United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
January 1979
Research and Development
Post  Biological
Solids
Characterization and
Removal from Pulp
Mill Effluents




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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.   Environmental  Health Effects Research
      2.   Environmental  Protection Technology
      3.   Ecological Research
      4.   Environmental  Monitoring
      5.   Socioeconomic Environmental Studies
      6.   Scientific and Technical Assessment Reports (STAR)
      7.   Interagency Energy-Environment  Research and Development
      8.   "Special" Reports
      9.   Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY  series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                             EPA-600/2-79-037
                                             January 1979
           POST BIOLOGICAL  SOLIDS
        CHARACTERIZATION  AND REMOVAL
          FROM PULP MILL  EFFLUENTS
                      by

               R.  R.  Peterson
                J. L.  Graham
               CH2M Hill,  Inc.
           Corvallis,  Oregon 97330
           Contract No.  68-03-2424
              Project Officers

            John S.  Ruppersberger
               H. Kirk Willard
        Food and Wood Products  Branch
Industrial  Environmental  Research Laboratory
           Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI, OHIO  45268

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                                DISCLAIMER

     This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publi-
cation.  Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
                                     ii

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                                 FOREWORD
     When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollution con-
trol methods be used.  The Industrial Environmental Research Laboratory -
Cincinnati (lERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently and economi-
cally.

     This report summarizes the results of a study to characterize the post
biological solids of several pulp and paper mill waste treatment operations.
The nature of these solids did not suggest that these suspended solids would
adversely affect the receiving streams.  Several methods for removing these
post biological solids were investigated and rated for effectiveness.  If
these solids eventually show detrimental effects on aquatic life this report
will provide a useful guide for going about selecting the best technology to
reduce their concentrations.  The heavy metal content for 9 mills is also
tabulated.  For further information please contact Dr. H. Kirk Willard of the
Food and Wood Products Branch, IERL, Cincinnati, Ohio.
                                     David G. Stephan
                                         Director
                       Industrial Environmental Research Laboratory
                                        Cincinnati
                                    iii

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                                   ABSTRACT

     The objective of this study was to characterize the post biological
 solids  in pulp and paper mill secondary effluent and to evaluate various
 suspended solids removal techniques.  The study was initiated as a result of
 EPA  guidelines development work, which might potentially require post bio-
 logical solids removal to a level on the order of 10 mg/1.  This bench scale
 work comprised Phase I of the project.  A second phase of work has been pro-
 posed to extend these efforts to a pilot scale study (on site at several
 mills)  of the most promising of the removal techniques as determined in the
 Phase I work.  Phase II, however, has since been eliminated.  Phase I was
 formulated  in three parts; solids characterization; coagulation method opti-
 mization; and removal method evaluation.

     Phase  la, Solids Characterization, examined effluent samples from nine
 representative pulp and paper mills.  The post biological solids resulting
 from secondary treatment of the mill wastewater were "fingerprinted" by 11
 analyses for physical and chemical characteristics.  An attempt was made to
 correlate these findings with geographic location, pulping process, and type
 of treatment process used at each mill.  Results indicate that the suspended
 solids  are  mostly biological in nature. Biochemical and chemical oxygen
 demand  (BOD and COD), volatile content, and nutrient content (Kjeldahl nitro-
 gen  and total phosphate) test results and microscopic examination tended
 to support  this conclusion.  The predominance of negatively charged particles
 indicated the potential effectiveness of trivalent aluminum and iron salts as
 coagulants.

     Phase  Ib, Coagulation Optimization, included evaluation of three in-
 organic chemicals (alum, ferric chloride, and lime) in combination with five
 polymers to determine the optimum coagulant and dosage.  A jar-test appara-
 tus was used on effluent samples from mills number 1, 2, and 3.  Alum was
 selected for use with a cationic liquid polymer because this combination
 provided the best floe formation and the lowest supernatant total suspended
 solids  (TSS) content after settling, for all samples.  The cationic liquid
 polymer provided the most stable floe formation, and was the easiest to mix
 and feed.

     Phase Ic, Solids Removal Techniques, included bench scale testing of
 six tertiary treatment processes for their effectiveness in solids removal,
 and response to the range of solids characteristics measured in Phase la.
 The methods tested included:  Coagulation/Sedimentation; Mixed Media Filtra-
 tion; Sand Filtration; Microstraining; Dissolved Air Flotation; and Magnetic
 Separation.

     The results of the Phase Ic testing indicated that of the six methods
tested only sand filtration and mixed media filtration appeared to produce

                                     iv

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results which would warrant further testing.  Variable TSS removals, ranging
from 20 to 70 percent, were observed with the bench scale equipment used.

     The purpose of this study was to identify those solids removal methods
which exhibit enough potential for significant solids removal to justify
pilot scale testing on site.  However, a joint industry-regulatory task com-
mittee concluded from the Phase I data that none of the technologies investi-
gated appeared to remove suspended solids better than simple setting.   Thus,
no further work on this project was merited.

     This report was submitted in fulfillment of Contract No. 68-03-2424 by
CH2M Hill, Inc., under the sponsorship of the U.S.  Environmental Protection
agency.  This report covers the period June 1, 1976 to April 30, 1977,  and
work was completed as of June 15, 1977.

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                                 CONTENTS
Foreword	
Abstract	  iv
Figures	viii
Tables	   x
Abbreviations and Symbols	•	  xi
Conversion Table	.xiii
Acknowledgments	 xiv
    1.  Introduction 	   1
          General Description of Project 	   1
          Project Conception	   2
    2.  Conclusions;	   3
    3.  Recommendations	•	   8
    4.  Project Execution. 	   9
             Phase la:  Solids Characterization	   9
             Phase Ib:  Coagulation Experimentation	  10
             Phase Ic:  Solids Removal	  10
             Mills Selected for Use	  12
    5.  Results and Discussion	  23
             Phase la:  Solids Characterization	  23
             Phase Ib:  Coagulation Experimentation	  ^2
             Phase Ic:  Solids Removal Techniques	  51
References	  6U
Appendices	  67
     Appendix A.   Literature Review	  67
     Appendix B.   Analytical Methods	  73
     Appendix C.   Data Summaries	  7^
                                    vii

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                                   FIGURES
  Number                                                                 Page
  1  Mill Data Summary - Mill No. 1	 13
  2  Mill Data Summary - Mill No. 2	I1*
  3  Mill Data Summary - Mill No. 3	15
  4  Mill Data Summary - Mill No. 4	16
  5  Mill Data Summary - Mill No. 5	17
  6  Mill Data Summary - Mill No. 6	18
  7  Mill Data Summary - Mill No. 7	19
  8  Mill Data Summary - Mill No. 8	20
  9  Mill Data Summary - Mill No. 9	21
 10  Total Suspended  Solids Concentration	2k
 11  Percent  Volatile Suspended Solids	26
 12  BOD Content  of Solids	27
 13  COD Content  of Solids	28
 14  Nitrogen Content of Solids	29
 15  Phosphorous  Content of Solids	30
 16  Particle Charge  Characteristics	31
 17  Mean Particle Size - Direct Count Method	3^
 18  Effect of Sample Storage on Filtered BOD	 35
 19  Effect of Sample Storage on Total BOD	36
 20  Effect of Sample Storage on Total and Volatile Suspended Solids	37
 21  Effect of Sample Storage on Total Solids	38
 22   Effect of Sample Storage on Mean Particle Size	39
 23   Effect of Sample Storage on Particle Charge	^0
 24   Secondary Effluent Solids - Mills 1 and 2	^3
 25   Secondary Effluent Solids - Mills 4 and 5	^
 26   Secondary  Effluent Solids - Mills 6 and 7	^5
27   Secondary  Effluent Solids - Mills 8 and 9	^6
28  Secondary  Effluent Solids - Mills 4 and 9	^7

                                    viii

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                              FIGURES (Con't.)
29  Suspended Solids Removal Efficiency	 52
30  Coagulation/Sedimentation Data - Mill No.  1	 58
31  Coagulation/Sedimentation Data - Mill No.  2	 59
32  Coagulation/Sedimentation Data - Mill No.  3	 60
C-l Particle Size - Mill No. 1	 82
C-2 Particle Size - Mill No. 2	 83
C-3 Particle Size - Mill No. 3	 8k
C-4 Particle Size - Mill No. 4	 85
C-5 Particle Size - Mill No. 5	 86
C-6 Particle Size - Mill No. 6	 87
C-7 Particle Size - Mill No. 7	 88
C-8 Particle Size - Mill No. 8	 89
C-9 Particle Size - Mill No. 9	 90
                                     ix

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                                   TABLES



Number                                                                  Page




   1  Summary of Post Biological Solids Characteristics	  23




   2  24-Hour Refrigerated Storage Effects	  ^1




   3  Jar Test Results - Inorganic Chemicals	  ^9




   4  Jar Test Results - Polymers	  50



   5  Chemical Conditioning	  51




   6  Suggested Media Composition	  53



   7  Suggested Media Filtration Results	  53




   8  Modified Media Composition	  5^




   9  Mixed Media Filtration Results	  5^




  10  Dissolved Air Flotation Results	  %




  11  Microstraining Results	  56




  12  Sand Filtration Results	  6l




  13  Magnetic Separation Results	  62




 C-l  Raw Data - 1976	  75




 C-2  Raw Data, Metals (Total) - 1976	  77




 C-3  Raw Data, Metals (Soluble) - 1976	   79




 C-4  Supplemental Data - 1977	   8l

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          ABBREVIATIONS AND SYMBOLS
AC
ADT
AL
API
A/S
BK
BLMGO
BS
C
CST
D
DAF
DIA
DMS
DT
E      ,
gpin/ft^
GAL/T
H
LB/D
LB/T
MG
MGD
mg/1
ml/min
mm     2
m /s/m
N
NC
NCASI
NH
NO
NEX
NPDES
F
PS
RAS
S
SOL
SWD
T/D
TKN
TOT
TS
acre
air dryed ton
aerated lagoon treatment
American Paper Institute
activated sludge treatment
bleached kraft mill
MgO base bleached sulfite mill
ammonia base bleached sulfite mill
chlorination process
capillary suction time
chlorine dioxide process
dissolved air flotation
diameter
dimethyl sulfide
detention time
caustic extraction process
gallon per minute per square foot
gallon per ton
hypochlorite process
pound per day
pound per ton
million gallons
million gallons per day
milligrams per liter
milliliters per minute
millimeters
cubic meters per second per square meter
nitrogen
north central United States
National Council for Air and Stream Improvement
ammonia
oxides of nitrogen
northeastern United States
National Pollutant Discharge Elimination System
phosphorous
pumping system
activated sludge recovery
southern United States
soluble
side-wall depth
tons per day
total Kjeldahl nitrogen
total
total solids
                      XI

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                   ABBREVIATIONS AND SYMBOLS (Con't.)
TSS            total suspended solids
TVS            total volatile solids
VOL            volume
UBK            unbleached kraft mill
UF             ultrafiltration
VSS            volatile suspended solids
W              western United States
                                     xii

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To convert from

gallon  (U.S. liquid)

gallon per minute
        (gpm)

gallon per minute per_
  square foot  (gpm/ft )

pound (Ib)

pound per ton  (Ib/t)


pound per day  (Ib/d)
million gallons per day
       (MGD)

pounds per inch
       (psi)

tons per day
       (t/d)
CONVERSION TABLE

        to
   metre3(m3)
        3
   metre  per second
   metre  per second   „
     per metre  (m /s/m )

   kilogram (kg)

   kilogram/ kilokilogr am
     (kg/kkg)

   kilogram per day
     (kg/d)
   metre  per day
     (nT/d)

   pascal (Pa)
   kilogram/day
     (kg/d)
Multiply by
3.79x10
       -3
6.31x10
       -5
6.79x10
                                    -4
4.54x10
       -1
5.00x10
       -1
4.54x10
       -1
3.79x10
6.89x10-
9.07x10
                                                                 ,+3
aStandard for Metric Practice.  ANSI/ASTM Designation:   E  380-76E,  IEEE Std
268-1976, American Society for Testing and Materials, Philadelphia,
Pennsylvania, February 1976.  37pp.
                                    xiii

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                             ACKNOWLEDGEMENTS
     Appreciation is expressed to the environmental personnel at the parti-
cipating mills for their efforts in providing information, operating data,
and securing and shipping samples.

     Valuable input was provided by the following persons who compromised
the Technical Review Committee:

                          Dr. T. R. Aspitarte
                          Mr. Curtis A. Barton
                          Mr. Russell 0. Blosser
                          Mr. Andre Caron
                          Mr. Bob Herrmann
                          Mr. Joe Kolberg
                          Mr. Ralph Scott
                          Dr. H. K. Willard
                          Mr. Gene Zanella

     Mr, John Ruppersberger, Project Officer, provided additional valuable
assistance.
                                    xiv

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                                 SECTION  1

                               INTRODUCTION

GENERAL DESCRIPTION OF THE PROJECT

     The objective of this study was to characterize the post biological
solids in secondary effluent from nine pulp and paper mills throughout the
U.S. and to identify, through bench scale tests, the tertiary solids removal
steps which produce removals great enough to justify pilot scale testing.
The study was designed to provide a better understanding of the chemical and
physical characteristics of solids in the mill effluent, and to identify
patterns of variance in these characteristics as they occur within a variety
of pulping processes, geographical locations, and types of biological secon-
dary treatment.  The knowledge gained in this study should provide a basis
for designing a more detailed mill-specific pilot scale study of solids re-
moval techniques .

     The project was funded by the Environmental Protection Agency (EPA).  A
Technical Review Committee was formed to provide input to the project during
organization and data analysis.  The committee included representatives of
the industry, EPA, Institute of Paper Chemistry and NCASI (National Council
for Air and Stream Improvement).

     In developing 1983 effluent guideline limitations for the pulp and paper
industry, EPA considered several alternatives for additional end-of-pipe
treatment to remove suspended solids from biologically treated effluent.  The
technology identified in the development documents was based primarily on
municipal wastewater treatment experience, since few pulp and paper mills
had applied post biological solids removal technology.  As a result, the
data base from which to forecast suspended solids removals achievable on
pulp and paper effluents is severely lacking.  Moreover, the liquid-phase
chemical constituents in biologically treated pulp mill effluents have dis-
persant properties which make coagulation and particle separation difficult
in comparison to municipal effluent.

     These facts led EPA to undertake the characterization studies reported
herein, in an attempt to generate a more complete data base on the post bio-
logical solids characteristics and susceptibility to removal.

     The results of this study, coupled with the subsequent  pilot  testing,
should provide a better understanding of the technology necessary  to meet
future effluent suspended solids guidelines.

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PROJECT CONCEPTION

     An important factor  in the design of this study was the probable re-
quirement  for  tertiary  treatment to remove post biological suspended solids,
as a result  of application of effluent limitation guidelines.

     This  study was  conducted in three steps to provide both a knowledge of
the character  of post biological suspended solids, and to determine the most
promising  methods for removing these solids.

     The first step  (Phase la) consisted of a systematic study of the
quantity and character  of suspended solids in the effluents from nine mills,
to provide a current picture of the post biological solids which are present
in secondary-treated effluent.  A review of related literature provided back-
ground information on the quantity and character of typical pulp and paper
mill secondary effluent,  and on the most effective solids removal methods.

     Mill  samples were  analyzed for types of suspended solids present and
physical and chemical characteristics of those solids.  An attempt was made
to correlate these data with the type of pulping process as well as the
treatment  process employed at each mill.

     The second step (Phase Ib) consisted of an evaluation of the various
chemical coagulants  and organic polymers available, to determine the most
effective  chemical and  the optimum dosage.  The chemicals tested were chosen
on the basis of the  characteristics of the solids determined in the first
step.  On  this basis, the number of coagulants considered was reduced to
three inorganic chemicals and five polymers.

     The third step  (Phase Ic) included bench scale testing of six specific
alternative  processes which might be used for post biological solids removal.
The guidelines Development Document identified mixed media filtration as the
most likely  process, but  also suggested microstraining, coagulation/sedi-
mentation, flotation, and sand filtration.  These five plus magnetic separa-
tion were  tested on  samples from four of the nine representative mills.

     Analyses  were performed in both EPA and CH2M Hill Laboratories in
Corvallis, Oregon.

     Three of  the test  mills were located close enough to allow analyses
to be performed on "fresh" samples.  However, to try to determine the
effect of  time degradation on samples from more distant mills, the local
samples were split into two components.  One component was immediately
analyzed and the other  refrigerated for approximately 5 days  (the maximum
transport and  storage time from the other six mills).  The same analyses
were performed at the end of the storage period to try to develop factors
related to storage effects.

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                                 SECTION 2

                                CONCLUSIONS

     Characterization of the suspended solids in biologically treated efflu-
ent from nine pulp and paper mills covering a range of pulping processes,
geographical locations, and biological treatment processes was completed,
along with bench scale comparative evaluation of potential treatment proces-
ses for removal of the post biological solids for four mills.

     Coagulation/sedimentation, mixed media filtration, sand filtration,
microstraining, dissolved air "flotation and magnetic separation were com-
pared to determine the relative degree of suspended solids removal in each
process, and to identify the most promising process(es) for subsequent on-
site pilot testing in a later phase of the project.

     Conclusions from the characterization and bench scale comparison tests
are:

Characterization

     Average suspended solids (TSS) levels for the mills studied were gen-
erally between 50 and 100 mg/1.

     The physical and chemical characteristics of the post biological solids
were variable, but overall averages showed 0.4 kg(lb)BOD/kg(lb)TSS, 1.8 kg
(lb)COD/kg(lb)TSS, 0.83 kg(lb)VSS/kg(lb)TSS, 0.07 kg(lb)N/kg(lb)TSS, 0.01 kg
(lb)P/kg(lb)TSS.  The solids had a mean particle size by volume of 0.5 to
1.5 microns, and were negatively charged.

     The concentration of TSS, based on a mill to mill comparison, showed no
clear correlation to the type of pulping process, geographical location, or
type of treatment process (i.e., aerated lagoon versus activated sludge pro-
cess).  In general, the range of TSS levels measured in three separate com-
posite samples from the same mill was comparable to the difference in TSS
levels observed from mill to mill.  Examination of variations at individual
mills, from mill NPDES permit reports, indicates wide variations in TSS
levels at a given mill.  At some mills, the long-term NPDES data indicates a
seasonal increase in TSS levels during cold weather months.

     The BOD and COD per unit of TSS indicates a largely carbonaceous makeup
of the post biological solids.  The BOD and COD per unit of TSS were gen-
erally higher for higher-rate treatment systems (i.e., short lagoon retention
time or low activated sludge age), but otherwise did not differ according to
mill pulping process or location.

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      The volatile  solids content  (VSS/TSS) of the post biological solids
 shows a possible relation  to mill product in that high TSS ash content was
 observed at mills  using inorganic fillers and additives.  A secondary effect
 appears to be  treatment system loading rate, with the high-rate systems
 showing a higher volatile  (lower ash) TSS.

      The nitrogen  and  phosphorus content of the post biological solids sug-
 gest  that the  solids are primarily biological in nature.  Apparent solids
 crude protein  content  (Kjeldahl N x 6.25) ranged from 25 to 75 percent by
 weight, and averaged about 40 percent.  Comparison of N.and P content of the
 post  biological solids with bacterial culture data suggests that on average,
 perhaps one-fourth of  the  solids are of non-biological origin.  Individual
 mill  data indicate that the non-biological fraction may range up to one-half
 of the TSS.

      Negative  particle charges were observed in all samples.  There was no
 correlation between magnitude of particle charge and TSS concentration.

      The mean  particle size data show that a major proportion of the sus-
 pended solids  are  less than a few microns in diameter, and will likely re-
 quire coagulation  to be amenable to physical removal down to low TSS levels.
 Correlation between size distribution and TSS susceptibility to removal by
 treatment was  poor.

      Refrigerated  storage  for a period of up to 5 days shows no conclusive
 evidence of significant changes in the characteristic parameters measured in
 this  study when compared to fresh 24-hour composite samples.

      Storage during 24-hour composite sample collection showed no signifi-
 cant  difference in TSS concentration as compared to fresh grab samples col-
 lected during  the  same period.  However, solids characterization studies were
 performed on 24-houtx itpmpafeite samples only, so no data were obtained which
 would quantify the storage effects during the 24-hour composition period.
 Sample visual  appearance and Imhoff cone observations suggest that some type
 of natural coagulation may occur during the compositing storage period.  This
 emphasizes the need for pilot data intended for commercial  scale-up  to be
 collected on fresh effluent.

      Metals analysis of the effluent samples before and after filtration,
 by argon plasma emission spectrometry, were not sufficiently  sensitive  to
 allow assay of the inorganic constituents in the post biological solids by
 difference.  While the analytical sensitivity to determine  weight-percent
 metals in the  solids was not achieved, there was no evidence  of  gross  en-
 richment of metals in  the  solids such as might occur by adsorption on  floe
 particles.

     Microscopic observation of the samples showed the presence  of bacteria
and particulate debris of  unidentified origin.  Fiber-type  solids were  found
only on occasion and represented only a minor proportion  of the  total  parti-
cles observed.

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Coagulant Testing

     Analysis of alum, ferric chloride and lime as coagulants revealed that
alum provided the most consistent flocculation at minimum dosages.  Lime at
dosages short of those inducing complete precipitation  (including color)
was least effective.  Ferric chloride was comparable to alum in some tests,
but provided less consistent flocculation at a given dosage on samples from
the same mill.

     Of the five polymers tested, none appeared significantly superior to the
others.  Nalco  634 and Percol 722 produced slightly lower supernatant TSS in
jar testing.  Nalco 634 liquid polymer was selected for use in the bench tests
because it was  easiest to mix and meter.

     Considerable variability in optimum coagulant dose was observed, both
from mill-to-mill and on different samples from the same mill.  This suggests
that full-scale pulp mill effluent coagulation facilities would require fre-
quent monitoring and dosage adjustment.

     Three methods of selecting optimum coagulant dosages were studied:  jar
testing, Buohner funnel freeness testing, and capillary suction time (CST)
monitoring.  Visual observation of jar tests was most successful in these
studies.

     The Buchner funnel or CST methods might be perfected as a control techni-
que with further development.  The mixed results in these studies were ob-
tained because  of overall net decreases in freeness which resulted from coag-
ulant addition.

     Alum dosages for optimum floe formation ranged from 40 mg/1 to 180 mg/1
(as Al- (S0,)_) for the four mills studied.  A concurrent polymer addition of
2 mg/1 was judged optimum on the basis that significant further floe improve-
ment was not realized until very high (5 to 10 times greater) polymer dosages
were used.

     TSS levels typically increased by up to several hundred mg/1 upon coagu-
lant addition at levels sufficient to produce floe formation.  The implication
of this phenomenon on the disposal of post biological solids removed by tech-
niques requiring coagulation is significant.  The amount of solids (dry weight
basis) for disposal will be much greater than the apparent (influent minus
effluent) quantity.

Mixed Media Filtration

     Evaluation of five media combinations on one mill effluent indicated that
a mixture of 30 percent Ilmenite (0.2 mm grain size), 30 percent sand  (0.9 mm
grain size and 40 percent anthracite (1.5 mm grain size) gave best TSS removal.
Further study would be needed to determine if the optimum media combination
is variable by mill.

     TSS removal at a filtration rate of 3.4xlO"3m3/s/m2(5gpm/ft 2)  ranged from
43 to 69 percent without chemical coagulation, and from zero to 85 percent

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with coagulation.  The use of coagulants in an  attempt  to  improve micron-
size particle removal was generally ineffective because of the  large  in-
creases in TSS level upon coagulant addition.

     Consistent TSS removals to levels below 30-50 mg/1 were  not achieved  in
these tests; on-site pilot testing would be needed to define  actual achiev-
able TSS levels.

Dissolved Air Flotation

     Dissolved air flotation tests at air-solids ratios of 0.06, 0.03 and
0.01 showed poor TSS removals.

     On three of the four mills tested, TSS removals were  less  than 10 per-
cent in every case and averaged nearly zero.  On the remaining  mill,  re-
movals of the order of 20 percent were observed.

Microstraining

     Batch microstraining tests using 1 micron to 74 micron fabric mesh
showed TSS removals  in the range of zero to 37 percent  without  chemical
coagulant addition.  More than 20 percent removal was observed  at only one
of  the four mills tested; two of the mills showed zero  removal.

     TSS increases were observed whenever coagulants were  used.

     The small micron mesh (less than 10 microns) blinded  almost immediately,
and no data were collected for these fabrics due to the impracticality of
the short run times.

Coagulation/Sedimentation

     Settling column tests conducted on three of the mill  effluents  with and
without chemical coagulant addition showed TSS removals of zero to  20 percent
without chemical addition, and net TSS increases with chemical  addition.

     For the test runs with chemical coagulation, a definite floe formation
and settling occurred.  However, this appeared to result from the substantial
increase in TSS upon coagulant addition.  The final supernatant TSS from the
coagulated samples never recovered to less than the starting TSS,  in spite
of  the formation and settling of a floe.

     Massive chemical doses sufficient to precipitate  color might effect net
TSS reductions by coagulation/sedimentation, but this  level of coagulation
was excluded from this study.

Sand Filtration

     Batch tests with a single-media 0.4 mm sand at 3.4xlO~3m3/s/m2(5gpm/ft2)
showed TSS removals between 14 and 68 percent without  chemical addition and
zero to 71  percent with chemical coagulants.

     The results of the sand filtration tests were generally similar  to the

                                      6

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mixed media filter tests.  (See previous discussion.)

Magnetic Separation

     Magnetic separation tests using a Frantz Ferrofilter with both steel
wool and steel disc media showed typical TSS removals of the order of 20
percent or less.

     Sample conditioning treatments including polymer and magnetite, alone
and in combination, failed to significantly improve TSS removal.

Overview of Bench Testing Results

     Of the processes tested, filtration (sand or mixed media) showed the
greatest potential for post biological solids removal.

     Chemical coagulation with alum and polymer was generally ineffective in
improving TSS removal.  The TSS levels consistently increased upon coagulant
addition in levels sufficient to form a visible floe, and the net effect on
TSS removal was typically deterimental rather than beneficial.  (Color-pre-
cipitating chemical dosages were excluded from this study by design.)

     The effluents tested showed variable TSS removals, from a standpoint of
both mill-to-mill comparisons, and repeat observations at a given mill.  On-
site pilot testing is needed to adequately define consistently achievable
TSS removals.

     TSS removals down to the 5-10 mg/1 levels commonly observed in municipal
wastewater treatment were not achieved (an exception is mill 2, where initial
TSS levels were of the order of 10 mg/1).

     No definite correlation of TSS susceptibility to removal was observed
with respect to mill process, location, treatment process, or TSS chemical
and physical characteristics.

     The availability of a reliable analytical technique to determine parti-
cle size distribution by weight (rather than number of particles) is probably
a prerequisite to establishing reasonable correlations.

     Effluent monitoring data from some mills suggest that seasonal (temper-
ature-related) changes in TSS levels may be significant.

-------
                                  SECTION 3

                               RECOMMENDATIONS


     Pilot-scale studies to define performance levels for post biological  sol-
 ids  removal should be directed toward filtration (sand or mixed media).

     Pilot-scale studies should be run at individual  mill sites using fresh
 effluents.
                                               A O
     Pilot plants should be at least of the 10" m /s  (several  gpm)  size  to
 generate sufficient backwash for backwash solids testing.  Testing  should  in-
 clude  investigation of backwash disposal, fines recycle,  and headless buildup
 rate.  The pilot plant program should also include further evaluation of sea-
 sonal  variations.

     A good analytical technique to measure TSS size  distribution by weight
 should be established, to allow better evaluation of  observed solids removal
 performance.

     Analysis of the metals content of post biological solids - particularly
 calcium and magnesium - should be made to help identify the presence of  non-
 biological solids such as calcium-lignin precipitates.

     Further research to identify coagulants which can effectively  agglomer-
ate fine particles without increasing net TSS levels  (short of inducing  mas-
 sive color precipitation) is needed.

     Variation in post biological solids levels at individual  mills should be
studied to fully identify the effects of such variation on achievable solids
removal efficiency.  In particular, the effect of seasonal variation should
be included.

-------
                                  SECTION 4

                              PROJECT EXECUTION

PHASE la - SOLIDS CHARACTERIZATION

     An informal literature review provided the necessary technical  and per-
tinent industrial data to develop this study.   This information guided the
design of the study and analysis of results.  The review was compiled from
sources such as EPA, NCASI (National Council for Air and Stream Improvement),
API (American Paper Institute), and other published sources, and is  included
in Appendix A.

     The review was separated into three sections:  1) General  Studies on
Solids Characterization and Removal Processes, 2) Specific Solids Removal
Processes, and 3) Municipal Treatment Systems Solids Removal.

     Industry cooperation was a key to the success of this project.   Parti-
cipant mills provided data about mill processes and treatment designs, sam-
pling systems and special problems unique to each mill.

     Site visits to each of these mills provided data on the mill pulping
process, bleaching sequence, treatment design and past operating experience.
At the same time, provisions were made for three samples (24-hour composite)
of mill effluent to be taken.  All samples were refrigerated in transit ex-
cept the three samples from mills close to Corvallis, Oregon.  These three
fresh samples, analyzed immediately, provided a baseline for time degrada-
tion factors.

     To determine the full range of post biological solids present in these
samples and their physical and chemical properties, a number of tests were
run.  Eight of the tests were performed by EPA's laboratory analytical
support staff.  These tests were for COD (chemical oxygen demand; total and
filtered), total suspended solids, volatile suspended solids, total  and
dissolved volatile solids, phosphorus (total and filtered), Kjeldahl nitro-
gen (total and filtered), ammonia, particle size (Coulter counter) and metals
(total  and filtered).

     The following tests were run in the CH2M Hill Laboratory:

     1.  Particle size, by the direct count method using a microscope
         with a calibrated eyepiece.

     2.  Particle charge, by measuring zeta potential.

     3.  BOD (biochemical oxygen demand, total and filtered), by the

                                      9

-------
        standard methods procedure.  For purposes of this study, the filtered
        BOD was considered to be that passing the glass fiber filter used in
        the TSS determination.

     Results of these tests are included in Section 5,  Results and Discus-
 sion.

 PHASE  Ib - COAGULATION EXPERIMENTATION

     This phase included evaluation and optimization of chemical coagulants
 for use in the bench scale tests (Phase Ic).

     The chemicals tested included ferric chloride, alum and lime in combi-
 nation with five polymers, to evaluate their relative coagulation efficiency.

     The five polymers used were:  Nalco 634, Percol 722, Calgon WT-300,
 Hercules 859, and Dow C31.

     Four of the nine mill effluent samples were tested in Phase Ib.

     The analysis at this stage included:

     1.  Jar testing.

     2.  Sludge filterability (Buchner funnel method).

     3.  CST (Capillary Suction Time).

 PHASE  Ic - SOLIDS REMOVAL TECHNIQUES

     This phase covered evaluation of six potential tertiary unit processes
 for solids removal.  Bench scale testing was performed on effluent samples
 from the same four mills tested in Phase Ib.

     The purpose of this phase was to evaluate the relative efficiency of
 each process for post biological solids removal.  Analysis of these data
 provided a reasonable basis for determining which unit processes would merit
 further testing in the Phase II work.

     The results were analyzed to determine:  1) a relative ranking of each
 of the tertiary solids removal steps based on solids removal efficiency and
 performance consistency, 2) the impact of the range of solids characteristics
measured in Phase la on the performance and relative ranking of tertiary
 solids removal steps, and 3) a sound technical basis for subsequent larger
 scale  pilot testing of the two or three most attractive solids removal unit
processes.

     The specific procedures used in the bench scale analysis of each of 6
unit processes follows:
                                      10

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1.    Mixed Media Filtration.   Testing was conducted in 1-
     inch diameter laboratory filters operated in batch
     runs.  The actual testing was divided into two steps.
     The first step consisted of media evaluation, in which
     preliminary test runs of three different media combina-
     tions on one mill effluent were made.  The results of
     this initial testing were used to select the best media
     combination.

     Next, the performance tests were run using the selected
     media combination on the four mill effluents.  TSS
     analyses were run on effluents with and without the
     chemical conditioners selected in Phase Ib.

     These tests provided a measure of the solids removal
     performance capabilities of mixed media filtration.

     One effluent sample was also shipped to a filter vendor
     for independent batch tests, to capitalize on vendor
     experience in this area.

2.    Flotation.  Dissolved air flotation tests for post-
     biological solids removal were made using a 2-liter,
     batch pressure chamber.   Tests were conducted for three
     air/solids ratios on the four effluent samples, with
     and without the chemical conditioners selected in Phase
     Ib.

     Suspended solids removal efficiency was measured,
     together with float volume and float concentration.

3.    Microstraining.  Batch tests were run using four sepa-
     rate fabrics covering a range of micron sizes.  These
     tests were conducted on each of the four mill effluent
     samples selected, and were run with and without chemical
     conditioners.

     The results of these tests gave a qualitative assessment
     of the impact of fabric opening size on suspended solids
     capture, the impact of chemical coagulation on relative
     rates for strainer performance and a qualitative assess-
     ment of probable strainer flow rates.

4.    Coagulation/Sedimentation.  Batch tests run in a 6-inch
     diameter plexiglass settling column determined the sus-
     pended solids removal achieved by chemical coagulation and
     gravity clarification.  The coagulant dosage was based
     on the results of Phase Ib.  Suspended solids removal
     versus depth was measured to determine removal efficiency.

5.    Sand Filtration.  This test run simulated a single-
     media filter.  TSS removal and blinding rate were

                           11

-------
    measured.  A preliminary test run was made on a single effluent  source,
    using two sand grain sizes, to evaluate media effects.   After  a  grain
    size selection was made, each of the mill  effluents  was tested.

    Three test runs were conducted to simulate mechanical  cleaning of  the
    sand surface; two were run on a freshly drained sample, and  one  on a sam-
    ple allowed to air dry for 24 hours prior  to scraping  the  surface  layer.

    The thrust of the sand filtration experiment was to  pursue a low-cost
    technology which might apply where natural site conditions allow the use
    of large percolation beds for solids removal.

6.  Magnetic Separation.  Magnetic separation  is a relatively  new  process
    which has had very little commercial application for this  purpose.  A
    laboratory magnetic separation test unit (a Grantz Ferrofilter), loaned
    by the U.S. Bureau of Mines, Albany, Oregon, was used  for  this testing.

    The goal of the magnetic separation test was to obtain sufficient  data
    for a cursory evaluation of magnetic separation for  suspended  solids re-
    moval efficiency.

MILLS SELECTED FOR USE

     Nine producing pulp and paper mills participated in this  study.   Each
mill provided data in their operations, included herein  as  Mill  Data Summaries
(Figures 1-9).  The mills also allowed on-site visits and  provided samples of
their effluent.

     The mills were selected on the basis of location, pulping process type,
effluent treatment type, size and production,  and willingness  to participate.
The Mill Data Summaries which follow give information about the  mill and gra-
phic representations of the treatment system used.

     Of the nine mills, six were located in the west (mills 1  through  6), one
in the southern region (mill 7), one in the north central  region (mill  8),
and one in the northeastern region (mill 9).  Three of the western mills (mill
1, 2, and 3) were within one hour's drive of the EPA and CH2M  Hill laborator-
ies.

     The mill processes included bleached and  unbleached Kraft and bleached
sulfite with both magnesium and ammonia base.   Their production  ranged from
3.11 x 105 kg/d (343 tons per day (t/d)) to 1.45 x 10& kg/d (1,600 t/d) of
paper, kraft or sulfite products, or intermediary products such  as bleached
or specialty pulps.  All mills except 2 and 9  recovered  some by-products from
their in-piant processes.  All of the Kraft mills except mills 2 and 4 recov-
ered methanol and mill 8 operates a methanol stripper with off-gas combustion
in the lime kiln; mill 5 recovered crude tall  oil; and mills 6,  7, and 8 re-
used condensate.                                   \

     The mills treat their effluent with either aerated  stabilization  or acti-
vated sludge treatment systems.  Most of the treatment systems include primary
clarification and aerated ponds (mills 2, 3, 5, 7, and 8).  Mill 2 also in-

                                      12

-------
                                    Figure  1
                              MILL DATA  SUMMARY


 MILL NO. 1             LOCATION:  West

 TYPE:              Unbleached Kraft &  NSSC

 PRODUCTION:        Kraft Coarse & Corrugating Paper-670T/D
                    NSSC Corrugating Medium - 230 T/D
 PULPWOOD:



 BLEACH PLANT:


 PAPER MACHINES:

 ADDITIVES:
86% Softwood Chips
14% Waste Paper

N/A

3 Fourdrinier(164", 169", 184")
                   Wet end — Sizing: Alum Rosin;
                   Dry end — Wheat or Corn Starch
                            no Fillers; no  Defoamer
RECOVERY SYSTEM:  NSSC - 3 Stage Washing
                   Kraft - 4 Stage Washing
                   600 T/D Recovery Boiler
COMMENTS:
                   Turpentine Recovery — 1  Gal/T
                   30-40,000 LB/D Na2SO4 Lost to Sewer
                                   Guargum; UF  Resin
 EFFLUENT TREATMENT SYSTEM
   FROM
   MILL
                    PRIMARY
                 SETTLING POND

                  VOL - 7 MG
                  D.T. = 3.5 HR
                    @  10 MGD &
                    POND 80% FULL
                    OF SOLIDS
                                 O     O     O

                                 O     O     O    O

                                 O     O     O    O
                               V.	/


                                   AERATED POND
                                VOL = 90 MG

                                D.T. = 9 DAYS @ 10 MGD
                                TOT.  AERATION  - 550 HP
                                                                                     TO
                                                                                     RIVER
                                                                                    -*
 SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:
                                       FLOW

                                       BOD
                                       TSS
TYPICAL SECONDARY TREATED EFFLUENT: BOD
                                      TSS
                             10.2 MGD (8.8 MGD-AVG TO
                             RIVER) (11,300 GAL/T)
                             257 MG/L (21,800 LB/D) (24 LB/T)
                             105 MG/L (7,732 LB/D)  (9 LB/T)

                             31 MG/L (2,286 LB/D) (2.5 LB/T)
                             62 MG/L (4,556 LB/D) (5 LB/T)

-------
                                   Figure  2
                             MILL DATA  SUMMARY
MILL NO. 2


TYPE:


PRODUCTION:
   LOCATION:  West

Bleached Kraft/Tissue

Tissue - 250 T/D
Bleached Pulp - 93 T/D  Air dry
PULPWOOD:



BLEACH PLANT:


PAPER  MACHINES:


ADDITIVES:
65% Chips (Softwood)
35% Sawdust  (Softwood)

CEHH - With Ca(OCI)2 Oxidation of E Stage Effluent for
Color Reduction  or  CHEH
2 - 194" Yankee Machines

Wet End - Dyes, CaCl2, Slimicide
Dry End — Yankee Release Agent
 RECOVERY  SYSTEM:   4 Stage Washing
                    1 B&W 400 T/D Recovery Boiler
COMMENTS:
No By-Product Recovery
EFFLUENT TREATMENT SYSTEM
SOLIDS ACID SEWER (3.5 MGD)
PRESS LAND 1
DISPOSAL ^ 1 r
ALKALINE 1 1 I '
SEWER JL,. ± JjK O
11.5MGD^O +(\ ,8 ,<%
O

O 0 I x.
O O [— >
0 0 -^
O O ^1
V
TO
RIVER
s
PRIMARY CLARIFIER AERATED PONDS (2) SETTLING
200' DIA. TOT. VOL = 216 MG BASIN
12' SWD D.T. = 12 .DAYS
TOT. AERATION = 600 HP
SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:    FLOW   =  14.9 MGD (43.000 GAL/T)
                                      BOD    =  NO DATA
                                      TSS    =  NO DATA

TYPICAL SECONDARY TREATED EFFLUENT: BOD    =  1,550 LB/D; 12.5 MG/L (4.5 LB/T)
                                      TSS    =  2,465 LB/D; 20 MG/L (7 LB/T)


                                          14

-------
                                   Figure  3
                             MILL  DATA SUMMARY
MILL NO. 3


TYPE:


PRODUCTION:
   LOCATION:   West


Unbleached  Kraft

Kraft Paperboard - 1260 T/D
PULPWOOD:
100% Softwood Chips
BLEACH PLANT:


PAPER  MACHINES:


ADDITIVES:



RECOVERY SYSTEM:



COMMENTS:
N/A

2 Fourdrinier Machines (148" & 256")

Wet End - H2S04, Alum, Cationic Starches, Polymers
Dry End — Potato or Corn Starch
Fillers   - 5-6 LB/T Simplot Clay, <1  LB/T Defoamer, Sizing Agent
Washing - Cont., 3 Stage; Batch - 4 Stage
2 CE 2400 T/D Recovery Boilers

Recover Turpentine & Methanol

EFFLUENT TREATMENT SYSTEM
FROM /""""X
(5.0 MGD) y / 1
CH»
FROM ^ P.S.
PAPER MILL fc, -^->. I
(4.3 MGD) IV ^r\ 1

L^ -^
PRIMARY FLOTATION
SCREEN CLAHfFIER THICKENER
130' DIA. 45' DIA.

f ^\
O O
e o
o o
© 0
0 0
^ J
AERATION POND
VOL = 69 MG
TO
RIVER
P.S.
                                                        D.T. = 5.5 DAYS @ 10 MGD
                                                          & 14 MG SLUDGE
                                                          ACCUMMULATION

                                                        TOT. AERATION = 750 HP
SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:
                  FLOW
                  BOD
                  TSS
TYPICAL SECONDARY TREATED EFFLUENT:  BOD
                                       TSS
10 MGD; 8,000 GAL/T
25,000 LB/D;300 MG/L;20 LB/T
17,000 LB/D; 144 MG/L; 10 LB/T

3,200 LB/D; 38 MG/L
8,300 LB/D; 100 MG/L
                                        15

-------
                                    Figure  4
                              MILL DATA  SUMMARY
 MILL NO. 4


 TYPE:


 PRODUCTION:
   LOCATION:  West

MgO Base Bleached Sulfite

Dissolving Pulp  - 225 T/D
Specialty Pulps  - 225 T/D
 PULPWOOD:



 BLEACH PLANT:


 PAPER MACHINES:


 ADDITIVES:
75%  Roundwood
25%  Chips
(Mostly Softwood)
CEH

None

None
 RECOVERY SYSTEM:
 COMMENTS:
4 Stage Washing
3 Recovery Boilers

Treat Evaporator Condensate & Venturi Scrubber Water
EFFLUENT TREATMENT SYSTEM
(16 MGD - LOW STRENGTH) RAS

a
mr\tiH Rflii i __^_ ^* *
(4 MGD - HIGH STRENGTH)
STORAGE
POND
VOL = 12 MG
(SPILL STORAGE)

J OOOOOOO
X. ^
M ooooooo
> V f
J
M ooooooo
> <
* ooooooo
t ^
AERATION BASINS*4'
TOT. VOL = 20 MG
D.T. - 5 DAYS @ 4 MGD
TOT. AERATION = 3200 HP
|U
n
SECON
CLARI
(1) 50
(1) 60
12
^
DARY
FIERS
' DIA. TC
' DIA- D
SWD °'
t
TO
RIVER
SETTLING PONDS*4'
)T. VOL = 32 MG
T. = 1.6 DAYS <°> 20 MGD
SELECTED EFFLUENT DATA
TYPICAL PRIMARY TREATED EFFLUENT: FLOW - 4 MGD; 9,000 GAL/T
(EXCLUDING LOW STRENGTH FLOW) BOD = 110,000 LB/D; 3,300 MG/L;240 LB/T
TSS •* = 5,000 LB/D; 150 MG/L;11 LB/T
TYPICAL SECONDARY TREATED EFFLUENT: BOD
(BEFORE SETTLING  PONDS)                Tss
                             6,000 LB/D;180MG/L
                             26,000 LB/D; 780 MG/L
                                           16

-------
                                     Figure  5
                              MILL DATA SUMMARY
 MILL NO. 5


 TYPE:


 PRODUCTION:




 PULPWOOD:
   LOCATION:  West

Bleached  Kraft

Paperboard  - 880
Tissue      —  50
Market Pulp- 200


100% Softwood Chips & Sawdust
 BLEACH PLANT:

 PAPER MACHINES:


 ADDITIVES:



 RECOVERY SYSTEM:



 COMMENTS:
Chips - CEHHD
Sawdust - CEHD
3 Fourdrinier Machines (216", 216",  173")
1 IMPCO Wet Machine
Wet Strength    Coating - Clay
Sizing Agents
Dyes
Recovery Boilers:
                      Recover Tupertine
                      & Crude Talc Oil
                      Soda  Losses: 71 LB/T
       Ti02

CE 150 T/D
CE 300 T/D
B&W 300 T/D
B&W 400 T/D
Slimicides
Corrosion Inhibitor

4 Stage Washing
EFFLUENT TREATMENT SYSTEM
FROM
BLEACH PLANT
(10 MGD)
FROM / \
(20 MGD) V J
SOLIDS -
VACUUM FILTER
^ PRESS
HOG FUEL
PRIMARY
CLARIFIER
C\
P.S.

X" ~^v
o o o N.
o o o >v
000 0\^ R?VER
V )
AERATED POND
110 AC.
VOL = 500 MG
                    250' DIA.
                                                         D.T. = 16.6 DAYS @ 30 MGD
                                                         TOT. AERATION = 1,950 HP
SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:
                  FLOW
                  BOD
                  TSS
TYPICAL SECONDARY  TREATED  EFFLUENT: BOD
                                       TSS
            29.7 MGD (25,300 GAL/T)
            364  MG/L (90,200 LB/D) (80 LB/T)
            147  MG/L (36,400 LB/D) (32 LB/T)

            33 MG/L (8,175  LB/D) (7  LB/T)
            79 MG/L (19,600 LB/D) (17 LB/T)
                                             17

-------
                                    Figure   6
                             MILL DATA SUMMARY
 MILL NO.  6


 TYPE:


 PRODUCTION:
   LOCATION:   West

Bleached & Unbleached  Kraft; NSSC

Kraft Linerboard   - 450 T/D
NSSC Corrugating Medium — 250 T/D
Bleached Kraft     - 200 T/D
 PULPWOOD:



 BLEACH PLANT:

 PAPER MACHINES:


 ADDITIVES:



 RECOVERY SYSTEM:
70% Softwood Chips
25% Waste Wood
 5% Roundwood (Eucalyptus)
CEHPH

3 Fourdrinier (144", 155", 120")
Alum     Clay Coating
Rosins    Biocides
Polymers  Defoamer
Dyes
Onalon (Cr)
Waxes
 COMMENTS:
Turpentine Recovery  30 GPD
Soap Recovered — Burned
 EFFLUENT  TREATMENT SYSTEM

                 SOLIDS -
                 VACUUM FILTER
                 PRESS
                                  RAS
    BAR
  SCREEN
                              VOL  1 75 WIG
                              D.T.
                                   2.6 HR
                                  16 MGD
                          AERATION BASIN

                            VOL = 1.8  MG
                            D.T. = 2.7 HR
                              @ 16 MGD
                            HP = 500
                                                                                  EFFLUENT
                                                                                   HEAD
                                                                      SECONDARY  CONTROL
                                                                      CLARIFIERS   TANK
                                                                      (21 135' DIA.
                                                                         13" SWD
                                      12' DIA.
                                      22' HIGH
SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:
                                       FLOW
                                       BOD
                                       TSS
TYPICAL SECONDARY TREATED EFFLUENT:  BOD
                                       TSS
                            13 MGD; 14,500 GAL/T
                            27,000 LB/D;250 MG/L; 30  LB/T
                            11,000 LB/D;101 MG/L; 12  LB/T

                            4,300 LB/D;40 MG/L
                            7,600 LB/D;70 MG/L

-------
                                         Figure  7

                                   MILL  DATA SUMMARY


       MILL NO. 7             LOCATION: South

       TYPE:                Unbleached Kraft

       PRODUCTION:         Paperboard - 1200 T/D
                           Kraft Wrap & Bag - 400 T/D
                           (150 T/D Bleached Kraft)
       PULPWOOD:
                           40% Chips (All Softwood)
                           60% Roundwood
       PAPER MACHINES:


       ADDITIVES:
5 Fourdrinier Machines (134", 136", 167", 157", 216")

Alum   Rosin Sizing Agent
Wax
Defoamer
       RECOVERY SYSTEM:   2 Recovery Boilers
                           3 & 4 Stage Washing
       COMMENTS:
Recover Turpentine, Soap, DMS
Soda Loss - 180,000 LB/D
       EFFLUENT  TREATMENT SYSTEM

                        SOLIDS -
                       .VACUUM FILTER
FROM
MILL
(26 MGD)
                            000000

                            o  o  o   o  o   o  o

                                       o  o   o  o
                              PRIMARY
                              CLARIFIER

                              300' DIA.
                              11.5' SWD
      SELECTED EFFLUENT DATA

      TYPICAL PRIMARY TREATED EFFLUENT:
                                                                   AERATED POND

                                                                VOL = 247 MG
                                                                63 AC x 12' DEEP

                                                                TOT. AERATION   2025 HP
                                                                  (27-75 HP UNITS)
                                                                D.T. - 9.5 DAYS @ 26 MGD
                                            FLOW
                                            BOD
                                            TSS
      TYPICAL SECONDARY TREATED EFFLUENT: BOD
                                            TSS
                            27 MGD  (16^00 GAL/T)
                            76,000 LB/D; 337 MG/L; 47 LB/T
                            NO DATA


                            13,000 LB/D; 58 MG/L  (8 LB/T)
                            14,000 LB/D; 62 MG/L  (9 LB/T)
                                                  19

-------
                                    Figure  8
                              MILL DATA SUMMARY
 MILL NO.  8


 TYPE:


 PRODUCTION:
                       LOCATION:  (yjorth Central

                    Bleached Kraft

                    Coated Paper - 600 T/D
                    Bleached Hardwood Market Kraft - 325 T/D
                     83% Roundwood (~50% Hardwood)
                     17% Chips

                     Kraft - CEDED
                     Groundwood - Peroxide
                     2 Machines  (300",  167")

                     Filler Clay        Rosin Size
                     TiO2            Defoamer
                     Aluminum Hydrate
 RECOVERY SYSTEM:   1 B&W Recovery Boiler - 800 T/D
PULPWOOD:



BLEACH  PLANT:

PAPER MACHINES:

ADDITIVES:
 COMMENTS:
                    3 Stage Washing
                    Steam Stripper
                    Recover Turpentine & Soap
                    Soda Loss -20 LB/T
 EFFLUENT TREATMENT SYSTEM
                         S°UDS
                                                                         SOLIDS
                                  TOT. AERATION
                                    = 570 HP
                                  14' DEEP
                                                     D.T. = 7 DAYS
                                                       @ 30 MGD
                                                     TOT. AERATION
                                                       = 600 HP
                                                     VARIABLE DEPTH
                                                       (8-1 2 FT)
                                                                             FLOCCULATOR
                                                                              CLARIFIER
                                                                               270' DIA.
SELECTED EFFLUENT DATA

TYPICAL PRIMARY TREATED EFFLUENT:
                                       FLOW
                                       BOD
                                       TSS
TYPICAL SECONDARY TREATED EFFLUENT:  BOD
                                       TSS
                                                30 MGD (32,400 GAL/T)
                                                200 MG/L (50,000 LB/D) (54 LB/T)
                                                225 MG/L (56,300 LB/D) (61 LB/T)

                                                29 MG/L (7,260 LB/D)  (8 LB/T)
                                                57 MG/L (14,300 LB/DI (15 LB/T)
                                         20

-------
                                                Figure  9
                                         MILL  DATA SUMMARY


             MILL NO.  9             LOCATION: Northeast

             TYPE:               Ammonia Base Bleached Sulfite

             PRODUCTION:        300 T/D Pulp Capacity
            PULPWOOD:          85% Roundwood (All Hardwood)
                                15% Chips

            BLEACH PLANT:      Single Stage Hypochlorite with Post Wash

            RECOVERY SYSTEM;   2 Stage Washing
                                Liquor Evaporation and burn in steam boiler
            COMMENTS:
                    Papermaking effluent treated separately by
                    physical-chemical treatment
FROM
PULP MILL
(2.71  MGD)
            EFFLUENT TREATMENT SYSTEM
EQUALIZATION
    BASIN
                                                                             EFFLUENT
                                                                             MONITOR
                                      AERATION
                                      BASINS (2)
                                                                                           RIVER
                                BASIN 1: 510 HP - 1 MG VOLUME
                           /    BASIN 2: 510 HP - 1 MG VOLUME
                  NEUTRALIZATION
            SELECTED EFFLUENT DATA

            TYPICAL PRIMARY  TREATED EFFLUENT:
                                       FLOW
                                       BOD
                                       TSS
            TYPICAL SECONDARY TREATED EFFLUENT: BOD
                                                  TSS
2.71 MGD (4,500 GAL/T)
2375 MG/L (65,000 LB/D)  (216 LB/T)
239 MG/L (5,400 LB/D) (18 LB/T)


90 MG/L (2,030 LB/D) (6.8 LB/T)
137 MG/L (3,100 LB/D) (10 LB/T)
                                                 21

-------
eludes a primary settling basin and mill  3 a  flotation  thickener  for  primary
treatment.  Mill 1 uses a primary settling basin,  rather than  a clarifier.
Mills 4, 6, and 9 use activated sludge treatment systems.

     Flow rates range from 1.14 x 104 m3/d  (3MGD)  at  mill  9  to 1.14 x 105
nr/d (30 MGD) at mill 5.
                                     22

-------
                                  SECTION 5

                           RESULTS AND DISCUSSION

PHASE la - SOLIDS CHARACTERIZATION

GENERAL

     The analyses listed in Section 4 were run on the three samples from each
mill to determine the physical and chemical characteristics of the post bio-
logical solids.  The raw data from these analyses are included in Appendix C
(Tables C-l through C-4).  Average values of several parameters for each
sample have been plotted to provide a comparison of these parameters between
the various mills.

     Table 1 lists the observed physical and chemical characteristics of the
post biological solids.

                                   TABLE 1

                                 SUMMARY OF
	POST BIOLOGICAL SOLIDS CHARACTERISTICS	

                                         Average      Range of Averages for
                                       of all Mills      Individual Mills
BOD per unit of TSS (mg/mg")
COD per unit of TSS (mg/mg)
Volatile Suspended Solids
(% of TSS)
Nitrogen content (% of TSS)
Phosphorus content (% of TSS)
Zeta potential of TSS
(millivolts)
Mean particle size by
volume (microns)
0.40
1.8

83
7.0
1.03

-20

-
0.16-0.60
1.2 -2.8

59 - 96
4.0 -12.4
0.46-2.35

-5 - -40

0.5 - 1.5

TOTAL SUSPENDED SOLIDS  (TSS) CONCENTRATION

     Figure 10 shows a  comparison of TSS concentration of the samples
analyzed.  The range of concentrations observed was substantial, from under
10 mg/1 to over 2500 mg/1.  The greatest variation was at mill number 4,
where excess activated  sludge is wasted to the secondary clarifier effluent
and is subsequently resettled in holding ponds downstream of our sample
point.  The most extreme excursions observed at mill 4 occurred during


                                      23

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-------
treatment process operating problems.  Mill number 1  experienced a signifi-
cant increase of effluent TSS because of a seasonal  change in quantity of
effluent treated.  The majority of the mills, however,  averaged less than
100 mg/1 TSS.

     These data exhibit no significant differences attributable solely to
mill location.  The widest fluctuations both occurred in samples from mills
located in the west, but otherwise the variation in TSS levels at a given
mill were typically greater than the variation from mill-to-mill.

     Activated sludge treatment systems are sometimes considered to produce
better quality effluent.  However, this figure shows that, in general, the
aerated lagoon systems produce equal or better effluents (in terms of TSS
concentration).  This observation must be tempered by the higher feed BOD
concentrations at two of the three activated sludge plants.

     The type of pulping process showed no clear correlation with the TSS
concentration, with the variations in repeat samples of the  same mill  being
of comparable magnitude to the mill-to-mill variations.  Sulfite mill  4
showed higher concentrations, but is not directly comparable to other mills
because of high feed BOD concentrations and the previously noted sludge
wasting practices.

     The lowest TSS levels were observed at mill 2, a bleached Kraft mill
with high water use per ton of production.  This is also the newest of the
mills tested, and was designed with extensive flow segregation and spill
control facilities.

VOLATILE SUSPENDED SOLIDS (VSS)

     The percent VSS for each mill effluent sample is shown  on Figure 11.
VSS averaged 80 percent or greater for all but two of the mills tested.
VSS percent ranged from a low of 58 percent for mill  number 8 to a high of
near 100 percent for mills number 7 and 9.  Mill number 8 is the only one
that produces coated papers.  Mill 9 operates a relatively high rate acti-
vated sludge system with very low levels of influent TSS, with the result
that effluent TSS should be nearly all biologically generated.  The reason
for this high percent volatile content at mill 7 is unclear; it differs from
mills 1 and 3 primarily in its location (south) and pulpwood species.

     The lower average VSS present at mill 8 may be related to the presence
of a flocculating clarifier following the two stage lagoon,  which is used to
separate and recycle solids to the head end of the lagoon.  Also, heavy clay
and titanium dioxide usage occurs at mill 8 due to grades manufactured.  Mill
6 operates a fairly long sludge-age activated sludge process, runs some
coated grades, and also returns silt from the raw water treatment clarifiers
to the primary clarifier.  These factors may explain the lower volatile con-
tent at mill 6.

BOD/TSS RELATIONSHIP

     Figure 12 shows BOD per unit TSS data for each of the mill  samoles.

                                      25

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-------
 These data range  from a  low  of  0.16 for mill number 4 to a maximum of 0.6
 for mill  number 9.

      The  overall  average for BOD  per unit TSS was 0.4.  Correlation of BOD
 per unit  TSS with sludge age (activated sludge) and retention time (aerated
 lagoons)  shows a  general  decrease in the BOD per unit at longer sludge age/
 retention times,  except  for  mill  3 which did not follow this pattern.

 COD/TSS RELATIONSHIP

      The  relationship between COD and TSS is shown on Figure 13 for the
 mills studied. The COD  per  unit  TSS values indicate a highly carbonaceous
 material.  Average COD per unit TSS varies from 1.2 for mill number 4 to 2.8
 for mill  number 9.  Comparison  of the unit BOD with unit COD indicates that a
 considerable quantity of material not readily biologically oxidizable, is
 present in all of the effluents tested.  These data also indicate a fairly
 consistent correlation between  unit BOD and unit COD for the solids.

 NUTRIENT  CONTENT  (NITROGEN AND  PHOSPHOROUS)

      Total Kjeldahl Nitrogen (TKN as N) and total Phosphate (as P) are plotted
 as a percentage of the TSS by weight on Figures 14 and 15.  Nitrogen content
 ranged from about 4 percent  for mill number 6 to over 12 percent for mill
 number 5.  Phosphorous content  ranged from about 1/2 percent to over two per-
 cent.

      Newly-generated  bacterial  mass typically shows a nitrogen content of 11
 to 12 percent by  weight.  As the  bacterial mass undergoes respiration, the
 average percent by weight nitrogen of the mass decreases because of the
 accumulation of polysaccharide  cell wall residues.  Thus, the observed nitro-
 gen  content of a  mixed bacterial  culture having a mean cell age of 6 to 10
 days would be of  the  order of 9 percent N.  On this basis, the nitrogen tests
 suggest that,  on  the  average, the majority (approximately 75%) of the solids
 are  biological.   The  nonbiological fraction could be as high as 50% at some
 mills,  based on the individual  mill test data.

     The  phosphorous  content of biological solids averages about 1/5 the
 nitrogen  content, which  suggests  that observed phosphorous levels in the 2
 weight  percent range  would represent whole biomass.  The test results support
 the  view  that  the observed TSS  are mainly biological.

 PARTICLE  CHARGE

     Particle  charge  was  determined by measurement of the Zeta Potential of
 the  samples.   These data  are plotted on Figure 16.  Negative particle
 charges were observed in  every  sample tested, ranging from near zero to  -57
millivotls.  However,  the majority of the data were in the range of  -5 to
 -20.  The  negatively  charged particles provide a basis for the effective use
of the trivalent aluminum and iron salts as coagulants.

     There was no apparent correlation between particle charge and concen-
tration of TSS, which  suggests  that particle dispersion is due to causes

                                      32

-------
other than simple charge repulsion.  Limited observations of charge stabili-
zation by coagulant addition bears out the hypothesis that production of an
isoelectric charge condition will not insure effective coagulation and sepa-
ration.

     It is of interest to note that the third sample collected at mill 4
showed neutral particle charge, and that this sample contained several hun-
dred mg/1 of settleable solids.  As noted previously, this is representative
of an upset condition in which stable biofloc was carrying over the secondary
clarifier weirs.

PARTICLE SIZE

     Figure 17 is a plot of the mean particle size data for the nine mills.
All data shown on this figure were obtained by the microspic direct count
method.  The mean particle size for the majority of the samples was between
0.5 and 1.5 microns.
   /

     At attempt was made to refine the particle sizing by use of the Coulter
Counter.  Samples from mills number 1, 2, and 3 were analyzed by this method,
using equipment made available by the EPA laboratory in Corvallis.  Both
sizing methods resulted in similar mean particle size data for all three
mills.  However, the Coulter Counter method was subject to significant elec-
trical interference in the size range below about 0.5 microns.  Results of
analyses performed simultaneously by the EPA laboratory and Coulter Elec-
tronics, on a split sample, however, confirmed the accuracy of the data from
the EPA laboratory.  Typical plots of particle size distribution by the
direct count method are included in Appendix C (Figures C-l through C-9).

     Unfortunately, the analytical techniques did not allow determination of
the particle size distribution by weight, which is of more significance with
respect to tertiary solids removal.  It is possible that the weight fraction
greater than, say, 5 to 10 microns would correlate with percent removal by
tertiary filtration.  More research on particle size distribution by weight
is needed to explore the possibility of predicting removal efficiency, and
testing the efficiency of coagulation to create a more favorable size dis-
tribution for effective removal.

     Based on the results reported here, a major quantity of the post bio-
logical solids are less than a few microns in mean diameter, and will likely
require coagulation to be removed by physical methods.

STORAGE EFFECTS

     Since some of the samples analyzed in this study were kept in refriger-
ated storage for a period of up to a few days during shipment, it was of in-
terest to determine if storage significantly affected the solids' properties.
Analyses were performed on fresh samples and compared with those on samples
stored under refrigeration for a period of 5 days.  Figures 18 through 23
are plots of the comparative data for mills number 1, 2, and 3.  The various
fresh and stored sample data are plotted so that "no difference" is repre-
sented by the solid diagonal line on the graphs.  A consistent trend of  data

                                      33

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-------
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                            EFFECT OF SAMPLE  STORAGE ON  FILTERED  BOD

-------
                                                                                                            /
                                                                                                     INITIAL 230
                                                                                                     STORED 192
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        LEGEND
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                                         10
                                                      20
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 INITIAL SAMPLE
                                                   Figure  19
                                 EFFECT  OF  SAMPLE  STORAGE  ON  TOTAL BOD
                                                                                                         60
                                                                                                                      70

-------
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TOTAL SUSPENDED SOLIDS


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EFFECT  OF SAMPLE STORAGE ON TOTAL AND

       VOLATILE SUSPENDED SOLIDS
       100          200
        INITIAL SAMPLE


VOLATILE SUSPENDED  SOLIDS
                                                                                                                           300

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          -SAMPLE NUMBER
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                                                      Figure  21

                                EFFECT OF  SAMPLE STORAGE ON  TOTAL  SOLIDS

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           LEGEND

          *	MILL NUMBER

          '^-SAMPLE NUMBER
                                  1.6
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                                  EFFECT OF SAMPLE  STORAGE ON

                                       MEAN  PARTICLE SIZE
                                                                                                          2-3«
                                                                                     1.2       1.4       1.6      1.8

-------
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          LEGEND
         .-5—- MILL NUMBER .
        '~Z-»-SAMPLE NUMBER
                                           -10
     -30
INITIAL SAMPLE
                                                                              -40
-50
                                                                                                     -60
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                                           Figure 23
                                EFFECT OF SAMPLE STORAGE ON
                                       PARTICLE  CHARGE

-------
points above or below the diagonal would indicate a storage effect.   These
figures show no consistent significant differences resulting from 5-day
refrigerated storage of the samples, when compared with fresh 24-hour com-
posite samples.

     An additional comparison was made to determine the effect of 24-hour
refrigerated storage of a composite sample (during the sampling period) on
suspended solids concentration in comparison to grab samples collected over
the same period.  Four samples of aerated lagoon effluent were taken at dif-
ferent times during a 1-day period at mill 1.  Each sample was immediately
analyzed for total suspended solids (TSS), and the remaining portion stored
to make up a composite sample for the day.  The composite sample was also
analyzed for TSS.  Table 2 lists the average of five replicates for  each
sample, with standard deviation shown in parentheses.

                                   TABLE 2

	24-HOUR REFRIGERATED STORAGE EFFECTS	

     Sample No.                    	TSS (mg/1)
averaqe std. deviation
1 (8:00 a.m.)
2 (12:30 p.m.)
3 (4:30 p.m.)
4 (8:00 p.m.)
composite
111
104
119
108 1
101 1
10.11)
8.94)
9.89)
[ 7.30)
' 8.69)

     T-hese data provide no conclusive evidence of changes in suspended solids
concentration due to natural coagulation during 24-hour composite sampling
storage.  The.general tendency of the solids to blind the filter media before
accumulating sufficient TSS for accurate weighing contributes to the fairly
high standard deviation on replicate samples.  As a result, the variation in
individual TSS determinations overshadows any differences between the grab
and composite results.

     Although no significant increase in TSS due to natural coagulation was
observed during this test, subsequent observations of settleable solids at
the same mill suggest that some changes in solids characteristics may in fact
occur during compositing.  Grab samples placed in an Imhoff cone for 30 min-
utes showed zero to trace settleable solids, whereas the composite sample
typically contains a noticeable amount of particulate deposit in the bottom
of the container.  This amplifies the need to base final conclusions regard-
ing achievable TSS removals on pilot data collected on fresh rather than
stored effluent.

METALS

     Metal scans were performed on total and filtered samples using argon
plasma emission spectrometry.  This analytical technique was not sufficiently
sensitive to allow determination of metals content of the post biological
solids by difference (i.e., total sample minus filtered sample).  As a result

                                      41

-------
 no meaningful  data are available  on  the metal content of the TSS.

      Although  the necessary sensitivity for determining weight-percent metals
 in the TSS was not achieved,  there was no evidence of gross enrichment of
 metals on the  TSS, such as  might  occur by adsorption on floe particles.

      Metals content is an area which requires further research, since some
 researchers* have found evidence  that a significant part of bleached kraft
 mill  post biological  TSS is a calcium-lignin precipitate.  Further investi-
 gation of this hypothesis is  needed.  Particularly on the post biological
 TSS samples having low volatiles  (high ash) content, further research on the
 makeup of the  ash fraction  is also needed.

 MICROSCOPIC PHOTOGRAPHS

      Several methods  were investigated for preparation of samples to photo-
 graph.  These  included:   light microscopy - wet mount; light microscopy -
 dry mount (with and without staining), phase contrast microscopy; and electron
 microscopy.

      The wet mount method with the light microscope was not satisfactory be-
 cause of the following limitations:   A high magnification was required to
 make the small particles clearly  visible, thus making it very difficult to
 focus on a sufficient number  of particles at one time.

      Electron  microscopy was  rejected due to problems resulting from prepara-
 tion  of samples with  significant  salt concentration.  The salts crystalize
 during preparation, obscuring the solids particles.

      Phase contrast microscopy was attempted, as well as dry mount without
 staining.   However, dry mount with methylene blue staining appeared to pro-
 vide  the best  material  for  photography.  Photographs taken using this pre-
 paration method are shown on  Figures  24 through 28.

      The photos show  bacteria and some clumps of debris, but in general, do
 not indicate the presence of  fiber type solids.

 PHASE Ib -  COAGULATION EXPERIMENTATION

 GENERAL

      The purpose of this testing  phase was to evaluate the effect of various
 conditioning chemicals  on the effluent samples, and to select chemicals for
 use in the  Phase Ic bench scale testing.  The following chemicals were in-
 cluded in this  evaluation:
* See British Columbia Forest Products, Ltd., CPAR Project  Report 371-2;
Origin and Removal of Precipitated Suspended Solids  in Bleached  Kraft Pump
Mill Effluents, Sept. 30, 1976.


                                     42

-------
      50 MICRONS
          MILL NO.  1 - 450x
               UBK-AL-W
          MILL NO. 2 - 450x
              BK-AL-W
Figure 24 Secondary  Effluent Solids

          SAMPLE NO. 3
                  43

-------
    50 MICRONS
          MILL NO. 4 -  450x
              BMGO-ASW
    50 MICRONS
          MILL NO. 5 - 450x
               BK-AL-W
Figure 25 Secondary Effluent  Solids

          SAMPLE NO. 3

-------
      50 MICRONS
           MILL NO. 6 - 450x
                BK-AS-W
     50 MICRONS
          MILL NO.  7  - 450x
               UBK AL-S
Figure  26 Secondary  Effluent Solids

           SAMPLE NO. 3


                   45

-------
                  50 MICRONS
                      MILL NO. 8 - 450x
                           BK-AL-NC
fl  t'.
                 50 MICRONS
                      MILL NO. 9- 450x
                         BNHa-AS-NE
            Figure  27 Secondary Effluent  Solids

                      SAMPLE NO. 3
                              4!

-------
         MILL  NO.  4  - 1000x
             BMGO-AS-W
                              50 MICRONS
         MILL NO. 9 - lOOOx
             BNH3 AS-NE
                              50 MICRONS
Figure  28 Secondary Effluent Solids

         SAMPLE  NO. 3

                   -

-------
      Inorganic Chemicals
           Alum
           Ferric Chloride
           Lime

      Polymers
           Allied Colloids Percol 722
           Calgon WT-3000
           DOW Purifloc C-31
           Hercules Hereofloc 859
           Nalco 634

      The comparisons were made with a jar-test apparatus, using samples from
 mills 1, 2, and 3.  The general procedure for each sample was as follows:
                                  ;
      o Each inorganic chemical was tested over a range of concen-
        trations to determine the quantity required to produce
        adequate coagulation of the sample.

      o A coagulant concentration was selected and used in con-
        junction with several different concentrations of the
        polymers listed.

      o The best polymer and concentration for Phase Ic testing
        was selected from these tests, based on visual observation
        of floe formation and supernatant Total Suspended Solids
        CTSS) after settling.

RESULTS

Inorganic Chemicals

     Table 3 lists the results of jar tests using alum, ferric chloride and
lime.  Six different concentrations of each chemical were used, but TSS data
were obtained only for those concentrations which exhibited reasonable visual
flocculation characteristics (i.e.:  flocculation occured within 5 minutes
with floe particles which separated rapidly).
                                      48

-------
                                   TABLE 3

                              JAR TEST RESULTS
                             INORGANIC CHEMICALS
                                               Supernatant TSS  (mg/1)
Chemical
Alum (as Al? (SOJ.J
C* " O






Ferric chloride




Lime


Chemical Dose mq/1
0
40
80
120
160
200
240
40
120
160
200
240
120
160
200
Mill
1
87
-
_
77
98
56
28
«
80
53
47
-
175
_
-
Mill
2
4
_
_
61
7
5
-
_
-
4
0
2
_
11
-
Mil]
3
76
62
45
_
20
_
-
48
40
56
38
-
_
_
100
     Concentrations of lime ranging from 40 mg/1 to 240 mg/1  resulted in very
poor floe formation to no floe formation, and those concentrations tested
showed an increase in supernatant TSS.

     Ferric chloride additions in the range of 40 mg/1 to 240 mg/1 showed
variable results.  Mill 1 and 2 samples required about 200 mg/1  of FeClq to
achieve a reasonable supernatant TSS level.  The mill  3 sample produced good
flocculation, but the floe tended to float to the surface.

     Alum appeared to provide the most consistent flocculation and settling
for all samples, and was selected for use with polymers.  Alum also appeared
to remove some color, basically in proportion to alum dosage.

     Test runs involving varying pH during alum and ferric chloride coagu-
lation showed no dramatic effect of pH in the range of pH 5-7.  Terminal pH
for the alum coagulation was in the range of 6 to 6.5 for all samples.

     For the lime dosages tested, the terminal pH was 9.8 to 10.6 for those
                                      49

-------
 samples with  noticeable  floe development.  Higher lime dosages could have
 been used to  induce massive precipitation (including color removal) but this
 approach was  incompatible with the goals of this project.

 Polymers

      Selected polymers,  at various concentrations were added, in conjunction
 with alum at  a concentration slightly less than the minimum required to
 achieve maximum flocculation.  Polymer concentrations of 1/2 mg/1 through
 8 mg/1  were used in the  jar test apparatus.  The results of this testing are
 shown in Table  4.

                                   TABLE 4

                         JAR TEST RESULTS - POLYMERS
                           Polymer
                        Concentration
     Supernatant TSS  (mg/1)

 Mill          Mill      Mill
   1              2          3
(120  mg/1)   (160 mg/1)   (40 mg/1)
Polymer
Initial TSS
Calgon WT-3000
Hereof loc 859
Percol 722
Nalco 634
DOW C-31
(mg/1)
-
2
3
2
3
2
3
2
3
Alum
87
64
100
64
-
-
Alum
4
9
11
13
1
13
Alum
76
44
64
56
48
64
     The data indicate that most of the polymers tested showed some improve-
ment in the character of the floe, but none really stood out from the rest
in terms of TSS removal.

     Nalco 634 liquid polymer was selected for use in Phase Ic.  Percol 722
powder showed comparable TSS removals, but 634 was chosen because the liquid
was easier to work with and provided a more consistent stock solution for
polymer addition.

APPLICATION

     Jar tests were run on the samples obtained for Phase Ic testing to con-
firm the chemical concentration requirements.  The results for mill T and  2
samples showed an optimum alum concentration of 100 mq/1 (as A12 (SQ.)3).  The

                                     50

-------
 previous testing required 120 mg/1 for the mill 1 sample and 160 mg/1 for the
 mill 2 sample.  Cursory testing indicated that this change could be due to a
 greater pH shift which is presumably the result of change in alkalinity of
 the samples,  ..This .also.indicates..a substantial variability in chemical addi-
 tion requirements for these wastewaters.

      Polymer concentration requirements appeared to be about the same as that
 used previously.  Therefore, the concentrations were:  100 mg/1 alum; and
 2 mg/1 Nalco 634 polymer for mills 1 and 2; 40 mg/1 alum and 2 mg/1 Nalco 634
 for mill 3; and 180 mg/1 alum and 2 mg/1 Nalco 634 for mill 5.

      Terminal pH for the samples tested in this study was in the range of 6
 to 6.5 for all four mill samples.  Evidence from the jar testing work suggests
 that chemical dosages and terminal pH will be variable at a given mill, and
 it is probable that a pH control system will be needed to maintain proper pH
 conditions in a commercial scale plant.

      Testing of coagulation effectiveness by "freeness" measurements using
 the Buchner funnel and capillary suction time (CST) devices yielded mixed
 results for two reasons.  First, the chemical conditioning produced increased
 TSS levels to the uncoagulated samples.  Second, the wastewaters were suffi-
 ciently variable that repeat testing on the limited number of samples used in
 this study did not produce a reliable basis for comparison.  For the extent
 of data available, the freeness tests showed no advantage over jar tests for
 coagulant optimization.  It is possible that extensive testing at a specific
 mill site would yield a useful technique that is easier and faster than jar
 testing, but a larger data base is needed to refine these techniques.

 PHASE Ic -  SOLIDS REMOVAL TECHNIQUES

 GENERAL

      Bench scale tests were run on four samples using the following six solids
 removal techniques:  Mixed media filtration; air flotation; microstraining;
 coagulation/sedimentation; sand filtration; and magnetic separation.  Tests
 were run with and without chemical conditioning.  Table 5 lists chemical con-
 ditioning used in these studies.

                                   TABLE 5

	CHEMICAL CONDITIONING	

                               Alum Dose                  Polymer Dose
 Mill	mg/1  as Al?(S04h	mg/1 Nalco 634	

  1                                100                          2
  2                                100                          2
  3                                 40                          2
_5	180	2	

      Figure 29 is a bar diagram showing the relative solids removal efficiency
 of  each method,  for each of the four mills.  This figure shows that mjxetfy

                                      51

-------
cn
1 UU
10 .
SS
0
IJJ
O 60
3
ff
9
8
o
Ul
Z «0
D
in
20-

















1"



2













3













5












1












2














3














5
SAND FILTRATION
NO CHEM
W/CHEM








I — I


















1








2













3




i 	 |


	





5








1








2















3















5
MIXED MEDIA
FILTRATION
NO CHEM [ W/CHEM





































1 2



3


—
5















1235
MICRO STRAINING
NO CHEM


W/CHEM




















1















2















3















5































1235
DISSOLVED AIR
FLOTATION
NO CHEM











W/CHEM '





































1






2




	 .

3















5






























I —
1






2






35 12351 235
MAGNETIC SEPARATION
NO CHEM







w/ ] w/ w/
POLYMER MAGNITITE POLYMER
AND
MAGNITE
         •Mill No.
                                             Figure  29
                               SUSPENDED SOLIDS REMOVAL  EFFICIENCY

-------
 media filtration and sand filtration appear to be the most promising, removal
 methods.

      The results of these bench scale tests are discussed in the remainder of
 this chapter.

 MIXED MEDIA FILTRATION

 Media Evaluation

      The initial tests relative to mixed media filtration consisted of eval-
 uation of the various media to determine the optimum grain sizes and quanti-
 ties to use for the actual testing.  Table 6 lists suggested media combina-
 tions obtained from a manufacturer of mixed media filtration systems.

                                    TABLE 6

                          SUGGESTED MEDIA COMPOSTTION
Material
Standard
Ilmenite
Sand
Coal
Fine
Ilmenite
Sand
Coal
Coarse
Garnet
Sand
Coal
Grain Size

0.2 mm
0.4 mm
1.1 mm

0.2 mm
0.4 mm
1 .1 mm

0.5 mm
0.9 mm
1.5 mm
Depth*

1 in.
3 in.
6 in.

3 in.
3 in.
4 in.

1 in.
3 in.
6 in.

 * Fine media at top of column and coarse material at bottom.

      Two  runs  were made (mill  1  effluent,  without chemical  addition)  using
 each  of the media  combinations listed in Table  6.   The  resultant  total  sus-
 pended solids  (TSS) removals are listed in Table 7.

                                    TABLE 7

	SUGGESTED MEDIA FILTRATION RESULTS	

	Media	TSS Removal

                       Standard                    14
                       Fine                        11
                       Coarse  	      14
                                      53

-------
      Two runs were then  made  using modifications of the standard and fine
 media to try to improve  TSS removal.  Table 8 lists the composition of these
 modified media.

                                  TABLE 8

                         MODIFIED MEDIA COMPOSITION
       Media
Grain Size
Depth
TSS Removal (%)
Standard
Ilmenite
Sand
Coal
Fine
Ilmenite
Sand
Coal

0.2 mm
0.9 mm
1.5 mm

0.2 mm
0.9 mm
1 .5 mm

1 in.
3 in.
6 in.

3 in.
3 in.
4 in.


40



52


      On the basis of this  testing,  the modified fine media combination was
 selected for use in all  subsequent  testing.

 Filtration Tests

      All  tests  were run  at a  flow rate of approximately 1QO ml/min.2 This
 resulted in a filter loading  rate of about 3.4x10" m /s/m (5 gpm/ft ), based
 on the size of  the filter  column used.  Changes in flow rate occurred on
 some runs as a  result of the  variation in solids content of the samples.  The
 flow rate was measured periodically during each run.

      Table 9 lists average results  of mixed media filtration tests, with and
 without chemical  addition, for effluent samples from the four mills.

                                 TABLE 9

                       MIXED  MEDIA  FILTRATION RESULTS

Mill No.
1
2
3
5

Initial TSS
(mq/1)
160
6
70
60

TSS
W/Chemical
69
0
85
0

Removal (%}
s W/0 Chemicals


69
58
67
43

     The poor TSS removal for mills number 2 and 5 resulted from a  signifi-
cant increase in TSS concentration with chemical addition, and failure  of
the filter to remove a quantity of solids as large as that added.   Therefore,
a net increase in solids was measured, based on the original TSS concentra-
tion in the sample.
                                      54

-------
     The removal efficiency reported for mill number 2 is somewhat suspect
because of the very low initial TSS concentration.  A small  change in TSS
concentration would result in a major difference in removal  efficiency.
Chemical addition increased the TSS from the initial value of 6 mg/1  to  200
mg/1.  The filtrate TSS concentration with chemical addition was 16 mg/1
showing a net increase.

     A similar phenomenon occurred with the other samples.  Mill number  1
TSS increased from 160 mg/1 to 300 mg/1 and for mill number 3 the increase
was from 70 mg/1 to 120 mg/1, with the addition of chemicals.

     Additional samples from mills number 1 and 3 were secured and sent  to
a mixed media filter manufacturer for independent TSS removal evaluation.
The tests were conducted using a continuous filtration apparatus with a  sam-
ple volume of about 1.9x10" m^S gall.  Both samples were run with a filter
loading rate of about 3.4x10" mVs/m (5 gpm/ft2) without chemical addition.

     TSS removal recorded by the manufacturer for mill number 1 averaged 30
percent and for mill number 3, 41 percent.  The headless increased at a  rate
of about 1.3 to 1.6 feet per hour.  The manufacturer concluded that adding
chemicals directly to the filter did not appear to be feasible because of
the high solids loading.  They also concluded that chemical  treatment with
settling prior to filtration might be required to improve filter efficiency.

DISSOLVED AIR FLOTATION (DAF)

     Two runs were made on each sample at air/solids ratios of 0.06, 0.03 and
0.01, with extremely poor results.  Most of the samples tested showed no re-
moval at all.  The only significant removals observed were on samples from
mill number 3.  Table 10 lists the DAF data (average of two runs).

MICROSTRAINING

     Results of microstraining tests using a batch laboratory unit are pre-
sented  in Table 11.  Several different fabric mesh sizes were tested, ranging
from 1 micron openings to 74 micron opening, both with and without chemical
conditioning.  In general, poor results were obtained.  The fabrics tended
to blind very rapidly, resulting in short filter runs.  Only samples from
mill number 3, without chemical addition, produced any significant TSS re-
movals.  The best removals were observed with the 74 micron openings, the
largest tested.  This was an unexpected phenomenon because particle size
measurements showed that most of the solids were less than 2 microns in
size.  This condition may be the result of stapling and bridging effects of
the solids on the strainer media.
                                      55

-------
                                  TABLE 10



                       DISSOLVED AIR FLOTATION RESULTS
Mill
1
(110)*
2
(5.5)
3
(70)
5
A/S Ratio
0.06
0.03
0.01
0.06
0.06
0.03
0.01
0.06
Final TSS TSS Removal
w/chem w/o chem w/chem
145
160
170
100
40
66
113
152
100
125
110
7.5
60 43
53 6
53
60
(«)
w/o chem
9
0
—
14
25
25
0

* Initial

TSS concentration.


TABLE 11

MICROSTRAINING RESULTS

Will
1 (110)*
2 (5.5)
3 (70)
5 (60)
Fabric
35 micron
35 micron
17 micron
21 micron
74 micron
35 micron
21 micron
35 micron
21 micron
10 micron
Final TSS TSS Removal
w/chem w/o chem w/chem
290
190
220
100
135
120
330
no
12
8
45
50
50
64
60
48
w/o chem
0
—
37
29
29
0
20

* Initial TSS Concentration
                                      56

-------
COAGULATION/SEDIMENTATION

     Settling column tests were run on samples from mills number 1, 2 and 3.
Two columns were used and tests were run simultaneously, with and without
chemical addition.  No settling column tests were run on mill number 5 efflu-
ent because the volume required and the distance involved made shipping such
a large sample under refrigerated conditions impractical.

     Figure 30 is a plot of the settling data for the mill number 1 sample.
This figure shows the relationship between TSS concentration at each column
port and settling time, both with and without chemical addition.  The settl-
ing was monitored by periodic sampling at each port over a 6-hour period.

     These results illustrate the characteristic increase in TSS with chemi-
cal addition.  They also show that, while settling was rapid during the first
hour, the overall settling after six hours did not reach a TSS level as low
as the concentration in the untreated sample.  Therefore, it appears that
chemical addition, at least the concentration used in this test run, was not
beneficial in reducing the effluent TSS concentration.

     With no chemical addition, the TSS concentration at all ports, after
six hours settling, was essentially the same as the initial concentration.

     Figures 31 and 32 are similar plots for mills number 2 and 3 respective-
ly.  These samples exhibited settling characteristics similar to those of
mill number 1.

     An attempt was made to develop a settling rate correlation between the
three samples tested and the sample from mill number 5 because an inadequate
quantity of sample for a settling column test was available for mill number
5.  Jar tests were run simultaneously with the settling column test on sam-
ples from mills number 1 and 3.  Similar jar tests were run on the sample
from mill number 5.  However, due to the poor settling characteristics of
the solids, no trends were observed and no significant comparisons could be
made.

SAND FILTRATION

Media Evaluation

     Two runs each were made using fine sand (0.4 mm) and coarse sand
(0.9 mm), and TSS removals were measured as a basis to select a media for use
in the actual testing.  No significant difference in TSS removal was observed
between the two media grain sizes.  The fine sand was selected for testing.

Filtration Tests

     The sand filtration tests were run using the same filter columns as for
the mixed media tests.  The filter loading rate was approximately 3.4x10
m /s/m (5 gpm/ft ), which required a flow rate of about  .100 ml/minute.

     Table 12 lists average TSS removals for test runs on each sample, with

                                     57

-------
                                  3OO
                                  ZOO
  100

    o
*~ 5OO
J
Z 4OO
                                Of 30O
                                i
                                2 200
                                  '00
                                2 soo
                                Q
                                01
                                  400
                                  300
                                  2OO
                                  100
                                                      I     1
                                                     PORT NO. 7
                      PORT NO, 8
                                             2345
                                              TIME hrs.
        LEGEND
      -• With Chemical Treatment
o——-o No Chemical Treatment
                       figure 30
    COAGULATION/SEDIMENTATION  DATA MILL NO.  1
                            58

-------
          200
          1OO
\
V




p<

>RT N

J. 2

O zuu
4
P- too
UI
o
2 A
0 °
1
8
a
UJ o
Q
29ftn
UI
t/> f OO

o
\
N


\
\


*\
N
0~»^<






>—«••»<


^^.
>— — t











P(



PC



p<


)RT N



>RT N

to 	

>RT N


1. 4



1. 6

	 j

3. 8

——•3
                  1234

                       TIME, hrs.
                                    5    6
            LEGEND
          -• With Chemical Treatment
    o———o No Chemical Treatment
                    Figure 31
COAGULATION/SEDIMENTATION DATA MILL NO.  2
                          59

-------
           zoo
           too
           2OO
           too
         = 200


         J


         o



         E
         h-
• jl
V,


r"«L
""--<


>---.__

PO
RT NC
L~f~..
t
1. 2




\
<**. 3


*
too
           200
         §
         O


         8
         o
         
-------
and without chemical addition.

                                  TABLE 12

                           SAND  FILTRATION RESULTS
                                                     TSS Removal (35)
Mill	Initial TSS  (mg/1)	w/chem	w/o chem
1
2
3
5
no
5.5
70
60
64

71

14
36
68
23

     Mills number  2  and  5  showed  no TSS  removal with chemical addition,
again, as with  the mixed media filtration  tests, due to the significant in-
crease in TSS with chemical  addition.  These data  indicate that, with the
exception of mill  number 1,  there was  no significant advantage to chemical
addition.

MAGNETIC SEPARATION

     Magnetic separation tests were run  using a device called a Frantz Ferro-
filter.  This device operates on  the basis that by placing the proper type
of steel media  into  the  magnetic  field generated,  concentrated magnetic force
sites will be produced,  which will tend  to attract particles with a net
charge.  The flow  rate through the filter was maintained at approximately
750 ml/minute for  each run.  Two  different media were tested—packed steel
wool and steel  discs.

     Several runs  using  steel wool media were made.  The use of steel wool
was discontinued after these runs for  the following reasons:  a review of
the literature  on  magnetic separation  revealed that steel wool is very diffi-
cult to magnetize  because  of its  high  void content, and the Ferrofilter does
not have the capacity to generate the  magnetic intensities needed to ade-
quately magnetize  steel  wool; and the  steel wool tended to act as a filter,
thus, removing  solids from the flow by physical rather than magnetic means.

     Test runs  included  untreated samples, and those treated with polymer.
alone, magnetite alone,  and  a combination of polymer and magnetite.  The con-
centration of magnetite  added was varied for each  sample to try to improve
its function.   The concentration  added for mill Number 1 was 3 times the TSS
concentration;  for mill  number 2  was 2.5 times TSS; and for mill number 3
was 1 times the TSS  concentration.

     Table 13 lists  the  TSS  removal data for mills number 1, 2, and 3.  The
data for mill number  1 includes both steel wool media and disc media tests.
Steel wool  media removal  was greater than that of  the discs because of the
physical  solids removal  as discussed previously.

     TSS removals for mill number 2 appeared to be reasonably good.  However,
these data may  be misleading because of  the very low TSS concentration in the

                                      61

-------
 sample.   As  the table  shows, a very small difference in TSS concentration
 results  in a large  change  in percent removal.

      In  each case,  TSS removal appeared to be better for runs with untreated
 samples  or with only polymer addition.  This is an indication that the addi-
 tion of  magnetite to the samples not only failed to improve TSS removal, but
 was detrimental  to  removal.

      This condition was likely due to the failure of the suspended solids to
 strongly adhere to  the magnetite.  The magnetite being strongly magnetic in
 character, would be attracted to the media much more rapidly than the
 weakly-magnetic or  non-magnetic suspended solids particles.  This would likely
 have the effect of  reducing the magnetic attraction for the suspended solids.
 Thus, even though the  magnetite may have been completely removed from the
 liquid,  fewer of the suspended solids would have been removed.

                                  TABLE 13

                         MAGNETIC SEPARATION RESULTS
 Mill
  No.
Run
No.
Magnetite
           Effluent
Polymer  TSS (mg/1)
                           TSS
                        Removal  %
 (HO)'
  (5)
1
2
3
4
    No
    No
    Yes
    Yes
    Yes

    No
    No
    Yes
    Yes
No
Yes
No
Yes
Yes

No
Yes
Yes
Yes
             90
             90
            100
            110
            100

              3
              3
              4
              4
18
18
 9
 0
 9

40
40
20
20
3 ,
(65)'
1
2
3
4
No
No
Yes
Yes
No
Yes
No
Yes
50
50
70
60
23
23
8

   Initial TSS Concentration

2  Steel Wool Media

OVERVIEW OF BENCH SCALE TEST RESULTS

     In general, the bench scale testing showed several common  elements.
Attempts to chemically coagulate the TSS to facilitate  removal  were  variable
and - short of a massive chemical dose to induce full precipitation  of both
TSS and color - frequently resulted in net increases  in effluent  TSS.   The
fact that coagulants invariably increased the TSS  levels  before subsequent
removal (e.g., filtration) is an important factor  in  determing  the quantity
of sludge for disposal.  Sludge disposal quantities for the  coagulated efflu-
                                     62

-------
ent may be several times the value calculated from the net change in efflu-
ent TSS.  The generation of increased TSS through coagulation will  also
affect the commercial plant operating condition, for example, filter run
times and backwash fines recycle.

     The effluents were highly variable, from a standpoint of both mill-to-
mill comparisons, as well as repeat observations at a given mill.  To ade-
quately define effluent TSS variability factors for a tertiary removal pro-
cess will require on-site pilot testing over a period of at least several
weeks.  Furthermore, review of effluent monitoring data from some mills
suggests that seasonal (temperature-related) changes in TSS levels may be
significant, which indicates the need for "summer" and "winter" pilot data.

     The low effluent TSS levels (10 mg/1 TSS or less) commonly achieved in
municipal secondary effluents were not achieved by even the best of the post
biological solids removal process tested.  (An exception is mill 2, where
initial TSS levels before testing were normally 10-20 mg/1.)  Because of the
variability, it  is impossible to state a generalized "achievable TSS level."

     The performance of the TSS removal processes tested did not correlate
with a single identifiable attribute of the mill production process or treat-
ment system.  A  comparison of mills 3 and 5, both west coast kraft mills with
aerated lagoons,  shows that mill 3 effluent TSS was consistently more sus-
ceptible to removal than mill 5.  Mill 5 is bleached, whereas mill  3 is un-
bleached.  The aerated lagoon at mill 5 has a much longer retention time than
the one at mill  3, and operates at slightly lower average effluent TSS levels,

     Mills 1 and 3 are both unbleached kraft with aerated lagoon treatment.
In spite of higher initial TSS levels at mill 1 during these tests, the TSS
from mill 1 were less susceptible to removal than mill 3.  Mill 1 has a
slightly longer  lagoon retention time (9 days, versus 5.5 days at mill 3)  and
mill 1 also has  an NSSC plant coupled-with the kraft process.

     No definitive correlations between TSS susceptibility to removal and
TSS physical and chemical characteristics were observed.  As noted earlier,
availability of  size distribution by weight rather than volume might yield
a meaningful correlation.

     Finally, it appears that filtration processes - either sand or mixed
media - offer the greatest degree of TSS removal of the processes tested.
                                      63

-------
                                 REFERENCES

  1.   "Preliminary  Report:  Fate and Effects of Suspended Solids  from Secon-
      dary Biological Treatment of Wastewater."  Report published by the  Acad-
      emy of Natural Sciences of Philadelphia, Division of Limnology and  Ecol-
      ogy, Philadelphia, Pennsylvania, (June 1976).

  2.   Smith, O.D.,  Stein, R.M. and Adams, C.E., Jr., "Analysis j)f Alternatives
      for Removal of Suspended Solids in Pulp and Paper Mill  Effluents."   Tap-
       _, 58, 10, 73 (1975).
  3.   Beak Consultants Limited.  "The Nature, Fate and Impact of Primary Non-
      Settleable-Solids."  CPAR Project Report 241-1, Canadian Forestry  Ser-
      vice, Ottawa, Ontario, Canada, (1974).

  4.   Stein,  R.M. and Adams, C.E., "Analysis of Alternatives for Reduction  of
      Effluent Suspended Solids."  AWARE, Inc., Nashville,  Tennessee,  (1974).

  5.   Berov,  M.B., Shapchenko, V.M., and Lobko, V.V., "Optimum Conditions for
      Chemical Purification of Effluents."  Bumazh.  Prom. No.  2:   17-19  (Feb-
      ruary 1975). (Russ.) A.B.I.P.C., 46., 2 (1975).

  6.   Gove, G.W. and Gellman, I., "Paper and Allied Products." Annual  Litera-
      ture  Review, Journal Water Pollution Control Federation. 47, 6  (1974).

  7.   Gove, G.W. and Gellman, I., "Paper and Allied Products."  Annual Litera-
      ture  Review, Journal Water Pollution Control Federation, 47, 6  (1975).

  8.   Gove, G.W. and Gellman, I., "Paper and Allied Products."  Annual Litera-
      ture  Review, Journal Water Pollution Control Federation. 46_, 6  (1974).

  9.   Gove, G.W. and Gellman, I., "Paper and Allied Products."  Annual Litera-
      ture Review, Journal Water Pollution Control Federation, 45, 6  (1973).

10.   Kendall, D.R., "Investigation of the Problem of Determining Total  Sus-
      pended Solids in Pulp and Paper Effluents."  Tappi .  59, 9 (1976).

11.  Baskerville, R.C., and Gale, R.S., "A Simple Automatic Instrument  for
     Determining the Filterability of Sewage Sludges."  Journal of the  Insti-
     tute of Water Pollution Control, 67., 2, (1968).

12.  Lee, E. G-H. , Mueller, J.C., and Walden, C.C., "Analysis and Characteri-
     zation of Suspended Solids in Pulp and Paper Mill Effluent."  B.C. Re-
     search, Vancouver, British Columbia, Canada, (No Date).
                                     64

-------
13.  Surcheck, J.G. and Tutein, T.R., "Simplified Method Determines  Cost Per-
     formance of.Polymeric Flocculants."  Water and Sewage Works.  January
     I j IO •

14.  Sakuma, M., Kimura, M., and Takahashi, 0., "Application of Polyacryla-
     mide to Pulp Mill Effluents."  Japan Tappi. 27, 6, (1973), A.B.I.P.C.,
     45, 11 (1975).

15.  Neptune Microfloc, Inc., "A Report on an Effluent Treatment Pilot  Study,
     for Georgia Pacific Corporation, Toledo, Oregon, and Cornell, Howland,
     Hayes and Merryfield, Engineers and Planners, Corvallis, Oregon."   Un-
     published report (1968).

16.  Das, B.S. and Lomas, H., "Flocculation of Paper Fines.   I*  Adsorption
     of and Flocculation by Polyelectrolytes.  II.  Study of the Nature of
     the Solid Surface and Soluble Impurities."  Pulp and Paper Magazine  of
     Canada. 74, 8 (1973).	

17.  New Brunswick Research and Productivity Council, "Removal  of Post  Bio-
     logical Solids by High Rate Granular Media Depth Filtration."   Project
     Report 80-1, Canadian Forestry Service, Ottawa, Ontario, Canada, (1972).

18.  "Pilot Plant Studies of Turbidity and Residual Cell  Material Removal
     from Mill Effluent by Granular Media Filtration."  NCASI Stream Improve-
     ment Technical Bulletin No. 266 (1973).

19.  Nachbar, R.H., "Pilot Plant Evaluation of Multi-Media Filters for  Terti-
     ary Treatment."  Preliminary Report (unpublished) (1968).

20.  Envirocon Limited, "Assessment of Filtration and Straining for  the Re-
     duction of Effluent Suspended Solids."  CPAR Project Report No.  236-1,
     Canadian Forestry Service, Ottawa, Ontario, Canada (1973).

21.  Kolm, H., Oberteuffer, J. and Kelland, D., "High Gradient Magnetic Sep-
     aration."  Copy of paper - Source unknown.

22.  Mitchell, R., Bitton, G., and Oberteuffer, J.A., "High  Gradient Magnetic
     Filtration of Magnetic and Non-Magnetic Contaminants from Water."   Sep-
     aration and Purification Methods. £, (2), (1975).

23.  Helfgott, T., Hunter, J.V., and Rickert, D., Analytic and Process  Class-
     ification of Effluents."  Journal of the Sanitary Engineering Division.
     ASCE Proc., 96, SA3 779 (ISTOT

24.  Rickert,  D.A.,  and Hunter, J.V., "Collodial  Matter in Wastewaters  and
     Secondary Effluents."  Journal Water Pollution Control  Federation. 44_,
     1  (1972).

25.  Tchobanoglous,  G. and Eliassen, R., "The Filtration of Treated  Sewage
     Effluent."  Proc. 24th Industrial Waste Conference, Purdue University
     (1969).


                                      65

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26.  Faust, S.D. and Manger, M.C., "Distribution  of Electromobility Values of
     Particulate Matter in Domestic Wastewater."   Presented at the 37th Ann-
     ual Conference, WPCF, Bal  Harbour, Florida,  (1964).

27.  Sundaram, T.R. and Santo,  J.E., "Microfiltration  of Military Waste Ef-
    fluents."  Paper presented  at the Seventh  Annual Symposium of Environ-
     mental Research:  "Environmental Technology  - Military Waste Effluents
     and Installation Restoration," Edgewood Arsenal,  Maryland,  (1976).

28.  Barton, C.A., Byrd, J.F.,  Peterson, R.C., Walter, J.H., and Woodruff, P.
     H., "A Total Systems Approach to Pollution Control at a Pulp and Paper
     Mill."  Journal Water Pollution Control Federation. 40_, 8 (1968).

29.  British Columbia Forest Products, Ltd,  "Origin and Removal  of Precipated
     Suspended Solids in Bleached Kraft Pulp Mill  Effluent," CPAR Project Re-
     port 371-2, 30 September 1978.

30.  "Characterization of Dispersed Residual Solids in Biologically Treated
     Pulp Mill Effluents," NCASI Stream Improvements Technical Bulletin 303,
     February 1978.

31.  Bewers, J.M. and Pearson,  "The Behavior of Particulate Material in the
     Treatment Lagoons of a Bleached Kraft Mill."   Water, Air, and Soil Pol-
     lution, 1 (1972) 347-358 (Reidel Publishing  Company, Dordrecht, Holland).

32.  "Pulp and Paper Mill Effluent Nitrogen  and Phosphorus Requirements for
     Biological Treatment and Residuals after  Treatment," NCASI  Stream Im-
     provement Technical Bulletin No. 296, August 1977.

33.  Herrman, R.B., "Character  and Environmental  Impact of Pulp  Mill Treat-
     ment System Particulates," Environmental  Technology Department Report,
     Weyerhaeuser Company, (1977).
                                     66

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                                 APPENDIX A

                              LITERATURE REVIEW

     This informal technical review provided both theoretical  scientific and
practical industrial background for this study.  Three areas of study were
examined.  General Studies on Solids Characterization and Removal  Processes
summarizes broad-spectrum solids characterization studies, and multimedia
removal processes.  Specific Solids Removal Techniques examines studies of
individual types of solids removal techniques:  coagulation/sedimentation,
filtration, microstraining, and magnetic separation.  These studies cover
both jar testing and paper mill applications.  Finally, the Municipal Treat-
ment Systems examines secondary treatment systems for their potential capa-
bility in solids removal.  This section includes studies of solids character-
ization and removal techniques which have been tested in secondary treatment
systems in both domestic and military wastewater.

GENERAL STUDIES ON SOLIDS CHARACTERIZATION AND REMOVAL PROCESSES

     Solids characterization studies were performed on nine samples of efflu-
ent from an activated sludge system at an ammonia-base, bleached sulfite
mill.   The major conclusions were:

     o  The effluent suspended solids were almost exclusively biological
        in nature.

     o  The particles ranged in size from 1 to 6 microns.

     o  The majority of the particles observed were dispersed cells
        (1 to  6 microns), with the next most common being floe
        particles (5 to 15 microns).

     o  The samples contained suspended solids concentrations of 90
        to 379 mg/1 (milligrams per liter), with no significant
        settleable material.

     o  <€4 to 90 percent of the suspended solids were volatile.

     o  A preliminary bio-assay test indicated no toxicity to
        test organisms.

     Effluent suspended solids removal studies were conducted at an un-
bleached Kraft-NSSC (neutral sulfite semi-chemical) cross recovery pulp and
paper mill in the southern U.S.   The studies included analyses of:  coagu-
lation; clarification; and multi-media filtration.  Coagulation studies pro-
                                      67

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 vided  the following conclusions:

     o  Suspended solids levels increased with the addition of polymer.

     o  Alum was determined to be the best coagulant.

     o  Optimum coagulation occurred with 70 to 100 mg/1 of alum at
         pH  4.5.

     Sedimentation studies showed that, for a 24 hour settling time, pH
 adjustment  and approximately 70 mg/1 alum were required to achieve signi-
 ficant suspended solids removals.  Multi-media filtration tests showed sus- «
 pended solids removals of about 50 percent at a flow rate of 1.35x10" m /s/ra
 (2 gpm/ft  ), without  chemical addition.  The effective media sizes were:
 coal - 0.95 mm  (millimeters); sand - 0142 mm; and garnet - 0.3 mm.

     A Canadian report3 lists the physical and chemical characteristics of
 both settleable and non-setteable primary clarifier effluent solids from a
 Kraft  pulp  mill.  They reported a solids size range of 6 to 80 microns.  The
 authors concluded that Kraft mill effluents may be expected to contain non-
 proteinous  organic nitrogen, making Kjeldahl nitrogen values suspect in terms
 of the actual food potential of the solids.

     Particle size analyses were performed using a Coulter Counter industrial
 model  B, with a 200 micron aperture.  The samples were pre-filtered through
 a 100  micron mesh filter.
                    A
     Stein  and Adams  studied the feasibility of suspended-solids removal
 from an integrated unbleached Kraft-NSSC pulp and paper mill.  They concluded
 that optimum sedimentation of the solids occurred with the addition of 70 to
 100 mg/1 alum at pH 4.5.  They also reported suspended solids?removals of
 about  50 percent at a flow rate of 1.35x10  m/s/m   (2 gpm/ft ) without chem-
 ical addition.
                    5
     A Russian paper  discussed treatment of biologically purified Kraft
 mill effluents with aluminum sulfate (alum).  The conclusions were that the
 pH after alum treatment steadily increased to acceptable levels through re-
 action of hydrogen ions with dissociated hydroxyl groups of ligm'n.

     Gove and Gellman ' * '  presented a review of the literature pertaining
 to  pulp and paper wastes.  Their review included many papers related to
 solids removal and advanced treatment of pulp mill wastewater.

     Five techniques for determining total suspended solids in pulp and paper
 effluents were investigated by Kendal.    The most promising method appeared
 to  be  centrifugation, followed by filtration through a 2.4 cm (centimeter)
 fiberglass filter in a porous-bottomed crucible.

     Baskerville and Gale   described the use of an  instrument for determin-
 ing the filterability of sludge easily and rapidly.  The instrument, called
a capillary suction time (CST) meter, measures the specific resistance to
filtration of the sample, using the principle of capillary suction of  a


                                      68

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filter paper such as chromotography paper.  Good, reproducible results were
reported.
                12
     Lee, et al.   reported on the nature of suspended solids in the efflu-
ent from bleached and unbleached Kraft and groundwood pulp mills and a fine
paper mill.  The analyses performed included:  total suspended solids (using
three different filter types); non-setteable solids; BOD-n; total Kjedahl
nitrogen; total phosphates; color; and bio-assays.  They concluded that non-
settleable solids settle and degrade very slowly in receiving waters, and
that BOD30 and nutrient loading was very low.  They also found that the
solids were not toxic to fish.
                                     29
     British Columbia Forest Products   identified calcium-lignin precipi-
tates as a significant source of non-setteable suspended solids in bleached
Kraft mill aerated lagoon effluent.  Addition of a brownstock washer at a
mill, to reduce soda losses from 2.4x10 kg(55'lb)/ADT down to 5.6 kg(12.4 lb)/
ADT (as saltcake), resulted in improved effluent TSS levels.

     NCASI  , in studies conducted at 3 mills and a pilot plant, found that
the suspended solids in biologically-treated effluent were biological in
nature, and consisted of particles from 1 to several, but generally less than
eight microns in diameter.  On the order of 25% of the solids were said to
be viable biomass.  Resistance to coagulation was attributed to adsorption of
hydrophilic colloids, rather than charge repulsion.
                       31
     Bewers and Pearson   used serial filtration on Millipore and Whatman
filters to determine the size distribution by weight at a modified natural
lagoon system serving a bleached Kraft mill in Nova Scotia.  They found that
about 2/3 of the suspended solids were 0.5-1.0 micron or smaller, and that
only 13% of the suspended solids were 5 microns or larger.
          op
     NCASI   reviewed the nitrogen and phosphorus of biological solids, and
reported typical values of 9-10 percent nitrogen and 2-3 percent phosphorus.

     Herrmann3  studied the characteristics of pulp mill treatment system
particulates from 3 mills, and found that the solids were nonfibrous material
of high carbon and protein content.  The particulates were small (<30 micron),
and were said to contain appreciable concentrations of calcium and magnesium.
Metal-lignin precipitates were postulated to represent a portion of the
particulates.

SPECIFIC SOLIDS REMOVAL PROCESSES

COAGULATION/SEDIMENTATION
                                                  13
     A method was presented by Surcheck and Tutein   for developing a cost-
performance factor to determine the best polymer for a given wastewater.  The
method consists of jar testing using different polymers at different concen-
trations and then relating optimum dosage to polymer cost.

     Sakuma, et a!.14 discussed the clarification of bleached Kraft mill  ef-
fluents by addition of polyacrylamide (PAA).  The variables considered were:

                                     69

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 alum dosage;  PAA molecular weight and dose rate; and the effect of pH on
 coagulant  efficiency.  They concluded that the PAA molecular weight must be
 greater than  5  x 10  for  satisfactory results.

      A pilot  study to evaluate sedimentation equipment developed by Neptune
 Microfloc, Inc., and evaluate treatment processes capable of producing re-
 usable water  was conducted.

      Das and  Comas   reviewed theoretical adsorption of water-soluble macro-
 molecules  onto  suspended  solids to give either stable dispersions or sensi-
 tized flocculation.  They also developed a new procedure for use of cationic
 polyelectrolytes as flocculants for paper fines.

 FILTRATION

      Canadian researchers  studied filtration of a bleached Kraft mill sec-
 onday effluent.  Secondary treatment consisted of an aerated lagoon system
 producing  an  effluent suspended solids (SS) concentration of 50 to 60 ppm
 (parts per million).  The study concluded that SS removals by filtration were
 in the range  of 40 to 50  percent, mainly due to the fine particle size (one
 micron range) of the dispersed bio-mass solids.  The best performance was
 achieved using  a medium grade sand (effective size, 0.56 mm).  Granular
 media filtration by itself was not recommended for solids removal because
 of the voluminous floe formed after chemical treatment.  They also found the
 optimum alum  dosage (at pH 5) to be about 90 ppm, and that 260 ppm alum was
 required at pH  7.3.

      They  concluded that  lime addition was not an economical coagulation
 method because  of the large quantity required (1,000 ppm).
              I Q
      The NCASI   studied  the applicability of granular media filtration
 for removing  suspended solids from secondary effluents, from boxboard,
 bleached Kraft, filled and coated fine paper mills.  The study demonstrated
 on a pilot scale that application of a variety of granular media filtration
 systems to such diversified effluents could remove only 25 to 50 percent of
 the residual  suspended solids.  Backwash materials could not be readily de-
 watered alone.
            19
      Nachbar   conducted  a pilot plant study of multi-media filtration of
 activated  sludge secondary effluent from a Virginia pulp mill.  He concluded
 that multi-media filtration can remove about 50 percent of the^suspended
 solids  and about 30 percent of the BOD at a loading of 3.4x10  m/s/m
 (5  gpm/ft  ).  Backwash was reported to be a continual problem.

 MICROSTRAINING

                                20
     A  report by a Canadian firm   reviewed current filtration and straining
methods  and research.  One of the methods reviewed was microstraining.  One
 installation  claimed to obtain 97 percent removal of suspended solids  with,
coagulation,  using 35 micron mesh openings, a hydraulic loading of 3.1x10
m/s/m   (4.6  gpm/ft ) and a feed concentration {of suspended solids) of about
130 mg/1.  Problems tended to occur with adhesive solids blinding the  fabric

                                     70

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media and requiring large quantities of backwash water.

MAGNETIC SEPARATION

     The concept of high gradient magnetic separation is described by Kolm,
et al.    They also discussed the work of Samual Frantz, who developed a
lab scale separator called the Frantz Ferrofilter.  They found that this
unit could not economically achieve the magnetic field intensities required
to magnetically saturate steel wool or to magnetize weakly magnetic materials,
and, thus, has limited application.

                     22
     Mitchell, et a!.   described the use of a magnetic device designed to
remove weakly magnetic particles from solution.  They reported greater than
90 percent removal of coliform bacteria using a device called a high-gradient
magnetic separator, with the addition of magnetite to the sample.  They also
claim 69 percent BODg removal from pulp mill effluent, using the same tech-
niques in their laboratory.

MUNICIPAL TREATMENT SYSTEMS SOLIDS REMOVAL

     Identification of the components found in secondary effluents (domestic)
was presented by Helfgott, et al.    Both chemical analyses (organic) and
physical properties were discussed.
                        24
     Rickert and Hunter,   working with municipal wastewater, studied the
nature and origin of colloidal meterials present in secondary effluents.
They concluded that most of the  colloidal particles were formed during secon-
dary treatment rather than being present in the raw wastewater, and were,
therefore, biological in nature.
                               25
     Tchobanogious and Eliassen   reported on a studies of filtration of
treated domestic wastewater, including information on effluent characteris-
tics.  They found the particle size distribution to be bimodal in nature,
with the mean size of the smaller particles ranging from 3 to 5 microns and
the larger particles ranging from 80 to 90 microns.  The weight fraction of
the smaller particles was estimated to be 40 to 60 percent of the total.  The
method used was dark field observation with a stereoscope.

     The mean charge on the particles in terms of zeta potential, was about
-20 millivolts.

     Effluent suspended solids varied between 7 and 14 mg/1.  Removal effi-
ciency varied from 15 percent with a 1.0 mm sand size to240 percent with a
0.5 mm sand size, at a filtration rate of 3.4x10" m /s/m (5 gpm/ft ).
                     yc
     Faust and Manger   studied  the electromobility of colloidal and supra-
colloidal particles (less than 100 microns) in domestic wastewater.  They
concluded that the particles were predominantly negatively charged, and that
the chemical composition of membrane-filtered particles may be homogeneous.

     Sundaram and Santo27  described  the  results  of  laboratory tests  on micro-
filtration using microporous  tubes.  They  reported  almost  total  removal  of

                                     71

-------
suspended solids from military wastes (including  laundry,  sewage, oil-water
emulsions, and turbid water)  at filtration  pressures  of about 3.4x10  pascals
(5psi).
                                     72

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                                 APPENDIX B

                             ANALYTICAL METHODS

     The methods used for analyses of samples in the work covered by this
report and performed by CH2M Hill are listed below.  The standard method
number given refers to the method in the 14th edition of Standard Methods
for the Examination of Water and Wastewater, APHA (1975).  Methods modified
by CH2M Hill are available on request.

TSS and VSS - Standard Methods 208D and 208E, respectively, modified by
          CH2M Hill; samples filtered through Reeve Angel 934AH, 4.25 cm
          filter.

Zeta Potential - Procedure as specified in the Zeta-meter Manual 2nd
          Edition, as established by Zeta-meter, Inc., New York, N.Y.
          (1968).

BOD - Standard Method 507.

Particle Size Distribution - Direct count method by visual measurement
          using a calibrated eyepiece.
                                     73

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                                   APPENDIX C

                                 DATA SUMMARIES
                                    TABLE  C-l
                                RAW DATA — 1976
SAMPLE
NO.
1
2
3
1
2
3
1
2
3
1
2
3
PARAMETER
BOD (TOT)
BOD (SOL)
BOD (TOT)
BOD (SOL)
BOD (TOT)
BOD (SOL)
COD (TOT)
COD (SOL)
COD (TOT)
COD (SOL)
COD (TOT)
COD (SOL)
TSS
VSS
TSS
VSS
TSS
VSS
TS
TVS
TS
TVS
TS
TVS
MILL NO.
1
29
11
22
8
230
30
288
188
290
231
824
236
48
42
37
34
354
287
777
210
920
260
960
430
2
22
4
11
5
20
' 12
249
192
310
292
237
222
8
7
13
11
12
8
1,330
410
1,600
380
1,310
304
3
11
3
24
4
50
10
214
39
224
46
304
70
70
63
77
61
124
108
1,090
200
880
112
1,030
222
4
114
18
124
84
413
103
3,175
1,940
800
630
5,665
2,630
928
850
151
145
2,510
2,310
6,000
3,030
1,360
7,885
4,020
5
38
12
35
9
78
23
660
528
665
520
694
545
81
71
79
61
90
74
2,100
544
2,100
1,370
2,205
480
6
27
6
31
10
36
10
670
519
425
346
593
478
120
91
72
50
78
55
1,840
326
1,970
336
1,960
390
7
32
8
118
36
41
20
615
476
805
584
945
739
52
50
76
76
91
85
1,200
432
1,240
478
1,370
540
8
10
3
16
4
27
12
230
208
285
240
405
306
19
11
30
18
62
36
1,090
230
1,220
1,240
300
9
90
40
87
56
89
42
3,050
2,700
3,035
2,975
3,325
3,070
92
92
50
42
74
67
5,900
4,750
6,300
1,730
6,340
2,430
NOTE: All units in mg/l
                                      74

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                               TABLE C-l  (continued)
                                 RAW DATA — 1976
SAMPLE
NO.
1

2

3

1


2


3


1
2
3
1
2
3
1
2
3

PARAMETER
P (TOT)
P (SOL)
P (TOT)
P (SOL)
P (TOT)
P (SOL)
TKN
NO. /NO,
NH3
TKN
NO2/N03
NH,
J
TKN
NO2/NO3
NH3
PARTICLE SIZE
PARTICLE SIZE
PARTICLE SIZE
ZETA POT.
ZETA POT.
ZETA POT.
MERCURY
MERCURY
MERCURY
MILL NO.
1
.35
.05
.24
.05
__
—
5.9
.26
.16
4.2
.03
.14
_
—
—
.54
.68
1.1
-11.4
-21.5
-44.3
<.025
0.5
<.025
2
.95
.59
.93
.62
__
—
5.8
.16
3.3
8.1
.04
4.7
— _
—
	
.60
.68
1.4
-6.8
-28.2
-12.0
<.025
<013
<.025
3
.78
.06
1.1
.04
1.1
.05
5.4
.16
.12
8.0
.04
.23
_
.06
.02
*
.57
.60
.95
-5.4
-15.6
-21.2
<.025
<.003
<.025
4
7.8
3.5

—
_
—
31
.02
.08
_
.04
.05
	
—
—
.92
1.0
.68
-12.0
-32.7
0
<.025
—
<.025
5
.84
.18
.84
.15

—
5.2
.12
.15
_
.04
.30
_
—
_
1.0
.95
.95
-10.8
-8.5
-15.3
<.025
<.025
<.025
6
2.4
1.4

4.9
3.5
3.5
8.6
.12
1.2
_
.28
1.8
4.5
.50
.28
.62
1.1
1.3
-10.0
-15.7
-20.5
<.025
<.01
<.025
7
.54
.08

.06

—
5.0
.18
.28
_
0
.13
	
—
—
.78
.74
.97
-19.9
-27.2
-37.0
<.025
<.01
<.025
8
.82
.61

—

—
4.7
.10
.83

—
	
__
—
—
.58
.70
1.3
-12.5
-17.4
-20.3
<013
—
<025
9
8.3
6.2
4.3
4.0
5.2
4.7
6.7
.05
9.74
9.0-1
.03
44
9.0-f
.25
52
.96
.65
.80
-4.0
-5.3
-5.3
2.0
<.002
<.025
NOTE: All units in mg/l
                                      75

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                                    TABLE C-2
                       RAW DATA — METALS (Total) — 1976
SAMPLE
NO.
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3

PARAMETER
CALCIUM
CALCIUM
CALCIUM
MAGNESIUM
MAGNESIUM
MAGNESIUM
IRON
IRON
IRON
MANGANESE
MANGANESE
MANGANESE
ALUMINUM
ALUMINUM
ALUMINUM
ANTIMONY
ANTIMONY
ANTIMONY
ARSENIC
ARSENIC
ARSENIC
BORON
BORON
BORON
MILL NO.
1
>100
17.1
25.8
3.1
1.6
2.1
.84
.43
1.2
.40
.19
.40
.65
1.4
>2.0
<.04
<.04
<.04
<.04
<.04
<04
<-005
.25
.30
2
>100
199
152
3.1
3.3
3.3
.84
.90
1.3
.40
.51
.48
.65
.66
.51
<.04
<.04
<.04
<.04
<.04
<.04
<.005
.03
.03
3
7.8
32.0
41.0
2.7
3.2
3.7
1.2
1.2
.94
.20
.43
.53
1.4
1.8
1.8
<.04
<04
<.04
<.04
<.04
<.04
<.005
.07
.14
4
29.6
14.2
30.0
230
63.9
286
1.2
1.1
2.0
<1.0
.71
4.0
.75
.31
.85
<.04
<.04
<.04
<.04
<04
<.04
.04
.13
.74
5
131
113
151
5.3
5.2
5.8
1.3
1.5
1.5
.57
.68
•71
1.8
1.9
1.8
<.04
<04
<.04
<.04
<.04
<.04
<.005
.06
.05
6
49.0
14.6
32.0
29.8
1.3
30.5
.99
.77
.70
.33
.57
.30
>2.0
2.0
2.0
<.04
<.04
<.04
<.04
<.04
<.04
.29
.14
.35
7
22.1
>100
11.4
1.7
33.8
1.5
.83
.92
.98
.48
.26
.59
>2.0
>2.0
>2.0
<.04
<.04
<.04
<.04
<.04
<.04
<.005
.29
.11
8
76.0
85.0
72.0
15.3
15.8
15.6
.62
.72
.71
.63
.67
.76
.94
.99
1.3
<.04
<.04
<.04
<.04
<.04
<.04
.09
.10
.08
9
328
314
305
10.3
6.3
7.2
1.1
1.0
1.2
.81
.76
>1.0
1.6
1.4
1.6
<.04
<.04
<.04
<.04
<.04
<.04
.07
.06
.07
NOTE: All units in mg/l
                                      76

-------
                              TABLE C-2 (continued)
                        RAW DATA — METALS (Total) — 1976
SAMPLE
NO.
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3

PARAMETER
COLUMBIUM
COLUMBIUM
COLUMBIUM
CHROMIUM
CHROMIUM
CHROMIUM
COBALT
COBALT
COBALT
COPPER
COPPER
COPPER
LEAD
LEAD
LEAD
MOLYBDENUM
MOLYBDENUM
MOLYBDENUM
NICKEL
NICKEL
NICKEL
VANADIUM
VANADIUM
VANADIUM
ZINC
ZINC
ZINC
SELENIUM
SELENIUM
SELENIUM
STRONTIUM
STRONTIUM
STRONTIUM
ZIRCONIUM
ZIRCONIUM
ZIRCONIUM

1
.01
<-005
.01
.05
.02
.04
<.04
<.04
<04
<.20
.01
.03
<.04
<.04
.08
.04
<.02
<.04
<1.0
<.04
<.04
.07
.03
.04
<.20
.04
.08
<.04
<.04
.05
.22
.07
.10
<.01
.01
.01
MILL NO.
2
<.02
0
<.005
.07
.02
.02
<.08
<.04
<.04
<.14
.01
.02
.20
<.04
<04
.31
.09
.10
<1.0
.01
<.04
.03
.01
.01
.30
.05
.09
.06
.01
<.04
1.1
.39
.35
.01
<-005
.01
3
<.005
<.005
.01
.11
.03
.03
<.04
<.04
<.04
<.11
.03
.09
<.14
<.04
.07
.12
<.02
.11
.07
<.04
<.04
.10
.02
.02
<.40
.07
.10
.08
<.04
.05
.36
.17
.20
.01
<.005
.01
4

.01
.02

.05
.02

<.04
<.04

.02
.03
_
<.04
<.04
	
<.04
.14
	
<.04
<.04
—
0
.03
	
.06
.36
	
<.04
.10
„_
<.04
.22
	
<.005
.01
5
<.01
	
.01
.05
—
.04
<.04
—
<.04
<.05
—
.01
<.08
—
<.04
.08
—
.11
<.04
—
<.04
.01
—
.01
<22
—
.05
.08
—
<.04
.27
—
.28
.01
—
.01
6

.01
<.005

.04
.07

<.04
<.04

.03
.35
_
.08
<.04
—
<.04
<.04
	
<.04
<.04
	
.01
<.005
	
.06
2.1
—
.05
<.04
—
.09
.31
—
<-005
<.005
7
<.01
<.005

<.13
—
—
.04
<.04
—
.10
—
—
<.19
<.04
—
<.02
<.04
—
<.05
<.04
—
.01
<.005
—
<.25
3.6
—
.09
<.04
—
.27
.33
—
.20
<.005
	
8
<.005
.01
.01
.01
.02
.02
<.04
<.04
<.04
.01
.01
.03
<.04
<.04
<.04
<.02
.09
.09
<.04
<.04
<.04
.01
.01
.03
.07
.08
.13
<.04
.05
.05
.18
.20
.18
<.005
.01
.01
9
.01
.01
.01
.03
.03
.08
<.04
<.04
<.04
.04
.03
.09
.07
<07
<.04
.18
.16
<.04
<.04
<.04
<.04
.01
.01
<.005
.07
.05
.14
.06
<-04
<04
.29
.18
.38
.01
.01
.02
NOTE: All units in mg/l.
                                     77

-------
                                     TABLE C-3
                        RAW DATA — METALS (Soluble) — 1976
SAMPLE
NO.
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3

PARAMETER
CALCIUM
CALCIUM
CACLIUM
MAGNESIUM
MAGNESIUM
MAGNESIUM
IRON
IRON
IRON
MANGANESE
MANGANESE
MANGANESE
ALUMINUM
ALUMINUM
ALUMINUM
ANTIMONY
ANTIMONY
ANTIMONY
ARSENIC
ARSENIC
ARSENIC
BORON
BORON
BORON
MILL NO.
1
>100
13.4
16.9
5.3
1.4
2.4
<1.0
.55
1.6
.55
.17
.36
5.3
1.6
5.3
<.04
<.04
<.04
<.04
<.04
<.04
.14
.23
.20
2
<100
—
117
11.6
2.8
2.9
<1.3
.84
1.3
1.6
.35
.20
2.3
.73
.65
<.04
<.04
<.04
<.04
<.04
<.04
<.005
.03
.19
3
100
—
112
7.3
—
5.1
<2.2
—
1.6
.81
—
.67
3.5
—
2.8
<.04
—
<.04
<.04
—
<.04
<.005
—
.15
6

10.8
27.0
_
1.1
26.0
_
.81
1.1

.51
.27
_
2.7
4.5
_
.05
<.04

<.04
<.04
_
.10
.20
7
>20.0
27.2
—
5.7
25.7
—
<3.0
1.4
—
1.6
.15
—
8.5
4.5
—
<.08
<.04
—
<-05
<.04
—
.09
.15
—
8
54.6
72.7
57.0
13.2
14.2
13.0
.62
.74
.76
.58
.35
.66
1.8
2.5
4.8
<.04
<.04
.05
<.04
<.04
<.04
.04
.10
.08
9
133
111
234
8.4
5.8
5.8
.94
.84
1.3
.70
.75
.91
1.4
1.0
2.0
.06
.05
<.04
<.04
<.04
<.04
.07
.12
.18
NOTE: All units in mg/l.
                                       78

-------
                              TABLE C-3 (continued)
                       RAW DATA— METALS (Soluble) — 1976
SAMPLE
NO.
1
2
3
1
2
3
1,2,3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3

PARAMETER
COLUMBIUM
COLUMBIUM
COLUMBIUM
CHROMIUM
CHROMIUM
CHROMIUM
COBALT
COPPER
COPPER
COPPER
LEAD
LEAD
LEAD
MOLYBDENUM
MOLYBDENUM
MOLYBDENUM
NICKEL
NICKEL
NICKEL
VANADIUM
VANADIUM
VANADIUM
ZINC
ZINC
ZINC
SELENIUM
SELENIUM
SELENIUM
STRONTIUM
STRONTIUM
STRONTIUM
ZIRCONIUM
ZIRCONIUM
ZIRCONIUM
M
1
<.005
<.005
<.005
.02
.02
.05
<.04
.01
.01
.04
<.04
<.04
.06
.06
<.02
.12
<.04
<.04
.04
.01
.04
.05
.06
.04
.08
^^^•^•^^•^^•^^
<.04
<.04
<.04
.28
.08
.12
.01
<.005
.01
2
<.005
.02
<.005
.02
.02
.03
<.04
.01
.02
.02
<-04
<-04
<.04
.07
.10
.12
<.04
.08
.06
.01
.02
.02
.06
.13
.11
^IHBHIBWBIH^l^H
<.04
<.04
<.04
.28
.40
.38
.01
.01
.01
3
<.005
<.005
.01
.02
.03
.02
<.04
.02
.02
.11
<04
<.04
<.04
.06
<.02
.07
<.04
.05
<.04
-.03
.02
.02
.06
.11
.09
••••••••••••^•••••••WHIBH
<.04
<.04
<.04
.10
.19
.22
.01
<.005
<.005
4
.01
.02
.03
.06
.06
.08
<.04
.02
.02
.11
<.04
<.04
.09
<.02
.03
.10
<04
<.04
.11
.02
.01
.04
.26
.09
.46
^^•IWHW^MIIM
<.04.
<.04
.05
.27
.09
.28
<.005
.01
;01
LL NO.
5
<.005
.01
.02
.02
.03
.03
<.04
.01
.02
.02
<.04
<.04
<.04
<.02
.40
.12
<.04
.04
.06
<.005
.01
.01
.05
.14
.07
^«^_^^^^_
<.04
<.04
<.04
.20
.30
.35
<.005
.0!
.01
6
.01
.01
.02
.01
.05
.03
<.04
.02
.03
.07
<.04
<.04
<04
<.02
.10
.10
<.04
<.04
<.04
.01
.01
.02
1.2
.12
1.9
^AAO^^^^^BH
<.04
<.04
<.04
.40
.10
.38
<.005
.01
.01
7
<.005
.02
.02
.03
.03
.02
<.04
.03
.06
.03
.06
<.04
<.04
.02
.03
.10
<.04
.04
.06
<.005
.02
.01
.05
>2.0
.09
^^•^•••••••••••i
<.04
<.04
<.04
.09
.39
.11
<.005
.01
.01
8
.01
.01
.01
.02
.02
.03
<.04
.02
.02
.03
<.04
<.04
<.04
.03
.03
.12
<.04
<.04
<.04
.01
.01
.02
.08
.08
.15
••••••••••WMIIIIIII
<.04
<.04
<.04
.20
.22
.21
<.005
<.005
.01
9
.02
.02
.02
.03
.03
.03
<.04
.04
.03
.04
<.04
<.04
<.04
.17
.14
.17
.06
.06
.06
.01
.02
.02
.08
.06
.12
•••(••^••••Ml
.04
.04
<.04
.40
.33
.50
.01
.01
.01.
NOTE: All units in mg/l.
                                     79

-------
                        TABLE C-4
              SUPPLEMENTAL DATA — 1977
PARAMETER
TSS
VSS
TS
TVS
TKN (TOT)
TKN (SOL)
ORGANIC N (TOT)
ORGANIC N (SOL)
NH -N
MILL NO.
1
67
58
1,090
430
4.9
2.4
4.7
2.2
0.23
2
8
8
1,600
710
5.0
4.1
3.1
2.2
1.9
3
89
65
820
280
9.6
2.0
8.6
1.0
1.0
4
843
792
5,490
2,750
—
3.4
—
3.2
0.20
5
45
37
2,260
710
6.1
1.7
5.8
1.4
0.31
6
60
40
3,180
740
4.7
1.9
4.5
1.7
0.21
NOTE:  All units in mg/l.
                                80

-------
          100 1
           80 •
           60 -
oo
u
K
                            1.0
                                    2.0             3.0            4.0

                                                     SIZE - MICRONS

                                         Figure C-l

                                         MILL NUMBER  1


                             PARTICLE SIZE  (DIRECT COUNT METHOD)

-------
             40
oo
ro
             30 -
          u.

          O  20
          u>
          U
          oc
          111
          a.
             10 -
                                                             3              4


                                                               SIZE - MICRONS
                                                      Figure  C-2

                                                    MILL NUMBER 2


                                                     PARTICLE SIZE

-------
          40-1
00
CO
          30 J
o
,K
111
Q.
          10 4
                                                         3              4

                                                            SIZE-MICRONS

                                                     Figure C-3

                                                  MILL  NUMBER 3


                                                   PARTICLE SIZE

-------
          40  -
          30  -
          20  -
        UJ
        U
        cc
00
-ps.
          10  -
/
/v
                              \
                                                          3              4

                                                             SIZE-MICRONS
                                                       Figure C-4
                                                      MILL NUMBER  4

                                                      PARTICLE SIZE

-------
          40  -
00
cn
          30 -
       o

       u.
O
E
ui
          20  -
          10 -
                                                             SIZE - MICRONS
                                                       Figure C-5

                                                     MILL NUMBER 5
                                                      PARTICLE SIZE

-------
           40 -J
00
           30 -I
           20 -I
ut
O
K
ui
0.
           10 A
                                                            3              4

                                                               SIZE - MICRONS
                                                        Figure C-6
                                                       MILL NUMBER  6

                                                       PARTICLE SIZE

-------
          40 -
          30 -
oo
      o
      u.
      O
ui
U
K
LU
           20 -
           10 -
                                                         T
                                                                        T
                                                          3              4

                                                          SIZE - MICRONS

                                                      Figure C-7

                                                     MILL NUMBER 7
                                                      PARTICLE SIZE

-------
                                                          oe
                                                          OS
                                                              o
                                                              o
                                                              a
                                                              UJ
                                                        \- or
3MOHOIM - 3SI8
      8-0
    8 flaaMUM JJIM


     3SI8 3JOITflA9

-------
         40 -
         30  -
00
lO
      e

      O   20
ui
U
c
IU
a.
          10  -
                                                         3              4

                                                           SIZE - MICRONS


                                                      Figure  C-9

                                                    MILL NUMBER  9


                                                    PARTICLE SIZE

-------
                              TECHNICAL REPORT DATA
                        (Please read Instructions on the reverse before completing)
 1. REPORT NO.

  EPA-600/2-79-037
                                                   3, RECIPIENT'S ACCESSION-NO.
 4. TITLE ANDSUBTITLE
                                                   5. REPORT DATE
  Post Biological Solids  Characterization
  and Removal  from Pulp Mill  Effluents
                                                    January 1979 issuing date
           6. PERFORMING ORGANIZATION CODE
 7. AUTHOR(S)
  R. R.  Peterson
  J. L.  Graham
                                                   8. PERFORMING ORGANIZATION REPORT NO.
 9. PERFORMING ORGANIZATION NAME AND ADDRESS
  CH2M HILL,  INC.
  P. 0. Box  428
  Corvallis,  OR  97330
           10. PROGRAM ELEMENT NO.

             1BB610
           11. CONTRACT/GRANT NO.

             68-03-2424
 12. SPONSORING AGENCY NAME AND ADDRESS
  Industrial  Environmental  Research Lab - Cinn,
  Office of Research and Development
  U.S.  Environmental  Protection  Agency
  Cincinnati,  OH  45268
           13. TYPE OF REPORT AND PERIOD COVERED
             Final
           14. SPONSORING
7/76-1/77
3 AGENCY CODE
             EPA/6.0 0/12
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT

        The  study characterized the post biological solids  in  pulp and
  paper mill  secondary effluent and evaluated  various suspended solids
  removal techniques.  Characterization was performed on samples from 9
  mills, representing various  locations, pulping processes  and treatment
  system types.   Results indicate the solids are mostly biological in
  nature.  Coagulation by alum in conjunction  with a cationic  polymer
  appeared to  provide the best results.  Six solids removal  techniques
  were tested  but only mixed media filtration  and sand filtration
  appeared effective enough to warrant further investigation.
 7.
                            KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                                        b. IDENTIFIERS/OPEN ENDED TERMS
                         COSATI Field/Group
 Paper  mills,Pulp Mills,
 Filtration, Sand Filtration*,
 Coagulants*, Coagulation, Flotation,
 Flocculants, Effluents, Solids*,
 Sedimentation, Waste Treatment
 Mixed Media Filtra-
 tion*,  Dissolved Air
 Flotation*, Micro^
 straining*, Solids
 Removal,  Magnetic
 Separation, Secondar
 Effluents
        13B
 8. DISTRIBUTION STATEMENT


 Release  to  Public
19. SECURITY CLASS (This Report)
  Unclassified
   21. NO. OF PAGES
      104
20. SECURITY CLASS (Thispage)
  Unclassified
   22. PRICE
EPA Form 2220-1 (9-73)
                                                            » U.S. GOVERNMEin PRINTING OFFICE; 1979-657-060/1585

-------