock loading effect of inhibitory ammonia concentrations.  This in




turn provided an opportunity for the development of microorganisms




capable of extracting carbonaceous BOD.  As this group became established,




organic concentrations in the mixed liquor were reduced and this created




conditions suitable for the development of nitrifying organisms.  Growth




of these groups of microorganisms has resulted in the low effluent




concentrations of both BOD and ammonia.




     As seen in Table ]k, a considerable change in alkalinity occurs




during biological treatment.  There are two main mechanisms by which




this occurs.  First, the aeration causes some removal of gaseous




carbon dioxide, resulting in a shift of the carbonate equilibria and a



change in total bicarbonate alkalinity,  |t Is probable, however, that




in this case, nitrification has a more profound errect on alkalinity.




As a result of nitrification,  alkalinity is consumed and carbon dioxide




is produced.   Neglecting the effect of biomass synthesis, the




theoretical  value is 7.1** mg alkalinity as CaCO, destroyed per mg




NH.-N oxidized.  In this study a ratio of A,*»6 mg alkalinity per mg




NH.-N removed was observed after the development of the activated sludge




culture.   This is in excellent agreement with the theoretical  value if




                                -65-

-------
one considers that the observed value includes the effects of biomass



growth and ammonia stripping in the bjo-units as well as shifting



chemical equilibria in addition to those of nitrification.  These



conclusions are drawn from the data presented in Tables 15 (Column 7)



and 20 (Column 12) which represent activated sludge effluent and



influent values, respectively.




     System 1 was re-tested from January 1, 1978 through August 31, 1978,



following completion of the equalization pond,  Cold weather, the extreme



strength of the process influent,  and the high flows Inhibited



development of an activated sludge until April,  1978.  The sludge did not



become acclimated until July 1, 1978, following a process change from



parallel to series deployment of the aeration tank-secondary clarifier



system.  A schematic is shown in Figure 7.   The change was undertaken



in an effort to gain greater use of the available aeration capacity.



This was deemed necessary because of the tremendous process loadings



observed in 1978 (Table 35).



     The acclimated activated sludge performed well.  The average flow



into the biological- units was 10,000 gpd, whereas, during the same



period, the raw leachate flow was 50,000 gpd.  The difference is due



to the extreme strength of the leachate which inhibited the activated




sludge so that only a portion of the flow could be treated biologically,



(The entire flow was treated in the chemical/physical section of the



plant during this period.)



     The data for the re-test of System 1 are presented in Table 14,



and a summary of both tests appears in Table 15,  The results Indicate




                                  -66-

-------
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-68-

-------
that System 1  is able to handle large loading rates, and to achieve



high removal efficiencies.  Data collected during the warm weather



months  (August 1, 1976 to December 1, 1976 and July 1, 1978 to August



31, 1978) have been analyzed separatelyi  These data show that System  1



can produce an effluent of sufficient quality to meet the final effluent



criteria  (Table 16).



     Approximately equivalent results are obtained using the biological




reactors  in either the parallel (1976"77) or the series (1978) mode



(Table  17).  In terms of percent removal efficiency, the series and



parallel operations provided approximately equal performance with



respect to BOD and COD.  Removals of ammonia-N were much greater with



•the series operation.  This is due to the localization of NH.-N removal



in the  second tank following BOD oxidation in the first,  (Note that the




average flow during the series test was 10010 gpd, whereas during the



parallel test, the flow was 21034 gpd (Table 1*0,



     Operational Comments.   Operating problems were encountered !n the



biological treatment unit.  The most serious of these was a tendency of



solids  to float in the secondary clarifier.  The result of this has been



a decreased ability to achieve the expected level of solids separation.



The presence of the floating sludge has been investigated and is



characterized as being the result of three separate and distinct causes;



flotation, turbulence and denitrification.  It was apparent that there



was some carryover of floating materials to the clarifier from the



aeration tank.   The leachate contains considerable amounts of surface



active materials capable of flotation, and thjs contributes significantly



                                 -69-

-------
                              TABLE 16




                 WARM WEATHER  OPERATION  OF  SYSTEM  1

Parameter
Ammonia-N
BOD
Cadmium
Chromium
Copper
1 ron
Lead
Mercury
Zinc
Effluent Concentration
8.7
75.8
0.02
0.06
0.10
1.22
0.11
O.OOA5
0.37
Permit Standard
35.0
100.0
0.02
0.10
0.20
7.0
0.10
0.01
0.60

"Time periods included are 8/1/76 to 12/1/76 and  7/1/78  to 8/31/76.





 All units are mg per liter.
                                 -70-

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to the carryover phenomenon.  The original scum control device was not




capable of handling the unexpectedly large amount of these materials.




At the same time, an excessive amount of turbulence existed in the




secondary clarifier.




     The reduction of solids separation efficiency was compounded by a




propensity of the activated sludge to become anaerobic and to rise in




the clarifier due to denitrification.  This is seen clearly when one




follows closely the settleable solids test,  At first, the sludge




settles properly with a dense sludge layer overlain by a clear




supernatant containing little turbidity, so that at the end of 30 to 45




minutes the settleable solids are about 300 mg/liter.   If the test is




continued for another hour, the sludge comes to the surface in typical




rising sludge fashion.  This is not a case of filamentous bulking as




indicated by microscopic examination, the clear supernatant observed




in the settleable solids test, and the sludge volume index of approximately




80 ml/g.  Another indication of anaerobic denitrification as the cause




of the floating sludge is the repeated observation of very low DO levels




in the clarifier.  This problem was accentuated when a portion of the




plant aeration capacity was diverted to the ammonia-stripping lagoon.




     These problems were resolved by minor design and operational changes.




The installation of a more efficient scum removal system has ameliorated




the floating sludge problem.  Additional baffles were used to control




the turbulence in the clarifier.  Extra aeration capacity was Installed




to maintain appropriate concentrations of dissolved oxygen.




     Cost Data.  Costs incurred during the operation of the biological




units are indicated in Table 18.  The operation and maintenance costs




                                 -72-

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-73-

-------
are shown for the operational periods following acclimation: August 1,



1976 to May 1, 1977 and July 1, 197b to August 31, 1978.  The costs



include those for NaOH, added to the ammonia lagoon to enhance ammonia



stripping, and NaOCl, added to the final effluent to provide disinfection




prior to discharge and to provide ammonia oxidation during the cold



months.




     The data indicate a cost of $2,99 per thousand gallons treated.



The high power costs reflect the demand for electricity for leachate



pumping, effluent pumping, and maintenance of the laboratory in addition



to the requirements for actual treatment.



     The costs during the re-test of System 1 warrant discussion.  During



this period, the flow through the System 2 section of the plant was



approximately 50,000 gpd, while the flow through the activated sludge



units was 10,010 gpd.  The dosages of chemicals and the costs of treatment



shown in Table 18 take account of  these differences.  Thus the dosage



for lime is based on 50,000 gpd, whereas that for NaOCl is based on 10,010



gpd.  The costs during the re-test are somewhat higher than anticipated.



This results from two causes.  First, the final effluent was chlorinated



during the entire 1978 test period prior to land disposal.  The effluent



was chlorinated for a relatively small portion of the time during the



earlier test.   The second reason is that lime and sulfuric acid dosages




were greater during the re-test.  This was because more lime was added



to enhance ammonia removals in the ammonia lagoon, and, as a consequence,




sulfuric acid dosages were also high.  The labor requirement is




approximately 20 man-hours per week,



                                 -74-

-------
                                Nitrification



     Nitrification  is becoming a standard and widely used wastewater



treatment process.   It  is the aerobic microbiological conversion of



ammonia nitrogen to nitrate nitrogen.  As such, nitrification is




applied In situations where the pollution potential of ammonia  Is



severe, especially  in comparison with nitrate nitrogen.  The adverse



impacts associated with high concentrations of ammonia are promotion



of eutrophication;  toxicity, especially as a function of pH, to aquatic




organisms; Interference with chlorinatlon due to reactions leading to



the formation of chloramines; and, depletion of dissolved oxygen In



receiving streams concomitant with the oxidation of ammonia to nitrate.



As a result of considerations such as these, effluent ammonia standards



are often established by regulatory agencies.




     The nitrifying bacteria, typified by Nitrosomanas and Nitrobacter,



oxidize ammonia to nitrite and nitrite to nitrate, respectively.  These



microorganisms are chemoautotrophs, and the nitrogen oxidation reactions



provide the bacteria with a source of energy.  A stoichiometric



relationship can be written for the overall synthesis of biomass and



oxidation of ammonia and nitrite as follows:



NH^* + 1.83 02 + 1.98 HCO ~ - 0.020 C H N02 + 1.041 H20 + 0.98 NO" +



1.88 H2C03                                                           (1)




Nitrifying bacterial biomass is represented as C,-H7N02.  Eqn (l)



indicates that the theoretical  cellular yield Is 0.16 g biomass per g



NH.-N completely oxidized.   (Also evident from Eqn (1) is the destruction




of 7.1  g alkalinity per g NH.-N oxidized, as discussed previously,)



                                  -75-

-------
     Much of the literature concerned with waste treatment applications



of nitrification has been devoted to municipal sewage.  A recently



published design manual has summarized this literature.    The ammonia



content of municipal sewage is characteristically on the order of twenty



to forty mg per liter.  Occasionally, however, Industrial wastes with


                                           58-61
much higher concentrations are encountered.       In this section of



the report, data are presented and discussed showing that nitrification



Is inhibited at high substrate concentrations.  Substrate Inhibition



such as described herein must be considered during both the design and



operation of biological treatment plants intended for nitrification.



     Boon and Laudelot have investigated the nitrite oxidizing bacterium,


                         62
Njtrobacter winogradskyi.    They have shown that the rate of nitrite



oxidation,which is  inhibited by nitrite, is a function of the nitrite



concentration which can be expressed as
                                 K
                                                                    (2)
                                         -
where y is the specific growth rate, time  ;  y, the maximum specific



growth rate in the absence of inhibition, time  ;  S, the limiting



substrate concentration, mass per unit volume; K ,  saturation constant,



numerically equal to the lowest concentration of substrate at which y


               /\

is one-half of y, mass per unit volume; K. ,  Inhibition constant,



numerically equal to the highest concentration of substrate at which

                 A

y is one-half of y, mass per unit volume,



     The assumption of neglecting substrate inhibition Is not particularly



misleading at low substrate concentrations.   This Is because the third



                                  -76-

-------
term in the denominator of Eqn (2) becomes much less than the second



term.  As a result, as the value of S is reduced, Eqn (_2) approaches



the more conventional Monod expression
                                    S + K
                                         s
                                                                     (3)
This equation is a reasonable description of nitrification at low values



of S, as are encountered In municipal sewage treatment applications.



Equation (2) becomes increasingly invalid as S increases, as Jn the



treatment of leachate.   The purpose of this section is to consider



nitrification at high ammonia concentrations, and to discuss the results



in terms of designing and operating nitrification and leachate treatment



faci1i t ies.



     The data were collected during the period August 1, 1976 to May 1,



1977.  The fraction of nitrifying bacteria in the biomass has been



calculated directly from the amounts of BOD and NH.-N oxidized, and from



the estimated yields of the two groups of oxidizers.  The assumed yield



values  are 0.15 g biomass per g nitrogen oxfdized-day, and 0.55 g biomass



per g BOD oxidized-day.



     More detailed results of the removal of ammonia in the bio-units



are given  in Table 19.   The concentration of NH.-N is calculated from



the equation,



                          NH  + H-0 + NH^ + H20                    (4)




using the observed temperature to determine the equilibrium constant,



the observed pH and the analytical results of the sum of NH.-N plus



NH_-N (denoted as NT in Table 19).  Three removals are given in Table 19.



                                  -77-

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-78-

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                                                                          -79-

-------
The first, R., Is the percent removal efficiency based on influent and



effluent concentrations; the second, R-, is the fraction of N_ which



is oxidized in the aeration tank; and R_, is the specific oxidation



rate.   The units of R_ are g nitrogen oxidized per g biomass-day, and



it is  calculated as the daily mass of nitrogen oxidized divided by the



biomass.  R, is determined using the fraction of nitrlfiers In the



biological solids, expressed as volatile suspended solids.




     As indicated in Table 19 the overall removal of ammonia in the




activated sludge units was considerable.  Although this is primarily



due to the microblal process of nitrification, the physical stripping



of ammonia caused by aeration accounts for some or the removal.  It Is



the purpose of this discussion to consider the factors affecting the



ammonia converted by nitrification.  It  is apparent from Table 19 that



a profound inhibitory effect was placed on the specific oxidation rate.



as a result of extreme winter temperatures.  Since the result was to



decimate the nitrifying population, the following discussion is limited



to the data obtained up to 25 January 1977.  Data are not included from



the third year of operation because of changes in flow rates and loading



rates.



     No simple pattern could be perceived which related nitrification



measured as the specific oxidation rate  (R-, Table 19) with the




concentration of organic matter.  Nitrification did not occur when the



reactor BODj. exceeded one gram per liter and when the COD exceeded three




grams  per liter.  However, subsequent to the formation of a culture of



acclimated activated sludge, capable of nitrification and organics



oxidation, there was no consistent relationship between the specific



                                  -80-

-------
oxidation rate and the concentration of organic matter  in the reactor.



Nitrification proceeded even though the activated sludge influent



concentration of BOD- and COD averaged 3564 and 6481 mg per liter,



respectively.  This was true when the ammonia content of the bio-unit



influent did not exceed 300 mg per liter.  At higher ammonia levels,



the toxicity of ammonia predominated and very little oxidation of either



organ ics or ammonia occurred.



     It is reasonable to expect some inhibition due to the elevated
levels of BODr and COD recorded in Table 19,  The nitrifers, such as



Nitrosomonas and Nj trobacter , are chemol I thotrophs, i.e., they are



autotrophs, and their carbon source is  Inorganic.  These bacteria are



especially sensitive to organics in pure culture.  Certain heterotrophic



bacteria, fungi, and actinomycetes are capable of performing



nitrification,  '   although it is generally believed that the rate



of heterotrophic nitrification  is  much less than that of the autotrophic



nitrifiers.    The sensitivity of these organisms to organics is



presumably much less than it is for the autotrophs.  Wild e t a 1 .



observed no effect of BOD, in the  range of 5-110 mg per liter, on the



rate of nitrification in activated sludge processes.



     The effect of temperature  on  the specific oxidation rate Is shown



in Figure 8.   This curve agrees well  with curves developed and presented


                                                68
recently by the Environmental  Protection Agency.    The curve has been



fitted in the least squares sense  and the equation of the line Is




                           R3 „ Xe"E/RT                             (5)




                                 -81-

-------
 z
 o
                                 I

                                 a
                                 M
                                 •

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— LL. O I-
LuOHg

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                                 U»
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    OL

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 (£. =>

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                                                                                       aT

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                                             -82-

-------
          where, R- * specific oxidation rate, day
                                9    -1
                 X  =* 2.175 x 10  day   w Arrhenius frequency factor
                 E  * activation energy • 123^7 cal/mole
                 R  - gas constant « 1.99 cal/mole-K
                 T  = temperature, K
The curve of Figure 8 Is somewhat lower than the theoretical one
developed by the EPA,   and this is most likely due to an inhibitory
effect of some wastewater fraction such as heavy metals, organjcs, and
substrate.
     A number of values for E have been reported in the literature.
Wong-Chong and Loehr presented data showing the variation of E with
pH.    Their results indicated that for the ammonia oxidation, the value
of E ranges from 16 to 21.6 K cal per g mole.  Sutton ej^ a_1_. state that
E is a function of the treatment mode, and in particular of the staging
of the biological units, and the solids retention time.    For single
stage units, such as this one (August 1, 1976 - May 1, 1977), they report
that the values of E are 25.1, 21.25, and 11.9 k cal/g mole for solids
retention times  (SRT) of k, 7, and 10 days, respectively.  The figures
refer to the overall nitrification process.  The last number is of
particular importance since an SRT of ten days is considered to be the
                                         72                             7
minimum needed for thorough nitrification   (although Mutton and LaRocca
                                                        jL
considered thirty days to be more reasonable, and others   consider three
to four days as the minimum needed to ensure successful nitrification).
The value of 12350 cal  per g mole obtained here is in good agreement with
that of Sutton et a I.75

                                 -83-

-------
     A number of factors were investigated for potential inhibition of

nitrification.  As discussed above, there Is no consistent observed

effect of organic matter, measured as BOD,, and COD, on nitrification.

However, based on the literature,   it is probable that some of the

inhibition noted above results from the relatively high BQD and COD

concentrations in the aeration tank.  The heavy metals are another

likely source of inhibition, although an obvious relationship was not

observed.  Average heavy metals concentrations in the aeration tank

are listed in Tables 14 and 15 as effluent values,

     The clearest reason for the observed inhibition is that increasing

concentrations of substrate are the cause.  This is shown in Figure 9,

where the data show a reasonable fit to the classic substrate inhibition

model.  The model is based on the Hajdane   mechanism for the substrate

inhibition of enzymes, and is expressed here as
                                      /»
                                      Ri
                             R, - 	£	                       C6)
                              3   1 + ^s •*• i
                                      s    KI

                                             -1
where R, is the specific oxidation rate, day   ; R~ is the maximum

specific oxidation rate which would be obtained in the absence of

substrate inhibition, day  ; K  is the saturation constant; and, K. is

the inhibition constant.  K  and K. are numerically equal to the higher

and lower substrate concentrations, respectively, at which R, equals
            A
one-half of R_.

     The curve in Figure 9 has been developed using a quasi-least squares

procedure and Lineweaver-Burke plots to evaluate the kinetic constants,

                                  -8k-

-------
o

h-
< LU
O \-

U. <2

o: z
h- O
 O —
    X
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 — u.
 m —
 — o
 X LU
 Z O.
 — CO

 LU LU
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 DC
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 CO —
 m
 =>  t*t
 CO OC.
en
LU
cz:
                                                                                         o
                                                                                         o
                                                                                         
-------
The equation used to generate the line is
                           R, •   3'5°                              (7)
                                          *•
indicating that the value of R, Is 3.5 day  ,  K  is k.O mg per liter,



and K. is 36 mg per liter.



     Figure 10 shows a Michael is-Menton plot of the data obtained at




the lower concentrations.  These values correspond to the situation



encountered in the treatment of domestic sewage, and this figure therefore


                                           78
resembles the type curve usually presented,    |n the treatment of



industrial wastes where the Influent ammonia-N may be much higher, it



will be necessary to consider the substrate inhibition of nitrification,



It should be mentioned that the nature of the  situation, I.e., a full



scale plant treating a variable Influent, with differences in pH,



temperature, and other operating variables, contributes to the scatter



of the data observed in Figures 9 and 10,



     In the excellent review prepared by Focht and Chang, much of the


                                                       79
literature regarding nitrification has been summarized.    They report



that the saturation constant for the Michael is-Menton model Is in the



range of one to ten mg N per liter for ammonium oxidation, and five to




nine mg N per liter for the conversion of nitrite.  Poduska and Andrews




state that the saturation constants for Nltrosomonas and NItrobacter



are approximately one mg per liter for full scale activated sludge



systems.    The value of four mg N per liter reported here Is consistent




with these data.



                                 -86-

-------
 D_ Z
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 co i—
 z <
 O Q

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 < O
 t£.
 I- O

 LU U-
 O -
 Z O
 O LU
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O Z
-I O
O I-
O I-
UJ CO LU
U- OQ H-
Li_ 13 <
LU co o:
                                                                        + 1
                        l-
                           Aep  '
               -87-

-------
     Focht and Chang also state that the first observation of substrate



inhibition in nitrification was made in tne early studies of Meyerhof



who showed that Nitrosomonas and Nitrobacter are inhibited at



concentrations of NH.-N and NCL-N exceeding 60 and 350 mg per liter,


             8l
respectively.    Wild ££ aj_. found no evidence for Inhibition due to


                                                  82
ammonia in the range of six to sixty mg per liter.    Focht and Chang



also point out that end product Inhibition has been demonstrated with

                                  go

both Ni trosomonas and Nitrobacter.    This refers to the situation in



which accumulated nitrate or nitrite inhibits further nitrification,



     A number of Investigators have reported that inhibition of


                                                                84*-88
nitrification is due to ammonla-N and to unionized nitrous acid,



Verstraete et^ aj_. recommend that startup of nitrification units treating



highly nitrogenous wastes must consist of a gradual increase In the



nitrogen loading In order to avoid the deleterious effects of these


                                  89
undissociated species of nitrogen.    The data shown In Table 19 have



been examined in this light in order to assess nitrification inhibition



which could be attributed to the free ammonia concentration.  When



this is done, however, it is observed that there is no relationship



between the specific oxidation rate and the concentration of free



ammonia.  In this respect, the results of this study are In conflict



with those cited above, and the question merits further study,



     Kholdebarin and Oertli have reported recently their studies of



batch growth nitrification.    They observed that the Ionized NH^-N has



a stimulating effect on nitrite oxidation,  In the present study,



NH.-N was observed to exert an inhibitory effect.  As shown in Figure 9,

-------
the effect is not profound until the concentration exceeds ten to
twenty mg NH.-N per liter.  The ammonium ion levels used by Kholdebarin
and Oertl I were 2,8 mg N per liter, and in one experlenient, 28 mg N per
      91                         +
liter.    Thus, assuming that NH.-N inhibits nitrification, the
experiments of Kholdebarin and Oertli must be performed at higher
concentrations in order to be comparable with the results presented here.
     The approach which has been followed here has been to attempt to
simplify an exceedingly complex microbial process.  The conversion of
ammonia has been considered the rate limiting step, and has received
primary attention.  The maximum growth rate of Njtrobacter is larger
than that of Nitrosomonas and the value of the saturation constants
is approximately the same.  Thus, nitrite is oxidized more quickly than
is the ammonia, and this forms the basis of the above assumption.
Certain aspects of the inhibition of nitrification have not been
considered.  Examples are product inhibition due to nitrite and nitrate,
and the non-competitive inhibitory effect of nitrous acid.  A third area
of simplification is that the environmental factors are quite variable
at the leachate treatment plant, due to influent quality and quantity
changes.
     It is contended that this approach Is justified because of the
complexity of full-scale operation.  The value is that nitrification is
viewed from the overall perspective, and it is seen that substrate
inhibition is a phenomenon operating In this system.  This knowledge can
serve as a guiae in both the design and operation of nitrification
                                                               92
systems, and can ultimately be incorporated within steady-state   and
       93
dynamic   models of the process.
                                 -89-

-------
     Summary.  The rate of nitrification,  as expressed as the specific

oxidation rate, follows the van't-Hoff Arrhenius relationship which

indicates that the activation energy is approximately 12350 cal  per mole,
                                                    q    _ i
and that the Arrhenius frequency factor is 2.18 x 10  day  .   The data

indicate that substrate inhibition due to  ammonium ion concentration

occurs in this system.  This relationship  has been expressed as  a

Haldane inhibition model in which the maximum specific oxidation rate


is 3-5 g N oxidized per g biomass day, K  Is k mg per liter,  and K. is

36 mg per 1iter.

                  System 2.  Chemical/Physical Treatment


     This discussion is presented in two parts.  The first consists of

the results associated only with lime treatment, and the second  includes

the ammonia stripping lagoon.  Full-scale  data were collected for System

2a without the lagoon during the periods November 15, 1975 to January

12, 1976 and June 1^, 1976 to April  30, 1977, all dates inclusive.  The

results of this phase of the treatment plant operation are summarized

in Table 20, columns 1-7.  The distinction between the two periods permits

an assessment of the performance of the ammonia lagoon.

     Table 20 summarizes the changes in each parameter attributable to

the lime treatment.   In very approximate terms, the lime precipitation/

clarification sequence, System 2a, removed (see Column 7, Table  20)

one-quarter of the nitrogen; one-third of  the dissolved solids;  one-half

of the organic matter, hardness and alkalinity; three-quarters of the

suspended solids; and ninety percent of the phosphates.  The removal of

heavy metals was over one-half of the mercury and cadmium; two-thirds

                                 -90-

-------



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-91-

-------
of the chromium, nickel, and lead; three-quarters of the copper and




over ninety percent of the iron and zinc.  The increase in sulfate is




due primarily to contaminants in the chemicals, although oxidation of




sulfides may contribute somewhat,   in other words, this section of the




system performed as expected in pre-treating the leachate prior to




biological treatment.




     The results of the overall chemical/physical section including the




ammonia lagoon (System 2b) are listed in Table 20 (Columns 8-lA) which




shows the basic statistical relationships.  Treatment performance in




terms of percent removal efficiency of the lagoon alone and in




conjunction with lime treatment are also seen in Table 20.  The primary




goal of the lagoon was achieved as the concentration of ammonia-N was




reduced to a level which was found to be tolerable for purposes of




biological waste treatment.  A splash plate, which was installed to




promote air/water contact, did not produce an appreciable effect on




lagoon ammonia removals, and was therefore removed.




     Many parameters other than ammonia were altered while in the lagoon




(see Table 21).  There was some stabilization of organic matter as shown




by the reductions in BOD, COD and dissolved solids.   This was mediated




by biochemical processes and the increase in suspended solids is related




to the growth of microorganisms.  The reduction  in alkalinity is due to




aeration effects although nitrification reactions may partially contribute




to the observation.  The reduction of hardness, calcium and magnesium are




related and may be explained by the formation of calcium and magnesium




carbonates.   In this form, these would not be detected by the usual




tests.  Most of the other changes noted in the lagoon effluent vs. lagoon




                                 -92-

-------
                               TABLE 21

         SUMMARY OF EFFECTS OF CHEMICAL/PHYSICAL TREATMENT*




Suspended Sol ids
Dissolved Sol ids
COD
BOD5
Alkal ini ty
Hardness
Magnes ium
Calcium
Chloride
Sulfate
Phosphate
Ammon ia-N
Kjeldahl-N
Sod i urn
Potass ium
Cadmi um
Chromi um
Copper
1 ron
Nickel
Lead
Zinc
Mercury
pH


Influent
1044
13029
18553
10907
5404
4652
453
818
4240
462
2.74
1001
984
1354
961
0.086
0.28
0.39
312
1.55
0.67
21
0.007
6.85

Lime Treatment
Effluent+
239
7972
7188
5265
3052
2461
209
696
3516
426
0.26
890
867
830
613
0.03
0.09
0.10
3.8
0.57
0.24
0.61
0.003
8.46
Ammon i a
Lagoon
Effluent*
288
4650
8793
3600
2374
1587
117
424
2669
525
0.27
412
349
956
572
0.04
0.08
0.27
5.6
0.73
0.23
0.85
0.010
8.66

"The influent data are those collected during the entire operational
 period, whereas the effluent figures refer to those periods when the
 specific units were operating.

+A1 1  units are mg/liter except pH which is expressed in pH units.

                                 -93-

-------
Influent comparison are due to the limitations of the experimental



techniques or to the radically variable nature of the raw leachate.



     The overall treatment efficiency of the complete chemical/physical



section is summarized in Table 20.  These data do not include the effect



of neutralization.   The values in the last column (Column ]k) represent




removal efficiencies for the lime precipitation/sedimentation/ammonia



stripping sequence.  In terms of organic matter, 69.1 and 52.6 percent




of the BOD and COD are removed, respectively.  Approximately fifty to



sixty percent of the ammonia-N, total nitrogen, suspended solids,



alkalinity and hardness are removed.  The removal of metals was as



follows: 38-54 percent of copper, nickel and mercury; 59-68 percent of



chromium, cadmium,  and lead; 95 percent of zinc; and 98 percent of iron.



     Chian and Dewalle have formed an hypothesis, which is summarized  in


                                                     94

Table 6, concerning the treatability of raw leachate.    The BOD/COD



ratio observed in this study (Column 2 of Table 20)  of the leachate was



0.62 and the average COD was 16618 mg/liter.  This is also shown in



Column 9 of Table 20, in which it is seen that the ratio is 0.63, and



the average COD, 18566 mg/liter.   Thus, according to Chian and DeWalle,



the leachate treatment efficiency obtainable with lime should be fair.



In this study (Column 7, Table 20) the lime treatment efficiency for




BOD and COD has been about fifty percent.  Hence, in terms of the removal


                                                           95
of organics, the Chian and DeWalle hypothesis  is supported.    However,



it must be mentioned that their hypothesis did not include the removal




of heavy metals, and that the lime treated heavy metal removals have been



good to excellent at this facility.



                                   -Sk-

-------
     An additional effect of the ammonia stripping lagoon Is the



equalizing effect which, as noted by LaGrega and Keenan, can be measured


                                                           96
in terms of both flow variability and quality fluctuations.     The



presence of the lagoon has allowed the operator to control the flow



leaving the lagoon by control of the pump settings.  This has provided



additional flow equalization to the biological units.



     Operational Comments.  The primary operational factor has been the



chemicals required for precipitation and neutralization.  A summary of


these is presented in Table 22.  The rows labeled "average applied dose"



have been calculated by omitting those days on which chemicals could not



be added because of equipment malfunctions.


     Cost Data.  The cost of materials and electricity  is a part of Table



22.  The units are given in terms of dollars per one thousand gallons of



leachate treated.  The data indicate that the cost of System 2 with, and



without, operation of the lagoon has been $2.37 and $2.35 per thousand



gallons treated, respectively.  The total cost figures have been obtained


as the ratio of total costs to total volume of liquid treated.  The power



costs are quite high, reflecting energy consumption not only for chemical


treatment, but also for leachate pumping, air compressors and the


laboratory.  Manpower costs for operation and maintenance are approximately



twenty hours per week.



             Factors  Influencing Lime Treatment Performance



     The principal operating characteristics of the lime treatment system



are presented in Table 23 for data collected during the period June l*f,


1976 to April  21, 1977.   These data only are included as this was the


                                 -95-

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                                                         -97-

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                                                 -98-

-------
period of primary analysis, and also because of the change in the



leachate which occurred during the third year.



     The function of the lime treatment/clarification section of the



plant is to pre-treat the leachate prior to biological treatment, i.e.,



to remove a portion of the organic matter and toxic substances.  The



latter include ammonia as well as the heavy metals.  The lime



precipitation process has consistently produced an effluent which meets



the standards except for cadmium and lead.  (It should be noted that the



final effluent met these standards up to the onset of cold weather, and



that the probable mechanism for the additional removal is adsorption



onto the surface of the biological floe.)   It Is apparent that,



considering the variability of the incoming waste, equalization would



improve process efficiency and effluent quality.  The influent changes



occur so rapidly that the lime feed mechanism cannot maintain a constant



dose, with the result that there are occasions when the lime dosage is



inefficient and/or inadequate.  As a result of this consideration, the



raw leachate equalization lagoon was constructed.



     A desirable goal is to be able to operate the lime treatment process



selectively to improve the quality of the effluent with respect to one or



more of the heavy metals.  As the solubilities of the metals vary as


                         18
different functions of pH  , it is not possible to optimize the removal



of all metals at a given pH, and the pH becomes an operational indicator



the operator can use to achieve differential removals.  Thus, one can fine



tune the operation to provide an effluent of suitable characteristics.



With this goal in mind, the data of Table 23 were examined to discover a



                                 -99-

-------
relationship between pH, temperature, and the concentration of heavy




metals In the clarjfier effluent.




     In order to develop a relationship, which could be used as an




operational tool, between pH and the removal of heavy metals, the




effluent concentrations were examined as possible functions of pH.




Figures 11 and 12 show the relationship between pH and nickel and mercury




effluent concentrations, respectively.   |n these figures, the circled




data points were collected when leachate temperatures were less than




16 C, whereas the others represent higher tempratures (see Figure 13).




     The effects of pH and temperature on tne nicKei content of the




clarifier effluent are shown in Figure 11.  Process efficiency is not




a strong function of pH over the range of 8.9 to 11.7, and it does not




matter whether one measures nickel in the effluent or the fraction




removed.   Effluent concentrations of nickel  centered about 0.20-0.30




mg/1 over the entire pH range,  except at low temperatures.  For liquid




temperatures less than 16 C, the effluent nickel level increased




substantially.  This is shown in Figure 13.




     Iron concentration decre?sed with increasing pH with the lowest




concentrations resulting at pH  10.3-12.2,  The effect of low temperatures




(<16 C) was to increase the amount of iron in the clarifier effluent,  |n




terms of the iron removal efficiency, the fraction of iron removed was




independent of pH and temperature, as It was always greater than 0,98.




     The response of chromium,  lead and phosphate to pH was more or less




flat with no apparent relationship.  In each case, temperature did not




influence the effluent concentrations.   There was a tendency for lower




effluent chromium concentrations in the pH 9-10.5 range, and for better




                                 -100-

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                           -101-

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                                    -103-

-------
removals of lead at pH levels below 10.1.  However, these effects are


certainly not dramatic.


     The concentration of zinc In the clarlfler effluent decreased with


Increasing pH.  Minimum concentrations occurred at pH 10.*f to 12.2.  The


effect of low temperatures was to increase the zinc content of the


effluent.


     Chromium, copper and mercury concentrations show a tendency toward


a U-shaped response to pH.  The curve for mercury best illustrates this


relationship and is presented in Figure 12.  For each of these metals,


the effect of low temperatures is to reduce effluent concentrations.


The best pH values for chromium, copper and mercury removal are 10.2-


11.2," 10-11, and 9.8-10.8, respectively.


          Systems 3 and A - Biological Treatment of Raw Leachate


     These treatment sequences were tested In full-scale during the late


winter and early spring of 197&-  Severe problems were encountered in

                                  X
achieving successful treatment.  The primary reason underlying these


problems was the inability to develop a healthy activated sludge.


Approximately eight weeks were allocated to attempts to adapt a sewage


activated sludge culture to the law leachate.  After this did not succeed,


an investigation revealed that growth of activated sludge was not possible


because of ammonia  inhibition and phosphorus limitation.  The problems


were demonstrated by the observations thgt the average concentrations in


the biological units during this time were 9^0 mg/liter of ammonia-N and


less than one of phosphorus.  The data thus  indicated that In the aeration


tanks, the ratio of BOD:N:P was 6620:760:1 which is in marked contrast


to the usual recommendations which are in the range of 90-150:5:1.


                                -104-

-------
     The phosphorus limitation was investigated in two ways.  First,




replicate BOD tests were set up with varying additions of phosphate




buffer.  It was found that the BOD- increased with the phosphorus




addition up to an upper level, indicating that, within this range,




phosphorus was limiting.  As a result of this finding, the BOD




procedure was modified by the addition of sufficient phosphorus to




overcome the limitation.




     Second, a bench test was initiated to evaluate the hypothesis that




phosphorus limitation was the reason for the poor development of




activated sludge (see Table 2k).  The tests consisted of once daily




batch draw-and-fi11 experiments in which the increase in settleable




solids was used to monitor the growth of activated sludge.  The control




reactor received raw leachate only, whereas the sample reactor received




raw leachate plus seven ml of BOD phosphate buffer per liter of raw




leachate.  Thus, in the sample reactor, the BQD:N:P ratio was about




118:13-5:1.  The results are summarized in Table 2k,  It is seen that




over the short-term, there was an apparent positive Impact upon the




production of activated sludge and the utilization of COD.  However,




when the tests were continued for several  weeks, it became obvious




that there was no effect of phosphorus addition on either the development




of activated sludge or the removal of organics.




     The results of these experiments  have  been interpreted in the




following manner.   First,  the biochemical  oxygen demand tests,  and




the chemical  analyses showed that the leachate was severely phosphorus




limited.  This problem became more serious when biological treatment




                                -105-

-------
                              TABLE 2k

RESULTS OF BATCH DRAW-AND-FILL ACTIVATED SLUDGE EXPERIMENTS  TO DETERMINE
 THE EXTENT OF PHOSPHORUS LIMITATION.   RESULTS SHOW GROWTH OF ACTIVATED
     SLUDGE AS ML SETTLEABLE SOLIDS PER LITER, AND  COD  AS  MG/LITER

^x^ ' "

t i me , days^


0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Control
6620:760:1
^
influent effluent
COD COD SS
12813
7704
9339
—
8388 26
12868 10698 20
10193 15
11603
NR
9912
--
5963
9012 7115
1 3174
8606
8221
NR
--
6349
5625
Sample
118:13.5:

influent
COD
12813
7704
9339
—
8388
12868
10193
11603
—
9912
—
5963
9012
13174
8606
8221

--
6349


1

effluent
COD SS




40
7597 40
35





7115






5469

                              -106-

-------
 followed lime addition because of the precipitation of calcium phosphate



 salts In that unit.  Secondly, the batch draw-and-fil1 experiments showed



 that alleviation of the phosphorus limitation alone  is not enough to



 encourage the growth of activated sludge microorganisms.  It was concluded



 it would be necessary to reduce ammonia concentrations to a non-inhibitory



 level before successful biological treatment could be achieved.



 Consequently, the ammonia-stripping lagoon was started up prior to




 evaluating System 1.



      Systems 3 and k were re-evaluated during the spring and summer of




 1977.  The change-over from System 1 occurred on May 1, 1977, and data



 were collected until August 31, 1977-  Summaries of  the operating results



 for Systems 3 and k are presented in Tables 25 and 26, respectively.



 System k did not operate well enough to recommend its further use.




      System 3, biological treatment followed by chemical/physical



 treatment, achieved very good removal efficiencies,  as shown in Table 25:



 approximately three-quarters or more of nitrogen, all the heavy metals,



 and suspended solids; and, ninety percent or more of the organic matter.



 However, as shown in Table 27, the effluent quality  does not approach



' the standards placed on it,  in terms of ammonla-N and organic matter.



 In addition, the standard for lead has not been met  with System 3.   In



 sharp contrast, System 1 met all standards during the warmer months of




 late summer and early Fall,  1976 (see Table 16).




                       System 5 - Laboratory Studies



      Activated CarDon.  The preliminary evaluation of this system



 (System 5) has been carried out for raw leachate treatment.  These data




                                 -107-

-------
                               TABLE 25

                           SYSTEM  3 OPERATION'

Alkal inity, as CaCO-j
Ammonia-N
8005
Cadmium
Ca 1 c i urn
Chloride
Chromium
COO
Copper
Dissolved Sol ids
Hardness, as CaC03
1 ron
Kjeldahl-N
Lead
Magnesium
Mercury
Nickel
PH
Phosphates
Potassium
Sod i urn
Sulfate
Suspended Sol ids
Zinc
influent
n
12
12
13
13
13
13
13
38
13
39
13
13
12
13
13
13
13
39
12
13
13
14
39
13
X
5087
649
12649
0.11
937
4178
0.48
21152
0.27
14742
4463
348
708
0.76
350
0.007
2.0
7.6
2.3
1076
1536
658
1136
40
cv
0.20
0.17
0.22
0.52
0.17
0.19
0.33
0.21
0.38
0.20
0.21
0.39
0.16
0.28
0.22
0.51
0.50
0.56
0.57
0.13
0.09
0.23
0.47
0.42
effluent
n
8
8
9
10
10
9
10
32
10
33
10
10
8
10
10
10
10
32
8
10
10
9
32
0
X
1178
153
763
0.02
287
1496
0.08
2257
.07
5353
924
1.02
180
0.15
48
.002
0.27
10.20
0.56
476
719
513
180
0.51
cv
0.83
0.85
1.42
1.15
0.51
0.73
0.36
1.06
0.60
0.42
0.43
1.15
0.76
0.75
0.58
1.08
0.78
4.38
1.26
0.56
0.68
0.87
1.38
0.51
Percent
Remova I
76.8
76.4
94.0
81.8
69.4
64.2
83.3
89.3
74.1
63.7
79.3
99-7
74.6
80.3
86.3
71.4
86.5
—
75.7
55.8
53.2
22.0
84.2
98.7
     "Data collected from May 1, 1977 through August 31, 1977.  System
3_is biological treatment followed by chemical/physical treatment.
(x = mean, mg/1iter)
                                 -108-

-------
                               TABLE  26

                           SYSTEM 4  OPERATION'


Alkal inity, as CaC03
Ammonia-N
BOD 5
Cadmium
Calcium
Chloride
Chromium
COD
Copper
Dissolved Solids
Hardness, as CaCO-j
1 ron
Lead
Magnesium
Mercury
Nickel
PH
Phosphates
Potassium
Sod i urn
Sulfate
Suspended Sol ids
Zinc
Kjeldahl-N

n
12
12
13
13
13
13
13
38
13
39
13
13
13
13
13
13
39
12
13
13
14
39
13
12
influent
5
5087
649
12649
0.11
937
4178
0.48
21152
0.27
14742
4463
348
0.76
350
0.007
2.0
7.6
2.3
1076
1536
658
1136
40
708

cv
0.20
0.17
0.22
0.52
0.17
0.19
0.33
0.21
0.38
0.20
0.21
0.39
0.28
0.22
0.51
0.50
0.56
0.57
0.13
0.09
0.23
0.47
0.42
0.16

n
1
I
2
1
1
1
1
37
11
39
11
11
11
1
11
11
38
10
11
11
12
36
11
16
effluent
s cv
2788 0.13
312 0.35
2150 0.72
0.08 0.46
573 0.66
3778 0.23
0.37 0.39
468o 0.77
0.22 0.22
10081 0.20
2805 0.48
195 0.79
0.50 0.52
242 0.46
.0070.47
1.29 0.37
8.55 0.78
4.6 0.84
996 0.14
1412 0.09
853 0.44
1322 0.68
19 0.65
347 0.38
Percent
Remova 1
45.2
51.9
83.0
27.3
38.8
9.6
22.9
77.9
18.5
31.6
37.1
44.0
34.2
30.9
0
35.5
—
—
7.4
8.1
—
—
52.5
51.0
     -Data collected from May 1, 1977 through August 31, 1977.  System
4 is biological treatment only.   (x = mean; rug/liter)
                                 -109-

-------
                               TABLE 27

                  SUMMARY  OF SYSTEM 3 OPERATION DATA
                            (5/1/77-8/31/77)



Parameter
Ammonia-N
BOD5
Cadm ! urn
Chromium
COD
Copper
1 ron
Lead
Mercury
Nickel
Zinc
Raw
Leachate
m
-------
are presented in Table 28.  These tests have been performed with an



upflow column of depth 0,3 m and diameter 0,46 m, containing 15.9 kg



of granular activated carbon.  The influent flow was 38 liter/min, thus



providing a hydraulic loading rate of 232 liter/min-sq m.  As shown in



Table 28, no appreciable treatment can be attributed to the carbon




treatment.  It should be noted that excessive suspended solids loading




and influent variability contributed to this finding.  The effect of the



solids is to cause blockages and hence reduce process efficiency.  The



influent was not constant during any of the tests because it was drawn



from the actual plant influent.  Therefore it is impossible to calculate



removal efficiency.  However, it is evident from Table 28 that no



renovation is occurring in the carbon columns.  Hence, it is concluded



that carbon adsorption is not appropriate when applied to raw leachate,




although, as mentioned below, it may be suitable for final effluent



polishing.



     System 5 has also been assessed as an advanced waste treatment



technique.  This has been done using the effluent from the pilot



facility shown in Figure 5.  A summary of the data is given in Tables



29 and 30.  The data in Table 28 have been developed using small carbon



columns and a flow rate of 10 ml per min.  |n each case, a 25 ml sample



was collected at each sampling Interval.   Although batch data are more



amenable to such mathematical treatment,  a preliminary analysis has



been conducted to describe the results of Table 29 in terms of a Langmuir




adsorption isotherm.  The Langmuir isotherm results from assuming



reversible adsorption and an adsorbed monolayer:




                                -111-

-------









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-------
                          TABLE 30

       PILOT-SCALE CARBON TREATMENT OF  FINAL  EFFLUENT
Volume of Carbon Treated         Sorbate  Concentration  Following
  Final Effluent, liter          Carbon Treatment, mg COD/1iter

            0                                1900
           95                                  25
          189                                  35
          289                                 395
          379                                1312
          416                                1539
          454                                1695
          492                                1773
          530                                1828
          568                                1859
          606                                1875
          662                                1852
          719                                1891
          795                                1883
          871                                1848
                           -114-

-------
                           -= b(x/m)°Ce

                                  Hb Ce
m
     (—)  « value of — when mono layer has been completed
      mm


        x => moles of sorbate adsorbed



        m = weight of carbon



       C  => equilibrium molar concentration of sorbate



        b = adsorption coefficient



The analysis Indicated that (-)° is 9.709 mg per mg, and that b is 5,79



1iters per mg.



     The data shown in Table 30 have been collected from a larger column



charged with 120 Ib of carbon at a flow rate of k gal per min.  These



results have been plotted as a carbon breakthrough curve In Figure 14.



The cross-hatched area of Figure lA can be used to determine the



fractional capacity, f, of the adsorption zone.  The value of f is



estimated at 0.31.   From this, it is estimated that the depth of the



adsorption zone is 8.99 ft.  These values can be used as the basis of



the design of a full-scale unit.



     Additional Laboratory-Scale Studies.  A number of smaller scale



studies were undertaken during the third year.  These were designed to



evaluate a number of possible technologies which might be applied to more



efficiently treat the leachate.  In addition to the activated carbon



treatment discussed above, the following were also assessed: alkaline



chlorination, effluent filtration, and effluent breakpoint chlorfnation.



In addition, the use of additives In the lime treatment process was



investigated as a means of increasing the compaction of the lime sludge.



Each of these topics is discussed in subsequent paragraphs.



                                -115-

-------
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-116-

-------
     Alkaline ChlorinatIon.  During a part of the third year, difficulties




were encountered in the efficiency of the lime treatment process,  |t was




believed that the problems were possibly due to excessive hydraulic




loadings.  In this light, the use of compacting agents as discussed




below was studied, and minor design changes were Instituted.  One other




explanation for the difficulties encountered In the removal of heavy metal




is that the metals may have formed complexes with organic matter or with




cyanides.  In this chemical form, the metals resist removal by lime




treatment.  It might have been possible to improve the efficiency of lime




precipitation of heavy metals by adding chlorine during this step.




Alkaline chlorination has the effect of disrupting heavy metal complexes,




particularly those involving cyanides.  In this manner, the metals are




freed from the complex ing agents, after which they precipitate under the




alkaline pH conditions.




     Preliminary evaluations of alkaline chlorination were conducted.




The results were negative as shown In Table 31.  The samples of raw




leachate were supplemented with the chemicals indicated in Table 31,




mixed for 5 min with a magnetic stirrer, and then allowed to settle for




30 min.  The volume of sludge produced was recorded, and analyses for




heavy metals were performed on the clarified supernatant.  The addition




of NaOCl had no significant effect on sludge volume, nor on the




concentration of copper and cadmium, may have been associated with




reduced concentrations of zinc, nickel and lead, and was definitely




associated with reduced concentrations of iron and chromium.  The results




were deemed negative, because the addition of small  amounts of chlorine




                                -117-

-------














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-118-

-------
did not significantly affect the ability of the process to meet effluent



standards.  Very high concentrations of NaOCl may be helpful in attaining



the chromium standard (see Table 1).



     Compaction of Lime Sludge,  The second possible cause of poor lime



treatment performance to be investigated was that of inferior




settleability of the sludge.  A number of Jar tests have been conducted



in an effort to evaluate the effect of additives on the efficiency of



heavy metal precipitation and on the compaction of the resultant lime



sludge.  These tests have been performed to evaluate the performance of



lime, a commercial aluminate preparation, and sodium hydroxide.  The



results are presented in Tables 32 and 33.  The first of these tables



shows the experimental  protocol which was, in brief, to treat each flask



with lime to give a final pH of 11,7,  Aluminate was added at the rate of



300 mg/1 as recommended by the manufacturer's representative.  Sodium



hydroxide was added at the rate of 125 ppm in accordance with the



observation of the leachate treatment plant operator who noted a decided



improvement in process efficiency at this dosage of caustic.  It should



be noted that the use of aluminate did not result in an especially clear



supernatant and that it did result in a relatively large volume of



sludge.  On the other hand, the addition of NaOH provided a very clear



supernatant, at least equal to that obtained with lime alone, and a



relatively small  sludge volume.  The results, in terms of the removal



of heavy metals,  are presented in Table 33.  None of the additives were




an improvement over lime alone, in terms of meeting the standards (see




Table 1).   In absolute terms,  neither additive,  alone or in combination,



provided improved treatment across the board.   In fact, in several  cases,




                                -119-

-------
                             TABLE 32

            EXPERIMENTAL PROTOCOL AND PRELIMINARY RESULTS
              IN EVALUATION OF LIME TREATMENT ADDITIVES*





Preliminary Results
Experimental Protocol
Flask
Number
1
2
3
4
5

Lime, ml
0
18
18
12
15
Addi ti ves
Aluminate, ml
0
0
10
0
10

NaOH, ml
0
0
0
0.1
0.1
Supernatant Sludge
Clarityf Volume, ml
0
++ 110
120
++ 80
+ 120

      The experimental  flasks each contained raw leachate plus the
additives as indicated.

     iThe clarity of the supernatant was evaluated qualitatively as
follows: --, very turbid; -, turbid; +, clear; ++, very clear.  Also
the volume of sludge (in ml) produced was noted.
                               -120-

-------
                              TABLE 33

                   RESULTS OF ADDITIVE EVALUATION*

Experimental Protocol
Paramater
Analyzed
1 ron
Copper
Cadmium
Chromium
Lead
Zinc
Nickel
Mercury
Raw
Leachate
Control
52.0
0.2k
0.04
0.15
0.19
6.40
0.71
0.002
Lime
Only
0.45
0.14
0.06
0.09
0.16
0.03
0.56
0.002
Lime
+
Al uminate
1.21
0.16
0.04
0.07
0.19
0.12
0.52
0.002
Lime
+
NaOH
0.77
0.14
0.07
0.08
0.16
0.10
0.58
0.001
Lime + NaOH
T*
Aluminate
1.71
0.24
0.03
0.09
0.15
0.08
0.53
0.002

     J»
      All  units are mg per liter in the supernatant following
indicated  protocol.
                              -121-

-------
the removal decreased due to the additives.  The conclusion is that




neither NaOH nor aluminate, when added to lime and leachate at a final




pH of 11.7, results in improved removal of heavy metals.  However, the




addition of 125 ppm NaOH provides a significant reduction in sludge




volume, a fact which would improve the efficiency of the lime clarifier




operation.  Sludge handling and disposal will also be rendered more




efficient.  Therefore, the addition of NaOH was recommended.




     An added benefit is a higher pH in the ammonia lagoon which




increases the ammonia stripping capacity of the lagoon.   This is




illustrated by the observation that the supernatant pH where NaOH was




added had fallen to only 11.5, whereas, in the flasks not receiving




NaOH, the supernatant pH had dropped to less than 11.  This is a




demonstration of the strong buffering properties attributable to the




addition of NaOH.




     An additional recommendation was made which improved the efficiency




of the lime clarifier.  This was that the depth of the sludge blanket




be kept minimal.  This prevented solids carryover which occurred on




occasion in the past.  Sludge blanket depth may be minimized by




semi-continuous withdrawal of settled sludge.  An automatic timing




mechanism was installed to ensure sludge removal semi-continuously on




a 2k hr basis.




     Effluent Filtration.  The physical process of filtration has




several potential applications in leachate treatment.  Filtration of




activated sludge effluent would be needed before activated carbon or




ion exchange treatment,  if these operations are necessary.  This  is



                                -122-

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required to reduce the solids loadings on these units, and hence, to




minimize problems due to clogging.




     A second application of filtration would be to use it between the




ammonia stripping lagoon and the activated sludge process.  The purpose




of doing this is to remove residual heavy metal precipitates as well as




calcium carbonate which may form during lagooning or which may escape




the lime clarifier unit.  The benefits which would accrue include




lower heavy metals loadings and solids loadings on the biological




treatment units.




     The first step in evaluating the efficacy of filtration is a




number of small scale units.  The purpose of these would be to provide




a preliminary evaluation of the removal of heavy metals and particulates




from the ammonia lagoon effluent, and to determine the compatabi1ity of




a filtered effluent from the activated sludge process with granular




activated carbon.




     The principal design parameters which must be considered are filter




configuration; method of flow control; terminal headless (ft of water);




filtration rate (gal/min-sq ft); filter media, sizes and depths; and,



backwashing requirements.  The basic filter configurations are upflow




filtration through a relatively deep, coarse filter medium; using a




filtered water collection device within the filter medium and bringing




water in from both the bottom and the top; dual or mixed media with




conventional  downflow; and single medium downflow filtration.




     Preliminary testing of filtration has been conducted using filter




paper (Whatman No. ^0).   The results are presented in Table 3A, and




they show that additional removals of most of the heavy metals are




                                -123-

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achieved by filtration at any intermediate step of the treatment




sequences.




     Effluent Breakpoint Chlorination.  Although nitrification is an




extremely efficient process for the removal of ammonia-N, it is a




biological treatment method.  As a result, nitrification can be




temperamental and prone to upset.  As noted earlier, the nitrifying




organisms are very sensitive to temperature.  Also, the ammonia




stripping process is less effective during the winter.  Consequently,




the effluent in the colder months is very high in ammonia-N.  The




removal of residual ammonia in the final effluent may be accomplished




by breakpoint chlorination.  This procedure oxidizes the NH.-N to




gaseous end-products including N?.  Breakpoint chlorination has been




practiced at the GROWS treatment facility and is a proven technology




for meeting the effluent criterion for ammonia (see Table I).




     The chlorine demand, and therefore chlorination operating costs,




are expected to decrease as the degree of organics removal increases,




and this savings can affect some portion of the carbon costs.  An




economic tradeoff can be made here vis-a-vis the costs of activated




carbon treatment of the final effluent.




     Leachate Treatment Plant Startup.  The results of this study have




Indicated clearly that Systems 1 and 2 are very effective in the




treatment of leachate.  The best results were obtained with a process




train consisting of raw leachate equalization, lime precipitation and




clarification, ammonia stripping lagoon, activated sludge providing




for carbonaceous and nitrogenous oxidation, sedimentation, and




                                -125-

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effluent chlorination.  As noted in Tables 14, 15, 20 and 21, the




removal efficiencies observed with Systems 1  and 2 are extremely high,




and provide the best opportunity for meeting the effluent criteria.




     Nevertheless, in spite of the success of Systems 1 and 2, some




problems were encountered during startups.  Some of these have been




discussed elsewhere.  These include the nutrient deficiency due to




phosphate precipitation in the lime treatment unit; and substrate




inhibition resulting from excessive ammonia-N concentrations.




     Excessive loadings have been received by the plant in terms of




ammonia, metals, and organics.  For the past year, raw leachate flows




have been in the 50,000 to 80,000 gpd range,  which when coupled with




the extremely high influent concentrations yields process loadings In




excess of those which had been experienced during the initial




operational phase of the plant.  The combination of excessive




concentrations and loadings is the primary factor inhibiting rapid




successful process startup.



     There are a number of secondary reasons for the poor startup




performance.  The first of these is that the third year operational




effort was initiated in mid to late winter.  As a result, the




development of a healthy activated sludge culture was inhibited due to




low temperatures, as well as to the presence of high concentrations of




metals and organics.  These high concentrations resulted not only




because of the leachate strength, but also because of operational




problems.  Examples of these problems include instances where raw




leachate has by-passed the chemical/physical section, and Insufficient




air has been provided to the bio units.




                                -126-

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     Other secondary factors underlying the startup problems Include




those relating to plant operation and the behavior of the sedimentation




tanks.  Frequent problems were encountered which affected adversely the




performance of both the chemical/physical and the secondary clarifiers.




Eddy currents were occasionally noted in the secondary clarifier and




these resulted in carry-over of biological solids.  The high rate of




internal recycle in the activated sludge undoubtedly contributed to this




condition.  In the case of the chemical/physical sedimentation tank,




some reduction in clarification efficiency was observed as a result of




excessive sludge volumes.  Lime sludge production had increased as the




acidity and the rate of generation of leachate increased.




     Many of the problems mentioned above are essentially different




aspects of plant reliability.  Each section of the plant needs a high




level of reliability.  This  is especially true of the lime treatment




section.  It is recommended that, in the future, as these plants become




more sophisticated, greater consideration be given to automatic process




control techniques.  As an example consider the lime slurry system.  At




the present time, if this system malfunctions such that the lime feed




stops, then raw leachate passes to the ammonia lagoon and thence to the




bio units where pronounced inhibitory effects are observed.  These




problems could be avoided by an automatic valving system which would




recycle the lime clarifier effluent to the equalization pond whenever




the effluent pH dropped below some set point such as pH 10 or pH 10.5.




Process reliability is important at plants such as this because they




normally operate at very close to inhibitory concentrations of



                                -127-

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materials such as ammonia, metals, and organics.  Thus, small
perturbations can result in process upset followed by an extensive
period during which the discharge standards are contravened.
     Most of the startup problems, however, are related directly to the
increased leachate flow and strength.  Higher flows have not diluted
the leachate, but have been associated with increased concentrations of
pollutants.   This, in turn, is partially a result of the introduction
of industrial liquid wastes.
     An indication of the extremely high loadings is provided in Table
35.  The data show process loadings applied to System 2 (lime treatment/
ammonia lagoon)  and to System 1  (activated sludge).  These data are for
the period April 1, 1978 through June 30, 1978.  This represents the
startup period for the most recent evaluation of Systems 1  and 2.  For
comparison,  the original design loadings, derived from Table 9, are
included.  It can be seen that the more recent loadings are very high
(except for the metals and suspended solids).  When this is coupled
with the high concentrations of inhibitory substances, the basis for
the poor startup performance becomes clear.
     The role of high concentrations relates to a previous discussion.
As noted in Figure 9, the phenomenon of substrate inhibition must be
considered.   Even substrates such as ammonia-N or BOD which are vital
requirements at low concentrations become inhibitory at higher
concentrations.   The significance for leachate treatment is that the
system operates at influent concentrations high enough to be inhibitory.
Slight perturbations result in process instability and/or poor startup.
                                -128-

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                                                          -129-

-------
Thus, the principal source of process startup problems are the
combination of excessive loadings and concentrations near the upset
threshhold.
     The activated sludge system has been operated most successfully at
a mixed liquor volatile suspended solids (MLVSS)  concentration of
6000-12,000 mg per liter, depending upon the influent BOD concentration.
During periods of satisfactory operation the food to microorganism
ratio has been in the 0.12 to 0.32 day   range,  as calculated by
                                  Q CQ
                              L = v~T~
                                     a
            where
                              L - F:M, Ib BOD per Ib MLVSS-day
                              Q. = Process hydraulic loading,  gpd
                             C  = Process influent BOD, mg per liter
                              V = Aeration tank volume, gal
                             X  = MLVSS, mg per 1iter
                              3
The operation of the activated sludge units in series (see Figure 7)
was accomplished by maintaining 12,000 mg MLVSS per liter and 6000 mg
MLVSS per liter, in the first and second stages,  respectively.
     The following recommendations are made in an effort to reduce
future startup problems:
1.  Raw leachate equalization is a valuable aid in dampening  peak
    concentrations of materials which are inhibitory to subsequent
    biological processes; and, in controlling chemical dosages in
    the lime precipitation units.
                                -130-

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2.  Ammonia removal by stripping via aeration reduces concentrations



    to a level below the point of inhibition.



3.  Nutrient supplementation may be necessary.  This is especially true



    for the case of a high carbon waste with biological treatment units



    preceded by lime precipitation.



4.  Excessive loadings may necessitate treatment of only a portion of




    the total waste flow during startup.  At these times, the balance



    of the flow should be recycled to the landfill.



5.  With a waste containing very high levels of ammonia-N, startup



    should occur during warm weather months.  Otherwise, nitrification



    will be inhibited, and the resulting ammonia concentrations will not



    permit biological activity.
                               -131-

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                             VI.  CONCLUSIONS




1.  The GROWS landfill leachate is characterized by high organic strength




    and by large day-to-day variations.  Much of the variability can be




    dampened by raw leachate equalization.




2.  Considerable experience has been gained in the operation of activated




    sludge units on raw leachate and on leachate which has received




    chemical/physical  treatment.  It has been concluded that this raw




    leachate must be pre-treated in order to render it amenable to




    activated sludge processing.  The results indicate that the raw




    leachate inhibits the growth of the activated sludge microorganisms.




    System 3 (biological  treatment of raw leachate) has yielded an




    average effluent BOD,, of 763 mg per liter, a concentration which is




    clearly not acceptable.




3.  The operation of the chemical/physical units (System 2) has continued




    for some time to gain experience under a wide variety of operating




    conditions and sufficient data have been collected to provide an




    evaluation of this method of treating raw leachate.  Lime treatment




    alone (System 2a) provides removal efficiencies of approximately 50




    percent of the organic matter, 75 percent of suspended solids,




    one-half of mercury and cadmium, and at least two-thirds of the




    other heavy metals.




4.  The complete chemical/physical treatment sequence consisting of




    lime precipitation/sedimentation/ammonia stripping (System 2b)




    achieved the following removals of efficiency: 48 to 69 percent




    of the organic matter, ammonia-N and total kjeldahl-N; 70 percent




    of the suspended solids, and 50 percent or better of the heavy




                                -132-

-------
    metals except copper, for which the removal efficiency was 37.8




    percent.  In the final year of the project, System 2b was augmented




    with an initial raw leachate equalization step.




5.  Temperature and pH have an effect on the concentration of heavy




    metals in the lime treatment effluent.  However, the response is




    not identical for all heavy metals.  If the differences were more




    thoroughly characterized, it might be possible to use them in an




    operational  control procedure.




6.  Activated sludge treatment of the effluent from the chemical/physical




    units has been extremely successful (System 1).  It is apparent that




    the reduction in ammonia-N afforded by the ammonia stripping lagoon




    provides conditions suitable for the growth of activated sludge




    microorganisms.  The ammonia lagoon, in conjunction with the balance




    of System 2, provides ammonia removals of approximately 50 percent




    resulting in activated sludge influent concentrations of 1^9-423 mg




    NH-N/liter (95 percent confidence interval).   During the final




    year of the project, these concentrations increased somewhat due




    to the maintenance of a lower pH in the lagoon.  Under this condition,



    the activated sludge quickly adapted to the leachate with the result




    that effluent BOD- concentrations were consistently low except  during




    cold weather.  Nitrifying organisms  developed and produced a




    nitrified effluent with very low concentrations of ammonia.  Cold




    winter weather inhibited the biochemical  oxidation of organics  and




    ammon i a.




7.  Activated sludge treatment has been effective in both the series




    (Figure 7) and parallel (Figure 4)  modes  of operation.   That is, the




                               -133-

-------
    plant configuration has had the aeration tanks in either parallel
    or series, with approximately equal results.
8.  Overall, the treatment sequence consisting of chemical/physical
    (lime precipitation, sedimentation, ammonia stripping, and
    neutralization) followed by activated sludge (System 1) has
    produced an excellent final effluent with the following
    characteristics:
         a.  Organic matter has been reduced to 153 mg BOD^/liter.
             This  is a 99 percent removal.  The corresponding COD
             removal efficiency is 95 percent.  The effluent BOD
             co COD ratio is 0.16.
         b.  The effluent ammonia concentration is 75 mg/liter,
             representing 90 percent removal.
         c.  Heavy metals are found in the effluent at the following
             levels (percent removals are shown in parenthesis):
             0.017 mg cadmium/liter (78.2 percent); 0.07 mg
             chromium/liter (73.1 percent); 0.11 mg copper/liter
             (72.5 percent); 2.7 mg iron/liter  (99.2 percent);
             0.12 mg lead/liter (83.8 percent); 0.004 mg mercury/
             liter  (27.4 percent); 0.75 mg nickel/liter (57.4
             percent); 0.53 mg zinc/liter (97.3 percent).
9.  The kinetics of nitrification have been followed during System Ib
    operation.  The rate of nitrification, expressed as the specific
    oxidation rate, follows the van't-Hoff Arrhenius relationship.
    The data Indicate that the activation energy is approximately
                                 -134-

-------
     12350 cal  per mole, and that the Arrhenlus frequency factor is



     2.18 x 109 day"1.



10.  The data show that substrate Inhibition due to ammonium ion



     concentration occurs in System Ib nitrification.   This relationship



     has been expressed as a Haldane inhibition model  in which the maximum



     specific oxidation rate Is 3.5 g N oxidized per g blomass day, K



     is k mg per liter, and K.  Is 36 mg per liter.



11.  Pilot scale operation of System 5 shows that activated carbon



     treatment of System 1 effluent is an effective way of removing



     much of the remaining organic matter.  In addition, considerable



     removals of heavy metals occur in the carbon columns.



12.  A bench-scale evaluation of alkaline chlorination as a means of



     improving heavy metals removal  Indicated that  the technique is not



     appropriate.




13.  Studies of lime sludge compaction and supernatant clarity reveal



     that the addition of sodium hydroxide (125 mg  per liter)  improves



     both factors.  The addition of a commercial aluminate preparation



     (300 mg per liter) had an  adverse impact on compaction and clarity.



1A.  Preliminary testing of filtration shows that additional  removals



     of most heavy metals can be achieved.



15.  Full-scale studies of breakpoint chlorination  have shown  that this



     method can be used to attain the ammonia effluent criterion.
                                 -135-

-------
                        VII.   REFERENCES
1.  Remson, I., A. A. Fungaroli, and A. W. Lawrence.  Water move-
         ment in an unsaturated sanitary landfill.  Journal of
         the Sanitary Engineering Division, Proceedings of the
         American Society of Civil Engineers, 94(SA2):307-317,
         Apr. 1968.

2.  Calvert, C. K.  Contamination of ground water by impounded
         garbage waste.  American Water Works Association
         Journal, 24:266-270, 1932.

3.  Carpenter, L. V., and L. R. Setter.  Some notes on sanitary
         land-fills.  American Journal of Public Health and the
         Nation's Health, 30(1):385-393, Apr. 1940.

4.  Merz, R. C., and R. Stone.   Factors controlling utilization
         of sanitary landfill site; final report to Department of
         Health, Education,  and Welfare, National Institutes of
         Health, United States  Public Health Service, May 1, 1960
         to May 31, 1963.  Los  Angeles, University of Southern
         California, [1963].  126 p.

5.  Longwell, J.  The water pollution aspect of refuse disposal.
         Paper no. 6261.  Institution of Civil Engineers
         Proceedings, 8:420-424, 1957.

6.  Great Britain Ministry of Housing and Local Government.  Pol-
         lution of water by tipped refuse; report of the
         Technical Committee on the Experimental Disposal of
         House Refuse in Wet and Dry Pits.  London, Her Majesty's
         Stationery Office,  1961.  141 p.

7.  Qasim, S. R.  Chemical characteristics of seepage water from
         simulated landfills.  PhD Dissertation, West Virginia
         University, Morgantown, W. Va., 1965.  145 p.

8.  Anderson, J. R., and J.  N.  Dornbush.  Influence of sanitary
         landfill on ground water quality.  American Water Works
         Association Journal, 59(4):457-470, 1967.

9.  Hughes, G. M., R. A. Landon, and R. N. Farvolden.  Summary
         of findings on solid waste disposal sites in
         northeastern Illinois.  Environmental Geology Notes no.
         45.  Urbana, 111.,  Illinois State Geological Survey,
         Apr. 1971.  25 p.
                           -136-

-------
10.  Steiner, R. L.  Chemical and hydraulic characteristics of
          milled refuse.  PhD Dissertation, Drexel University
          College of Science, Philadelphia, Pa., 1973.  319 p.

11.  Weaver, L.  Refuse disposal, its significance.  Ln Ground
          Water Contamination; Proceedings of the 1961 Symposium,
          Cincinnati, Apr. 5-7, 1961.  Robert A. Taft Sanitary
          Engineering Center Technical Report W61-5.  Cincinnati,
          U.S. Department of Health, Education, and Welfare,
          Public Health Service, Bureau of State Services,
          Division of Water Supply and Pollution Control.
          p.104-110.

12.  [Engineering-Science, Inc.] * In-situ investigation of
          movements of gases produced from decomposing refuse;
          final report.  Publication no. 35.  Sacramento, Calif.,
          State Water Quality Control Board, 1967.  116 p.

13.  Walker, W. H.  Illinois ground water pollution.  American
          Water Works Association Journal, 61(1):31-40, Jan. 1969.
                                                          t,
14.  Roessler, B.  Beeinflussung des Grundwassers durch Mull- und
          Schuttablagerungen.  Vom Wasser, 18:43-60, 1950/51.

15.  Chian, E. S. K., and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.  Journal of the
          Environmental Engineering Division, Proceedings of the
          American Society of Civil Engineers, 102(EE2):411-431,
          Apr. 1976.

16.  Remson, I., et al.  Water movement in an unsaturated sanitary
          landfill.

17.  Dass,  P., G. R. Tamke, and C.  M. Stoffel.  Leachate production
          at sanitary landfill sites.  Journal of the Environmental
          Engineering Division, Proceedings of the American
          Society of Civil Engineers, 103(EE6): 9-81-988, Dec. 1977.

18.  Calvert, C. K.  Contamination of ground water by impounded
          garbage waste.

19.  Carpenter, L. V.,  and L. R. Setter.  Some notes on sanitary
          land-fills.

20.  Merz,  R. C., and R. Stone.  Factors controlling utilization of
          sanitary landfill site.

21.  Longwell, J.  The  water pollution aspect of refuse disposal.

22.  Great  Britain Ministry of Housing and Local Government.  Pol-
          lution of water by tipped refuse.
                         -137-

-------
23.  Qasim, S. R.  Chemical characteristics of seepage water from
          simulated landfills.

24.  Steiner, R. L.  Chemical and hydraulic characteristics of
          milled refuse.  Adapted from Table 18 on p.55-60 et
          passim.

25.  Chian, E. S. K.,  and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.  Adapted from data in
          text.

26.  Great Britain Ministry of Housing and Local Government.  Pol-
          lution of water by tipped refuse.  Adapted from data on
          p.116, 128.

27.  Anderson, J. R.,  and J. N. Dornbush.  Influence of sanitary
          landfill on  ground water quality.

28.  Hughes, G. M., et al.  Summary of findings on solid waste
          disposal sites in northeastern Illinois.

29.  Qasim, S. R.  Chemical characteristics of seepage water from
          simulated landfills.  Adapted from Table 14 on p.81 et
          passim.

30.  Qasim, S. R.  Chemical characteristics of seepage water from
          simulated landfills.

31.  Weaver, L.  Refuse disposal, its significance.

32.  [Engineering-Science, Inc.]  In-situ investigation of
          movements of gases produced from decomposing refuse.

33.  Walker, W. H.  Illinois ground water pollution.

34.  Roessler, B.  Beeinflussung des Grundwassers durch Mull- und
          Schuttablagerungen.

35.  Chian, E. S. K.,  and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.

36.  Dass, P., et al.   Leachate production at sanitary landfill
          sites.

37.  Schoenberger, R.  J., et al.  Treatability of leachate from
          sanitary landfills.  In Proceedings; Fourth Mid-Atlantic
          Industrial Waste Conference, Newark, Nov. 18-20, 1970.
          University of Delaware,  p.411-421.

                           -138-

-------
38.  Western, R. F., and R. A. Morrell.  Treatment of water and
          wastewater for removal of heavy metals.  In J. A.
          Borchardt et al., eds.  Viruses and trace contaminants
          in water and wastewater.  Ann Arbor, M-ich., Ann Arbor
          Science, 1977.  p.167-182.

39.  Chian, E. S. K., and F. B. DeWalle.  Treatment of high
          strength acidic wastewater with a completely mixed
          anaerobic filter.  Water Research, 11(3) :295-304, 1977.

40.  Chian, E. S. K. , and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.

41.  Weston, R. F., and R. A. Morrell.  Treatment of water and
          wastewater for removal of heavy metals.  Adapted from
          Table 3 on p.171.

42.  Chian, E. S. K.  Stability of organic matter in landfill
          leachates.  Water Research, 11(12) :225-232, 1977.

43.  Chian, E. S. K., and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.

44.  Chian, E. S. K., and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.

45.  Uloth, V. C., and D. S. Mavinic.  Aerobic bio-treatment of
          a high-strength leachate.  Journal of the Environmental
          Engineering Division, Proceedings of the American
          Society of Civil Engineers, 103(EE4):647-661, Aug. 1977.

46.  Lawrence, A. W., and P. L. McCarty.  Unified basis for
          biological treatment design and operation.  Journal of
          the Sanitary Engineering Division, Proceedings of the
          American Society of Civil Engineers, 96(SA3):757-778,
          June 1970.

47.  Chian, E. S. K., and F. B. DeWalle.  Sanitary landfill
          leachates and their treatment.  Adapted from table on
          p.427.

48.  Personal communication.  Trenton, N.J. Weather Bureau to
          R. L. Steiner, Applied Technology Associates, 1976.
          Data calculated for 30-year period ending Dec. 1975.

49.  Industrial waste permit no. 0974203.  Issued by Commonwealth
          of Pennsylvania, Department of Environmental Resources
          to Geological Reclamation Operations and Waste Systems,
          Inc., 1975.  [3 p.]

                          -139-

-------
50.  Remson, I., et al.  Water movement in an unsaturated sanitary
          landfill.

51.  Standard methods for the examination of water and wastewater.
          14th ed.  Prepared for and published jointly by American
          Public Health Association, American Water Works
          Association, and Water Pollution Control Federation.
          Washington, American Public Health Association, 1976.
          1193 p.

52.  Annual book of ASTM standards; Part 23:  Water, atmospheric
          analysis.  Philadelphia, American Society for Testing
          and Materials, 1973.  1108 p.

53.  Manual of methods for chemical analysis of water and wastes.
          [2d ed.]  Environmental Protection Publication
          625/6-74/003.  Cincinnati, U.S. Environmental Protection
          Agency, Office of Technology Transfer, 1974.  298 p.

54.  Steiner, R. L.,  and A. A. Fungaroli, eds.  Analytical pro-
          cedures for chemical pollutants; research project on
          pollution of subsurface water by sanitary landfill.
          Series 1, no. 8.  Philadelphia, Drexel Institute of
          Technology, June 1968.  27 p.

55.  Weston, R. F., and R. A. Morrell.  Treatment of water and
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                                                              V01764
                                                              SW-758
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                                -143-

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                 1 Praectlon
230  South  C-^o-n cVeet
Ch'cago, Illinois  6C604

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