United States       Office of Water Regulations      EPA-440/1 -88-025 K
Environmental Protection     anc| Standards TWH-552)      March 1988
Agency         Washington, DC 20460
U.S. EPA/Paper  Industry
Cooperative Dioxin Screening
Study

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U. S.  ENVIRONMENTAL  PROTECTION AGENCY/PAPER  INDUSTRY

          COOPERATIVE DIOXIN  SCREENING STUDY
                        MARCH  1938
        U. S.  ENVIRONMENTAL  PROTECTION AGENCY
                    OFFICE OF WATER
      OFFICE  OF WATER  REGULATIONS AND  STANDARDS
                WASHINGTON, D.C.   20460
                          U.S. Environmental Protection Agency
                          Region 5, Library (PL-12J)
                          77 West Jackson Boulevard, 12Ul Floor
                          Chicago. IL  60604^3590

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                         ACKNOWLEDGMENTS
    Alexander C.  McBride  was  USEPA's  project director  for this
study and Gary A.  Amendola was USEPA's project manager.  Russell 0.
Blosser, NCASI, was  the  project manager  for  the  paper industry.
The principal  authors of  this  report  were  Gary A.  Amendola,
USEPA, and Raymond C.  Whittemore,  Ph.D.,  NCASI.   Francis Thomas,
USEPA, and Lawrence E. LaFleur, NCASI,  served  as quality assurance
officers.  Analysis  of samples for 2,3,7,8-tetrachlorodibenzo-p-
dioxin and 2 , 3,7,8-tetrachlorodibenzofuran  were  conducted at the
Brehm Laboratory, Wright  State University, Dayton, Ohio, under the
direction of  Thomas  0. Tiernan,  Ph.D.   Analysis of  samples for
selected chlorinated phenolics  were  conducted at the  NCASI West
Coast Regional Center, Corvallis,  Oregon, under  the direction of
Lawrence E. LaFleur.

    The authors  acknowledge  the  contributions  of  the following
people who  participated  in  the  conduct  of  the  field  studies:
David R. Barna, Jonathan  L. Barney, Danforth G. Bodien, Daniel S.
Granz, David A. Parrish,  and Raymond E. Thompson, USEPA;  Andre L.
Caron, James  J. McKeown, and Steven Norton,  NCASI;  and  the many
other people  from participating  paper  companies,  state pollution
control agencies, and  USEPA, whose assistance was  essential for
the successful  completion   of  this  project.   The  authors  also
acknowledge the assistance  of the Michigan Division of Dow Chemical
U.S.A. in  conducting  analyses   of  polychlorinated  dibenzo-p-
dioxins and  polychlorinated  dibenzofurans for selected  samples.
Ms.  Carol Kopcak, USEPA, typed this report.

    Finally, the authors  acknowledge  the efforts and contributions
of Russell 0. Blosser, senior vice president, NCASI, who provided
guidance and  direction throughout  the  conduct   of this  study.
                            DISCLAIMER
    This document  has  been  reviewed   in  accordance  with  U.S.
Environmental Protection Agency policy  and  approved for publica-
tion.  Mention  of  trade names  or  commercial  products  does  not
constitute endorsement or recommendation for use.

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                        EXECUTIVE SUMMARY
    As a result of the National Dioxin Study findings of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (2378-TCDD) in  native fish collected
downstream from a  number  of pulp and  paper  mills and subsequent
findings of  2378-TCDD  in  bleached   kraft  pulp  and  paper  mill
wastewater sludges,  the   United  States Environmental Protection
Agency (USEPA) planned a detailed process evaluation  study at one
mill.  Through  subsequent discussions  with  the  paper industry,
USEPA and the industry agreed  in June 1986 to conduct  a cooperative
screening study of five bleached  kraft pulp and paper mills on a
shared resource basis.  Three mills were selected on  the basis of
known 2378-TCDD levels in  sludges  and  two  mills were volunteered
by their  parent  companies  to  attain  the  geographical diversity
desired for  the  study.   The  selection of  the  five  mills,  which
represent about  6 percent  of the  bleached  kraft  mills  in  the
United States,  was  not  intended  to  characterize  the  entire
industry.  The principal  objectives of the study were:

    1.  Determine, if present, the source or sources  of 2378-TCDD
        and other  polychlorinated  dibenzo-p-dioxins  (PCDDs)  and
        polychlorinated dibenzofurans  (PCDFs)   at  five  bleached
        kraft pulp and paper mills; and

    2.  Quantify the  untreated wastewater discharge loadings, final
        effluent discharge  loadings,   sludge  concentrations,  and
        wastewater treatment  system  efficiency for  2378-TCDD and
        other PCDDs and PCDFs.

    Field work  for the five-mill  study was  conducted during the
period June 1986-January 1987  through the combined efforts of four
USEPA regional offices, five state environmental control agencies,
the National  Council  of  the  Paper  Industry  for  Air  and  Stream
Improvement, Inc.  (NCASI), and the participating paper companies.
The analytical methods development  program  and  analyses of samples
for selected PCDDs and PCDFs were conducted at the Brehm Laboratory,
Wright State  University.    Selected   samples  were   analyzed  for
certain chlorinated phenolics by NCASI.

    This report  is  limited to presentation  of the  complete data
and the  scientific  and   technical  findings  resulting  from  the
cooperative study.   Consideration  of  public  and   occupational
health, environmental,  consumer  product,  and  regulatory  issues
that may be associated with study findings is beyond  the scope of
this report.  Additional research  is being  planned and implemented
by both  government  and  industry  to  deal  with   such  issues.
                               111

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    To accomplish the first study objective,  it  was necessary to
design a general comprehensive  study plan  of  all major and minor
mill inputs,  intermediates, and mill exports.   The  general plan
was modified as necessary to conform to the specific circumstances
of each  mill.   Because  chlorine  and  chlorine  derivatives  are
first introduced  in  substantial  quantities   in  the  bleaching
process, emphasis  was placed   on  detailed process  sampling  in
bleacheries .

    The principal  mill  exports  sampled  were  bleached  pulps,
treated process  wastewater  effluents,   and  wastewater  sludges
dewatered for  disposal.   Although bleached  pulps are  converted
into paper products at each mill, bleached pulps were considered
mill exports  for purposes of  this  study.   This  eliminated  the
need to sample and quantify mass outputs of  numerous paper machines
which were  not  always  related  to   bleachery  operations  during
field sampling.

    The second  objective  was  addressed  by  sampling  combined
untreated wastewaters, intermediate and  final  wastewater sludges,
and treated process wastewater effluents.   Evaluation of noncontact
cooling waters and possible atmospheric emissions  were not included
in the study design.

    Initially, the analytical program required, where possible, for
each sample,  isomer-specific  analyses  of  tetrachloro  dibenzo-p-
dioxins (TCDDs)  and  tetrachlorodibenzofurans   (TCDFs)  and,  where
possible, for selected samples,, isomer-speci f ic analyses of 2378-
substituted penta-  through  hepta- CDDs  and CDFs,  and  OCDD  and
OCDF.  However, based  upon anal/ses of a limited number of prelimi-
nary samples  and  a  limited number of  USEPA analyses  of samples
from other mills, the scope of  the analytical program was reduced.
The preliminary analyses  indicate that 2378-TCDD  and 2378-TCDF are
the principal  PCDDs  and  PCDFs  found  in  the pulp  and  paper mill
matrices, particularly when considered in  light  of USEPA's 2378-
TCDD toxicity  equivalents approach.   Accordingly,  all  samples
were analyzed  for  2378-TCDD  a nd  2378-TCDF, since  the extensive
analytical methods development  work  required  for isomer-specifie
analyses of the other compounds did not  appear warranted.

    Specific findings  and  observations    from  this  study  are
summarized in  the  sections  thcit follow.   They are grouped  in  a
manner similar to the organization of the report.


                Data Quality and Data Limitations

1.  The analytical protocol for 2378-TCDD and 2378-TCDF developed
for this  study  was  found to be satisfactory  for isomer-specific
determinations of  2378-TCDD  and 2378-TCDF in selected  pulp  and
paper mill  sample  matrices.    Intra-laboratory method  validation
experiments for  pulp, sludge,  and  wastewater  effluent  samples
                                IV

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indicate the performance of the analytical method with respect to
precision and spike recovery is demonstrably uniform.  The method
performance does  not  appear  to  be  sensitive  to  any  specific
matrix or  chemical  effects which  might  be  associated  with  the
manufacturing processes at a given mill.   Limited inter-laboratory
comparisons incorporating different sample preparation, analytical
methods, and  calibration  standards  confirmed   the  presence  of
2378-TCDD and 2378-TCDF in selected samples.   However, a consistent
bias was observed  for quantitation of both  2378-TCDD and 2378-TCDF.

2.  With  few  exceptions,  the  data   quality  assurance  objectives
established for  this  study  for   2378-TCDD  and  2378-TCDF  were
achieved.

   (a)  Laboratory precision expressed as  relative percent differ-
        ence between duplicate analyses for thirty-five 2378-TCDD
        determinations was 15  percent mean (range 1-138 percent);
        and for thirty-three 2378-TCDF determinations,  16 percent
        mean (range 0-62 percent).

   (b)  Field  precision  for eight   2378-TCDD determinations  was
        14 percent mean  (range 4-19  percent); and  for  nine 2378-
        TCDF determinations, 22 percent mean  (range 0-99 percent).

   (c)  For  thirty-five  2378-TCDD  determinations,  accuracy  ex-
        pressed as percent  spike recovery  was   103  percent  mean
         (range 66-168  percent);   and  for thirty-five  2378-TCDF
        determinations, 102 percent  mean  (range 58-153 percent).

   (d)  Including results from intra-laboratory method validation
        experiments, 97  percent  of  the analyses met  the quality
        assurance objectives  for  laboratory precision  and accu-
        racy.  Ninty-five  percent  of   133  determinations   for
        2378-TCDD and  for  2378-TCDF resulted in  analytical  data
        suitable for project objectives.

   (e)  Target  analytical  detection  levels  of  1  ppt  for solid
        samples were achieved  for  all but  one sample for 2378-TCDD
        and all but one sample for 2378-TCDF (different samples) .
        Target analytical detection  levels of 0.01 ppt for liquid
        samples were achieved  for all but three samples for 2378-
        TCDD, and  all  but  two  samples  for  2378-TCDF  (different
        samples) .

3.  Mass  flow  calculations for  2378-TCDD and  2378-TCDF  combine
analytical results with mass flow rates of solid materials  (pulps,
sludges) and liquids  (waters,  wastewaters) .  The mass  flow rates
for pulps  and  final  treated wastewater effluents  are  considered
to be  accurate within  less  than  ±10  percent  while  mass  flow
rates for  sludges,  within  less than ±10  percent to  15  percent.
Mass flow rates for  internal plant wastewaters were generally based
upon best  engineering  estimates and are considered  accurate  to
                                v

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less than ±20 percent to 25 percent.  The reliability of reported
bleach plant chemical application  rates  varied  considerably from
mill to mill, and  in  two cases were  best  engineering estimates.
Non-detect analyses were treated as zero  for mass balance calcula-
tions.  The  calculations and  analyses  presented in  this  report
should be viewed accordingly.


      PCDDs and PCDFs Found in Pulp and Paper Mill Matrices

1.  Analyses  of  polychlorinated   dibenzo-p-dioxins   (PCDDs)  and
polychlorinated dibenzofurans  (PCDFs)  from  samples  obtained at a
number of bleached kraft pulp and paper mills processing primarily
virgin fiber  uniformly   show   that  2,3,7,8-tetrachlorodibenzo-p-
dioxin (2378-TCDD) and 2, 3,1,8-tetrachlorodibenzofuran (2378-TCDF)
are the principal  PCDDs and PCDFs found.   This  is particularly
evident when the data are considered in  light of USEPA's 2378-TCDD
toxic equivalents approach for dealing with mixtures of PCDDs and
PCDFs.

2.  Data for the five  mills included in this study show there is a
characteristic 2378-TCDF/2378-TCDD  ratio  associated  with  indi-
vidual bleach lines and  individual mills, ranging from about 2 to
about 18.    This  observation   suggests  that  once   2378-TCDD  and
2378-TCDF are formed, they are not altered in further processing
or in wastewater treatment.  Factors accounting for the differences
in 2378-TCDF/2378-TCDD  ratios   across bleach  lines  and  across
mills have  not   been  determined,   nor has  the  possible  process
significance been formulated.
                Sources of 2378--TCDD and 2378-TCDF

1.  2378-TCDD and  2378-TCDF are  formed  during the  bleaching  of
kraft hardwood  and   softwood  palps  with  chlorine  and  chlorine
derivatives at mills included in this study.

2.  2378-TCDD was  not detected  in  seven  unbleached  kraft  pulps
collected at the five  mills  at  detection levels ranging from 0.3
ppt to  1.0  ppt.   2378-TCDF  was?  not  detected  in  four  of  seven
unbleached pulps at  detection  levels  less than 0.3  ppt,  but  was
found in three pulps collected  at two mills at  levels ranging from
1.1 to  2.3  ppt.   The  positive  2378-TCDF  findings  in  unbleached
pulps may be  attributed  to reuse  of contaminated  paper machine
white waters for brownstock pulp washing or dilution.

3.  2378-TCDD was found in seven of nine bleached pulps collected
at the  five mills at concentrations  ranging  from 3 to 51 ppt and
2378-TCDF was  found  in  eight  of nine  bleached pulps  at levels
ranging from 8  to  330 ppt.  The median  and  mean  concentrations
are presented below:
                                vi

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                           2378-TCDD        2378-TCDF

            Median             5 ppt          50 ppt
            Mean              13 ppt          93 ppt

4.  2378-TCDD and  2378-TCDF  were found in most  untreated  bleach
line filtrates  sampled  from  the five  mills.   Wastewaters  from
caustic extraction  stages  (E  and  E0)  generally contained  the
highest concentrations and mass  discharges  from the bleach lines
sampled.

5.  The distributions of  2378-TCDD  and 2378-TCDF  in  bleach line
exports (bleached pulp and  bleach plant wastewaters)  were found
to be highly variable from  bleach line to bleach line.  However,
2378-TCDD and  2378-TCDF  were partitioned  similarly  to  bleached
pulps and  bleach  plant   wastewaters  within  each  bleach  line.

6.  2378-TCDD was found in paper  machine wastewaters from three of
five mills and  2378-TCDF  was found  in  paper  machine wastewaters
from each mill.   The  levels  of   2378-TCDD and  2378-TCDF  found in
paper machine  wastewaters were  significantly less than  found in
the respective  bleach plant  wastewaters  at  four of  five  mills.

7.  2378-TCDD was found  in one of  five sludge landfill leachate or
runoff samples at 0.025  ppt, while 2378-TCDF was found in four of
five samples at  levels ranging  from 0.01  to 0.11 ppt.  2378-TCDD
and 2378-TCDF  were not  detected  in coal-fired  power  boiler  ash
samples from  two mills  at  detection  levels  less than  1.0 ppt.

8.  2378-TCDD and other  TCDDs were  found  in a  sample of  blue dye
collected during  preliminary  sampling at  one mill  at  levels of
3.4 and 53 ppt, respectively.


               Formation of 2378-TCDD and 2378-TCDF

1.  The rates  of formation  of  2378-TCDD and 2378-TCDF normalized
to Ibs/ton (kg/kkg)  of  air  dried brownstock  pulp are summarized
below:

                      10~8 Ibs/ton  (kg/kkg)   of  Brownstock  Pulp

                     Bleach Line Exports     Total Mill Exports
  2378-TCDD          ^eight bleach lines)         (five mills)

    Range                 ND-20(10)           0.14(0.07)-11(5.5)
    Median                  4.1(2.0)                   3.0(1.5)
    Mean                    8.0(4.0)                   4.4(2.2)

  2378-TCDF

    Range              2.6(1.3)-360(180)     1.5 (0.75)-130(65)
    Median                     12.5(6.3)                19(9.5)
    Mean                       68   (34)                 41(21)
                               VII

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    The range  computed  from  bleach  line  exports  exceeds  that
computed from  total  mill  exports because  of the integration  of
results from mills with multiple  bleach  lines  in the  mill export
calculations.  The extent to which  these data  are representative
of long-term operations at the  five mills,  or  are representative
of the bleached kraft industry as a whole is not known.

2.  Although the  data  from this  study  are  limited,  the  results
suggest casual  relationships between  the formation of 2378-TCDD
and 2378-TCDF and (1) the degree of bleaching across bleach lines
as estimated by the  chlorine and  chlorine equivalents applied to
the unbleached  pulp, and  (2) the  amount  of  lignin removed in the
pulp across chlorination and caustic extraction stages as estimated
by the difference in  permanganate  number  (K) an,d CEK (permanganate
number after caustic extraction).   Attempts  were made to develop
statistical correlations  with   the  limited  data.  However,  the
results were generally poor.

3.  Bleach lines processing exclusively softwood pulps had higher
rates of formation  of  2378-TCDD and 2378-TCDF  than bleach lines
processing exclusively hardwood pulps.   However, bleaching condi-
tions on the softwood  and hardwood bleach  lines  were different,
and thus,  it is  not possible  to  conclude that  the general  wood
species bleached  is  the  determinant   variable   in  formation  of
2378-TCDD and 2378-TCDF.
               Wastewater Treatment System Findings

1.  2378-TCDD was found  in  treated wastewater effluents from three
of five mills at  levels  ranging  from  0.015  to  0.12 ppt  and 2378-
TCDF was found  in  four  of  five effluents at levels from 0.011 to
2.2 ppt.

2.  2378-TCDD was  found  in  wastwater  treatment sludges  collected
from each of the  five mills  at levels from  17  to 24 ppt (primary
sludges) , 11 to  710  ppt (secondary sludges)  and  3.3 to  180 ppt
(combined sludges).  2378-TCDF was  found at 32  to 380 ppt (primary
sludges), 75 to  10900 ppt  (secondary  sludges)  and  34 to  760 ppt
(combined sludges).

3.  Mass  balance  calculations  around  the  wastewater  treatment
systems for three mills  showed  that about 50  percent to 80 percent
of the  2378-TCDD  and  40 percent  to  60 percent  of the  2378-TCDF
found in treatment  system  exports (treated  effluent,  wastewater
sludge)  can be accounted for by treatment system inputs.  For two
mills the  treatment  system  input loadings  exceeded the  export
loadings by more  than  200 percent.   The poor mass  balances are
attributed to  uncertainties  in  sludge,  influent,  and  effluent
flow rates, the sequencing  of  sampling  at certain mills, and, to
some extent, analytical  variability  associated  with  trace level
analyses near method detection limits.
                               VI 1 1

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4.  There is no  evidence  to  suggest that 2378-TCDD and 2378-TCDF
are destroyed in wastewater treatment systems.  Rather,  they maybe
transferred, to varying degrees, to wastewater treatment sludges.
At two mills, about 10 percent to 15 percent of the 2378-TCDD and
2378-TCDF contained in untreated wastewater streams was transferred
to the sludges  in  the  wastewater  treatment  systems,  while at the
remaining three mills more than 80 percent transfer to sludges is
indicated.  The  precise  distribution of  these compounds  in the
effluent between  suspended  solids  and  the  liquid phase  was not
determined in this study.

5.  The distributions of 2378-TCDD and 2378-TCDF between wastewater
treatment exports  (treated effluents and wastewater sludges)  were
highly variable  from mill  to  mill.   However, the partitioning of
2378-TCDD and 2378-TCDF between  treated  effluents and wastewater
sludges was consistent within each mill.  Mills with higher total
suspended solids in effluents  had higher  levels  of 2378-TCDD and
2378-TCDF partitioned  to  the  effluent  rather than to the sludge.


                   Pulp and Paper Mill Exports

1.  The distributions  of  2378-TCDD and  2378-TCDF among  pulp and
paper mill exports  (bleached  pulp,  treated  effluents, wastewater
sludges)  were highly  variable from mill to mill,  but the parti-
tioning of 2378-TCDD and  2378-TCDF  to  the  exports was consistent
within each mill.

2.  Mass balance calculations  indicate  that  bleach plant sources
accounted for about 90  percent to 140 percent of 2378-TCDD measured
in mill  exports  at  three mills, and  more  than  300  percent  at
another mill.   2378-TCDD  was  not  detected  in bleached  pulp  or
bleach plant  wastewaters  at  one  mill.   For 2378-TCDF,  bleach
plant sources were  found  to account for  70 to 130 percent of the
amount measured  in mill exports at four mills, and more more than
300 percent  in the last  mill.   The poor mass  balance  results at
some mills are attributed  to  uncertainties  in mass flow  rates of
wastewater, sludge,  and  pulp,  and, to  some  extent,  analytical
variability associated  with   trace   level  analyses  near  method
detection limits.
                      Chlorinated Phenolics

1.  For this study,  chlorina-ted  phenolics  include selected chlori-
nated phenols, chlorinated  guaiacols,  and chlorinated vanillins.
Chlorinated phenolics  were  formed  in the  bleaching  process  at
each of the  five mills.   These compounds  were not  detected  in
treated intake process  waters  but  were  found  in  bleach  plant
filtrates and wastewater treatment  system  influents and effluents.
Chlorinated phenolics were  distributed differently  at each mill.
                                IX

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2.  Wastewaters from caustic  extraction  stage (E and Eo)  washers
accounted for most of the chlorinated phenolics.  This finding is
similar to  findings  for 2378-TCDD  and  2378-TCDF  in  bleach line
filtrates.

3.  The  amounts  of  chlorinated  phenolics  found in  C-stage and
E-stage filtrates  were  normalized  to Ibs/ton   (kg/kkg)   of air-
dried brownstock pulp and are summarized below:


        10-3 Ibs/ton (kg/kkg)  of Air-Dried Brownstock Pulp

                                      Sum of C-Stage and
         Sum of Chlorinated            E-Stage Filtrates
         	Phenolics	           (eight bleach lines)

               Range                    9.3-54  (4.2-24)
               Mean                         35  (17)
               Median                       34  (17)


4.  With  the  limited  data  available,  correlations  between the
presence of chlorinated  phenolics  and 2378-TCDD or  2378-TCDF in
wastewater treatment  system  influents  or  effluents  were  not
attempted.  Because chlorinated phenolics  were  analyzed  only for
the water  matrix,  an  evaluation  of  total  chlorinated phenolics
exports from  bleach  plants  (i.,e.,  pulp  and  wastewaters)  could
not be  made.   With  the  limited and  incomplete  wastewater data
available, mass  balance  calculations  between   internal   bleach
plant filtrates  and  wastewater treatment  system  influents were
not attempted.

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              USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
                                 TABLE OF CONTENTS
      EXECUTIVE SUMMARY	   ill

  I.   INTRODUCTION	     1

 II.   STUDY DESIGN 	     3

III.   THE FIVE BLEACHED KRAFT PULP AND PAPER MILLS	     5

      A.   Mill A                                                               5
      B.   Mill B                                                              11
      C.   Mill C                                                              15
      D.   Mill D                                                              20
      E.   Mill E                                                              25

 IV.   FIELD PROGRAM	    30

      A.   Sampling Plan                                                       30
      B.   Sample Collection, Sample Handling, and Sample Custody              32
      C.   Site-Specific Sampling                                              33

  V.   ANALYTICAL PROGRAM	    35

      A.   PCDDs and PCDFs                                                     35
          1.  Compounds Selected for Analysis                                 35
          2.  Preliminary Sanpling - March 1986                               39
          3.  Analytical Methods for 2378-TCDD and 2378-TCDF                  44
          4.  Identification and Quantitation of 2378-TCDD and 2378-TCDF      47
          5.  Intra-Laboratory Method Validation Experiments                  48
          6.  Inter-Laboratory Method Comparison                              54
      B.   Chlorinated Phenolics                                               55
      C.   Total Suspended Solids and Biochemical Oxygen Demand                55

 VI.   QUALITY ASSURANCE	    56

      A.   2378-TCDD and 2378-TCDF                                             56
          1.  Quality Assurance Objectives                                    56
          2.  Quality Assurance Results for 2378-TCDD and 2378-TCDF           58
      B.   Chlorinated Phenolics                                               62
                                          XI

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                            TABLE OF CONTENTS  (continued)
 VII.  RESULTS AND DISCUSSION
       A.  Observation on 2378-TCDF/2378-TCDD Ratio                             65
       B.  Background Satiples                                                   67
           1.  Treated Intake Process Water;; and Residuals                      67
           2.  Kraft Pulping Process                                            70
       C.  Bleach Plant Findings                                                72
           1.  Bleach Plant Chemical Applications                               72
           2.  Unbleached and Bleached Kraft Pulps     ->                         76
           3.  Bleach Plant Wastewaters                                         78
           4.  Distributions of 2378-TCDD and 2378-TCDF                         87
           5.  Formation of 2378-TCDD and 2:!78-TCDF                             89
       D.  Paper Machine Wastewaters, Utility Ashes, and  Landfill  Leachates   107
           1.  Paper Machine Wastewaters                                       107
           2.  Utility Ashes                                                   107
           3.  Landfill Leachates                                              107
       E.  Wastewater Treatment System Findings                                110
           1.  Influents to Wastewater Treatment                               111
           2.  Wastewater Treatment Sludges                                    113
           3.  Treated Process Wastewater Effluents                            113
           4.  Wastewater Treatment System Mass Balances                       116
           5.  Distribution of 2378-TCDD and 2378-TCDF in Wastewater          119
               Treatment System Effluents and Sludges
       F.  Pulp and Paper Mill Exports                                         120
       G.  Chlorinated Phenolics                                               127
       H.  Total Suspended Solids and Biochemical Oxygen  Demand               131

VIII.  FINDINGS AND CONCLUSIONS	   134

       A.  Data Quality and Data Limitations                                   134
       B.  PCDDs and PCDFs Found in Pulp and Paper Mill Matrices              135
       C.  Sources of 2378-TCDD and 2378-TCDF                                  135
       D.  Formation of 2378-TCDD and 2378-TCDF                                136
       E.  Wastewater Treatment System Findings                                138
       F.  Pulp and Paper Mill Exports                                         139
       G.  Chlorinated Phenolics                                               139

       REFERENCES	   141

       GLOSSARY	   142
                                             XII

-------
                       LIST OF ATTACHMENTS
A.  USEPA/Paper  Industry  Cooperative  Dioxin  Screening  Study;
    June 1986, Amendment July 16, 1986.

B.  USEPA/Paper  Industry  Cooperative   Dioxin  Screening  Study;
    Sampling Procedures, Sample Preservation,  and  Sample Handling.

C.  Analytical Protocol  for the  Determination  of  2,3,7,8-Tetra-
    chlorodibenzo-P-Dioxin and 2,3,7,8-Tetrachlorodibenzofuran  in
    Paper Mill Process   Samples  (Woodchips and  Paper  Pulp)  and
    Paper Mill Effluents (Sludge, Ash, Mud, Treated and Untreated
    Wastewater):   Dioxin  I  Analyses;  Wright  State  University,
    Dayton, Ohio, June 1987.

D.  NCASI Methods for  the Analysis of Chlorinated Phenolics in  Pulp
    Industry Wastewaters; Technical  Bulletin  No.  498; July 1986;
    Revised May 1987.

E.  Analytical Results for 2378-TCDD and 2378-TCDF
    (Master Sample Lists).

F.  Mass Flow Rates of 2378-TCDD and 2378-TCDF.

G.  Analytical Results for Chlorinated Phenolics, Total Suspended
    Solids, and Biochemical Oxygen Demand.
                               Kill

-------
     USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
I.  INTRODUCTION

    As a result  of National  Dioxin  Study1  findings  of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (2378-TCDD) in  native  fish collected
downstream from a number of pulp and paper mills (levels from <5 to
85 parts per trillion (ppt)),  and  subsequent findings of 2378-TCDD
in bleached kraft  pulp and paper  mill  wastewater sludges (levels
from <10 to 410  ppt),  the  United  States Environmental Protection
Agency (USEPA)  planned a detailed process evaluation study at one
mill.  Through  subsequent  discussions  with the paper industry,
USEPA and the  industry agreed  in June 1986 to conduct a cooperative
screening study of five bleached  kraft pulp and paper mills on a
shared resource basis  (Attachment  A).   Three mills were selected
on the basis of  known 2378-TCDD levels  in  sludges  and two mills
were volunteered  by  their parent  companies  to attain  the  geo-
graphical diversity desired for  the  study.   The selection of the
five mills, which represent about 6 percent of  the bleached kraft
mills in the United  States, was  not  intended to characterize the
entire industry.   The  principal  objectives  of the  study  were:

    1.  Determine, if present, the source or sources of 2378-TCDD
        and other  polychlorinated  dibenzo-p-dioxins  (PCDDs)  and
        polychlorinated dibenzofurans  (PCDFs)   at  five  bleached
        kraft  pulp and paper mills; and

    2.  Quantify the  untreated wastewater discharge  loadings, final
        effluent discharge loadings,  sludge  concentrations,  and
        wastewater treatment  system  efficiency for 2378-TCDD and
        other  PCDDs and PCDFs.

    Field work  for the five-mill  study was conducted during the
period June 1986-January  1987  through the  combined   efforts  of
four USEPA  regional  offices,  five  state  environmental  control
agencies, the  National Council  of  the  Paper Industry  for Air and
Stream Improvement,  Inc.   (NCASI),  and  the  participating  paper
companies.   The analytical methods development program  and analyses
of samples  for  selected PCDDs  and PCDFs  were conducted  at  the
Brehm Laboratory, Wright State University.  Selected samples were
analyzed for certain  chlorinated phenolics by NCASI.  Conventional
pollutants (total suspended solids (TSS) and five-day biochemical
oxygen demand  (6005)) were  determined for  selected  samples by mill
laboratories for three mills,  by a USEPA laboratory for one mill,
and by a local water  authority for the remaining mill.
                             -1-

-------
                               -2-
    This report is  limited  to  presentation of the  complete data
and the  scientific  and  technical  findings  resulting  from   the
cooperative study.   Consideration  of  public  and  occupational
health, environmental,  consumer  product,  and regulatory  issues
that may be associated with study findings is beyond the scope of
this report.   At   this   writing,  additional  research  is  being
planned and implemented  by  both government and  industry  to deal
with such issues.

-------
                                -3-
II.   STUDY DESIGN

     To accomplish the first study objective,  it  was necessary to
 design a general comprehensive study plan of  all major and minor
 mill inputs,  intermediates, and  mill  exports.   The  general plan
 was modified  as  necessary to conform to the specific circumstances
 of  each  mill.   Because  chlorine  and  chlorine  derivatives  are
 first introduced  in  substantial  quantities   in  the  bleaching
 process, emphasis  was placed  on  detailed  process  sampling  in
 bleachecies.   Mill   inputs   include  wood  chips,  treated  river
 waters used  for  processing,    and  numerous   process  additives
 including pulping chemicals, bleaching  chemicals and  paper mill
 additives (clays, alums, dyes, slimicides,  etc.).   Intermediates
 include river and well water supply treatment  residuals, chemical
 recovery muds,   brown  pulps, untreated  process  wastewaters,  and
 certain wastewater  sludges.  The principal  mill  exports  include
 bleached pulps,  treated process  wastewater  effluents,  and waste-
 water sludges dewatered  for disposal.   Although bleached  pulps
 are converted into paper products at each mill  studied, bleached
 pulps were considered  mill  exports for  purposes of  this study.
 This eliminated  the need to  sample and  quantify mass  outputs  of
 numerous paper machines which were not always related to bleachery
 operations during  field   sampling.   At   some  mills  wastewater
 sludge landfill   leachates   are   also  mill  exports.   They  were
 sampled but  assumed  to be  minor  sources  compared  to  bleached
 pulps, effluents, and sludges.

     The second   objective   was   addressed  by   sampling  combined
 untreated wastewaters, intermediate and  final  wastewater sludges,
 and treated process wastewater effluents.   Evaluation of noncontact
 cooling waters and possible atmospheric emissions  were not included
 in  the study  design.

     Initially,  the analytical program required, where possible, for
 each sample,  isomer-specific analyses  of tetrachloro  dibenzo-p-
 dioxins (TCDDs)  and tetrachloro  dibenzofurans  (TCDFs)  and,  where
 possible, for selected samples,  isomer-specific analyses of 2378-
 substituted penta-  through  hepta-  CDDs  and CDFs,  and OCDD  and
 OCDF.  However,   based upon  analysis  of  a  limited  number  of
 preliminary samples  and  a   limited  number of  USEPA analyses  of
 samples from  other mills,  the  scope of the analytical program was
 reduced.  The preliminary  analyses indicate  that 2378-TCDD  and
 2378-TCDF are the principal  PCDDs and  PCDFs  found in the pulp and
 paper mill matrices,  particularly  when  considered  in light  of
 USEPA's 2378-TCDD toxicity  equivalents  approach.2   Accordingly,
 all samples were analyzed for 2378-TCDD  and 2378-TCDF, since the
 extensive analytical  methods development work required for isotner-
 specific analysis of  the other compounds did not appear warranted.

-------
                               -4 -
    A considerable effort was  expended  to  develop the analytical
protocol used  in  this  study   for  isomer-specific  2378-TCDD  and
2378-TCDF determinations.  The results from field, laboratory and
native spike duplicate, and native spike recovery experiments are
presented herein.  Sample  analyses  were conducted  on a priority
basis to minimize the total analytical burden.   Limited experiments
were conducted to develop analytical  methods  for isomer-specific
determinations of  2378-substituted   penta- through  hepta-  CDDs
and CDFs,  and OCDD  and  OCDF.,   Limited inter-laboratory  method
comparisons were conducted for four  samples.

    Selected samples were analyzed for chlorinated phenolics, total
suspended solids  (TSS),  and  biochemical  oxygen demand  (8005).
The chlorinated  phenolics analyses   were conducted  to  determine
whether there  is any  relationship between  the  presence  of those
compounds and the presence of  PCDDs  and  PCDFs.   The TSS  and BOD5
analyses were  conducted principally  to  determine  whether  there
were any abnormal  wastewater  treatment  system  operations  during
the surveys.

-------
                                      -5-
     III.   THE FIVE BLEACHED KRAFT PULP AND  PAPER  MILLS

      A.   Mill A

           Mill A is an  integrated  bleached  kraft mill with  a  capacity
      of  580   tons  per  day  of  fine  papers.   Products  include  bond,
      business forms,  coating base, envelope,  ledger,  reprographic, and
      tablet  papers.   Four  batch digestors  are  used  to  pulp  400 tons
      per  day of hardwood and  softwood  chips with a typical  mix  of 70%
      hardwood and 30%  softwood.   Pulping capacity exists  for  365 tons
      per  day  bleached   kraft  (400  tons  per  day  unbleached  kraft) .

           The hardwood  and  softwood pulps are  bleached  separately  in
      three lines.  The  softwood line consists  of a  CEOH  sequence while
      the  hardwood line  is split following  common C  and Eo  stages.  One
      hardwood line has  a single H stage while the other consists of two
      H stages followed  by a peroxide  (P)  stage.  All three bleaching
      lines are schematically shown in Figures  III-l  and  III-2.  Sample
      identification codes and  flow  rates at  the time of  sampling are
      noted next to each sampling location.  Nominal operating conditions
      and  chemical usages are listed in  Table  III-l.   It  is significant
      to  note that chlorine use at this  mill was  estimated  from monthly
      inventory reports.
(DE020901)
180 Tons/day
 Air Dried
                                Eo
             H
                                                                       (DE020902)
                                                                      160 Tons/Day
                                                                       Air Dried
                    (DE020906)
                     1.73 mgd

     a) Possible Over Flow to S1 Seal Box
     b) Possible Over Flow to S2 Seal Box
(DE020907)
 1.44 mgd
(DE020908)
 0.68 mgd
            FIGURE III-l.   Mill A Softwood  Bleaching Line Schematic

-------
                                       -6-

(OE020803)
386 Ton«/d«y
Air Dried


C






( \
K6





                                                      (DE020904)
                                                     176 Ton«/d«y
                                                      Air Drl»d
(•) Poulbl* Ov*r Flow to K2 Seal Box
(b) PoHltal* Ov«r Flow to K4 3««l Bo«
(c) Po««lbl« Over Flow to K1 3<>l Box
                  (DE020909)
                   1.68 mgd
T

Ki


•v. 	 1

>

I




' 	 •



h




\




*-

*




K




3




                                  (OE0209I2)
                                  0.34 y
                                                                           Air Drl.d
           FIGURE  III-2.    Mill A Hardwood Bleaching  Line  Schematic
          The power  boiler  burns  gas  and approximately  350  tons per
      day of bark to produce 650,000 Ibs of steam per hour.  Fly ash from
      the boiler  is  collected  by electrostatic precipitation, combined
      with the  wastewater  treatment plant  sludge  and  disposed  of in  a
      landfill.   There is no contact  of the boiler  ash  with the general
      mill sewer.

          Raw water  to the mill  is pumped  from a nearby  river, treated
      with caustic,  chlorine, alum,  and mixed media  filtration prior  to
      use in  the  mill.    Residues  from  this  treatment  are  sewered.
      Approximately  20  MGD  of  treated  process  water   are   used.    In
      addition, another 5.0 MGD  is  used for noncontact  cooling water  on
      the turbine  condensers.    A  general  schematic of the  mill   sewer
      system  is  shown  in 'Figure III-3.   This figure provides identifi-
      cation  codes and flow rates  associated with each  sample location.
      The measurements or estimates  were the best available at the time
      of sampling.

-------
                               -7-
                           TABLE III-l
MILL A BLEACH PLANT
Parameter
Softwood
Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
°2
NaOCl
Residual C12 (%C12)
Wet Brightness
Permanganate No.
Hardwood 1
*Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
02
NaOCl
Residual C12 (%C12)
Wet Brightness
Permanganate No.
Hardwood 2
*Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
02
NaOCl
H202
Residual C12 (%C12)
Wet Brightness
Permanganate No.
OPERATING

C
w «
1
1.9
99

80
—
—
—
0.24
38.3
20.2
C
_ M
0.6
2.4
104

60
—
—
—
0.23
34
11.4
C
__
0.6
2.4
104

60
—
—
—
--
—
34
11.4
CONDITIONS
Bleachi
EO
— —
1.3
10.5
145


30
10-12
30

AND CHEMICAL USAGES
ng Stage
H H
184
1 1
9.0 8.4
95 95

*
— —
— —
110
1.1 0.85
55.5 77. 5-79. 5 79.0-81.0
2.5-3.0
EO
303
0.8
10.5
148

—
25.3
8
—
--
54
2.9
E0
303
0.8
10.5
148

—
25.3
8
—
__
—
54
2.9
_ — _ •_
H H
151.5
1.2 1.2
8.9
104

— __
— —
— —
70
1.1 0
79 79.5-80.5
_ — _ _
H H P
151.5
1.5 1.5 1.5
9.0 8.4 9.8
100 96 150

— — —
3.8
— — —
70
10
0.53 0.14 0.35(H202)
75.7 — 78.5-79.5
— — _ _ _ „
*303 BDT through Eo Stage, then split into two equal flows.

-------
                                 -8-
River Water

Treated
Water
(T>E020801)
20 mgd
                           (DE020915)
                           Bleach Plant
                            7.6 mj|d
            (DE020802)
            (DE020803)
            Raw Water Treatment
              1.6 - 2 mgd
    Evaporator
     drain
    0.5 mgd
                     To Waste Treatment

                        (DE020921)
                         20.1 mgd
                 (DE020806)
                  Pulping
                  3.6-4 mgd
(DE020807)
 Recovery
 0.17 mgd
Powerhouse
                                                           (DE0208J8)
                                                            0.6 mgd
                                               (DE020811)
                                             Paper machines
                                                4.3 mgd
            FIGURE III-3.   Mill A Sewer  System Schematic
     The  wastewater treatment (system consists of primary  clarifi-
cation  and  oxygen activated  sludge  (UNOX)  with 8.4 hours  aeration
time.   All  mill  wastewaters  go to  the  primary  clarifier  with no
bypass.   Combined primary  and secondary  sludge are dewatered with
belt filter presses  prior  to  landfill  disposal.   The  noncontact
cooling water mixes  with  the  secondary  effluent  prior  to  river
discharge.   The wastewater treatment plant schematic is  shown in
Figure  III-4.   Identification codes and  flow rates at the time of
sampling  are  noted  next  to   each   sampling  location.   Typical
operating conditions  and  performance  are  shown  in  Tables  III-2
and III-3.   These data reflect, average  operating  conditions  for
both winter and summer months.

-------
                             -9-
Primary
Clarlfler
r.

(D
<
A ,
J-
r^
Primary
Sludge
E020920)
66 T/D
i
UNOX
Activated
Sludge
4 '
Secondary
Clarlfler




V-
Cooling water
16.2 mgd
) (DE020922) River
/ 23.2 mgd


Secondary Sludge
(DE020820) 7.2 T/day
. Fly ash
(DE020919) *0ven drled
20 T/D
                 Combined Sludge
                 (DE020920) -82.2 T/D
FIGURE III-4.    Mill  A Wastewater Treatment  Plant  Schematic
                         TABLE III-2

   MILL A WASTEWATER TREATMENT PLANT OPERATING  PARAMETERS
  Parameter

  Flow  (MGD)
  Residence  Time (days)  .
  Mixed  Liquor  Suspended Solids  (mg/L)
  Return  Sludge Recycle (%)
  Aeration Horsepower (HP/million gallons)
Value

21-25
  0.5
 3200
   73
   33

-------
                            -10-


                        TABL1S 111-3

     MILL A WASTEWATER TREATMENT PLANT PERFORMANCE DATA


Parameter                               Winter       Summer
BOD5 Loading (Ibs/day)                  20,000       18,800
BOD5 Removal (%)                             94           83
Suspended Solids Loading  (Ibs/day)      18,800       20,700
Suspended Solids Removal  (%)                 68           58
Primary Sludge Production  (tons/day)                     55*
   Consistency  (%)                                   unknown
Waste Activated Sludge Production  (tons/day)            7.2*
   Consistency  (%)                                       1.6
Combined Dewatered
   Sludge Production  (dry  tons/day)          59           65
   Consistency  (%)                            37           39

*0ven dried basis

-------
                               -11-
B.  Mill B

    Mill B is  an  integrated  bleached kraft mill  with a capacity
for 875  tons  per  day  of  miscellaneous papers  plus  150 tons per
day of market  pulp.   Major  paper  products include  bond,  facial
tissue, toilet tissue, napkin tissue, freezer paper,  toweling, and
newsprint.  Two continuous  digestors (Kamyr ,  Bauer)  are used to
pulp both hardwoods and softwoods with a typical mix of 20% hardwood
and 80% softwood.   The bleached/semi-bleached kraft  pulp capacity
is 775 tons per day  with  an additional 300 tons  per day of pulp
generated by refiner  mechanical groundwood.  The  latter  is used
primarily for the newsprint production.
     The bleach  plant  consists  of  a
sequence; however, during the  survey,
CDEHHD sequence.   The  bleach  plant
                                       single  line with  a CEHED
                                       the  line  was operated in a
                   The bleach  plant  is   shown   schematically   in
Figure III-5.  Sample identification codes and flow rates  of both
pulp and washer filtrates are listed next to each sampling location.
Nominal operating  conditions  and  chemical usages  are  listed   in
Table III-4.
(86374611)
860 T/day
Air Dried


C











^



1 '
L E

>

*-!

<
\

^
(86374613)
6.06 mgd


^

1
i



»
- H






' (86374616) \

4
r
•
N 	
0.24
1

i
(86374616)
2.20 mgd
mgd


i
»
•




t










E












i
i




1
i



D






<86374617) i



1.36 mgd







r


i
>
(86374614
1.67 mgd

                                                             (86374612)
                                                             770 T/day
                                                              Air Dried
          FIGURE III-5.  Mill B Bleaching Line Schematic

-------
                               -12-
                           TABL:*: in-4

   MILL B BLEACH  PLANT  OPERATING CONDITIONS  AND  CHEMICAL USAGES

                                       Bleaching Stage	

         Parameter              C      E
               H
Throughput (ADT/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
   Cl2
   NaOH
   NaOCl (as available Cl2)
   C102
   Residual Cl2 (Ibs/ton)
Permanganate No.
Br ightness
 100
 3.5
19.8
         58
4.5
  34

Trace

  59
                      D
34.5
0.23
—
102
34.5
0.70
10.2
150
34.5
0.15
9.1
150
34.5
0.08
--
150
34.5
2.80
2.1
150
                        61
  10
Trace

  83
    The power boiler at the mill uses both gas and oil to produce
200,000 Ibs/hour  of steam.   There  is no  significant  contact of
residues from this operation with the mill general sewer.

    Raw water to  the mill  is taken from  a  nearby river, treated
with filtration,  and  chlorinated  prior  to  use  in  the  mill.
Approximately 40  MGD  of treated water  are used  in  the  process.
Filter plant backwash from this process is returned to the river.
The general mill  sewer is  shown schematically  in  Figure III-6.
This figure provides identification codes and flow rates associated
with each sample  location.   These  flow  values represent measure-
ments or estimates where flow is not routinely monitored.

    The wastewater  treatment  system  consists of primary clarifi-
cation and a holding  pond  with 8 hours detention time.  The pond
is followed  by  an  activated  sludge system  with  an  additional
8 hours  aeration  time.   The acid  sewer  from  the  bleach  plant
bypasses primary  treatment  and is put directly  into the holding
pond.  Primary  sludge  is  dewatered on  a coil  filter,  while the
waste activated   secondary -sludge  is dewatered with   a  Winkle
press.  Polymer  is   used  as  an  aid  in  dewatering  this sludge.
Primary sludge  is landfilled on  site while  secondary  sludge is
disposed off  site.   The   wastewater  treatment   plant   is  shown
schematically in  Figure  III-7.,   Identification  codes  and  flow
rates at  the  time  of  sampling  are  noted  next to each  sample
location.  Typical  operating  conditions  and  performance during
both winter and  summer months are shown in Tables  III-5 and III-6.

-------
                             -13-
                        TABLE III-5

   MILL B WASTEWATER TREATMENT PLANT OPERATING  PARAMETERS
  Parameter                                          Value
  Flow (MGD)                                           40.8
  Residence Time  (days)                                 0.8-0.9
  Mixed Liquor Suspended Solids  (mg/L)               3100
  Return Sludge Recycle  (%)                            97
  Aeration Horsepower  (HP/million gallons)            208
                        TABLE III-6

     MILL B WASTEWATER TREATMENT PLANT PERFORMANCE  DATA


Parameter                               Winter       Summer
BOD5 Loading (Ibs/day)                  55,000       55,000
BOD5 Removal (%)                            93           94
Suspended Solids Loading  (Ibs/day)      98,000       98,000
Suspended Solids Removal  (%)                88           88
Primary Sludge Production  (tons/day)        40           40
   Consistency (%)                           17           17
Secondary Sludge Production (tons/day)       3           15
   Consistency (%)                           13           13

-------
                                  -14-
Backwash
(86374602)
1.3 mgd
i
*Proc
To P
River Water
1
/" N Treated V/ater
• / * — *-
L
>
To River
ess Sewer
rlmary Treati
• Artificial Sample of
untreated wastewater made
by combining this sewer
with Acid Sewer (C Stage
Effluent 86374613). New
sample number Is 86374644
C Stage effluent bypasses
primary.
J (86374601) "
37.1 mjjd
i
nent
\
A
Pulp
Dryer
<
E Stage
filtrate
(86374615)
2.2 mgd
Corrosive Sewer
Recaust
Evaporators
Refiner
(86374607)
3.1 mgd
r
k
^#1, #2 Paper machine
(86374621)
6.9 mgd
,(86374609)
21.3 mgd
^ 0
(2.2 mgd)
^#3, #4 Paper machine
* (4.7 mgd)
Brown Stock Effluent
(86374606)
10.8 mgd
          FIGURE III-6.   Mill  B  Sewer  System Schematic
           Primary
           Clarlfler
                         Acid Sewer
                         (86374613)
                          6.05 mgd
31.3 mgd
Holding
Pond


AantlOfi
Pond
             <  Primary Sludge
                (86374641)
                 36 T/day
                Bone Dried
*(86374643 with polymer)
 t
                                  Effluent
                                -•	>•
                                (86374646)
                                  36.6 mgd
                Secondary
                 Clarlflers
Secondary Sludge
  (86374642)*
    17 T/day
   Bone Dried
                                                            (86374646)
                                                           Landfill Leachate
                                                            not added to
                                                           waste treatment
FIGURE  III-7.     Mill  B Wastetwater  Treatment  Plant  Schematic

-------
                                 -15-
 C.  Mill  C
     Mill  C  is an  integrated  bleached kraft mill  with a  capacity
  for 1170  tons per day  of printing  and  writing papers.   Products
  include business form paper,  carbonless copy paper,  cover  paper,
  and tablet  grade  paper.   Eight batch digesters are  used to  pulp
  2200  tons per day of hardwood chips.  Pulping capacity exists for
  1000  tons per day of bleached kraft, although  current production
  is 800 tons  per  day.

       The  brownstock pulp is bleached with a single C/DEOD sequence.
  The bleach plant is shown schematically in Figure  III-8.   Sample
  identification codes and flow rates  are noted next to each sampling
  location. Nominal  operating  conditions and  chemical usages  are
  listed in Table  III-7.
(DE026002)
1004 Air Dried
Tone/day
           C/D
Eo
                                                               (DE026003)
                                                               768 Air Dried
                                                               Tons/day
D
                    (DE026004)
                    2.96 mgd
                                        T
       (DE026006)
        4.9 mgd*
      (DE026006)
       6.03 mgd*
                                            Normally no discharge
            FIGURE III-8.  Mill C Bleaching Line  Schematic

-------
                                -16-


                              TABLE III-7

MILL C BLEACH PLANT NOMINAL OPERATING CONDITIONS AND CHEMICAL USAGES

                                          Bleaching Stage

                Parameter	           C/D        Eo      D
       Throughput (ADT/day)             1000
       Residence Time (hours)            0.3     0.62     4.5
       PH                                1.7     11.5     4.0
       Temperature (°F)                   130      170     170
       Chemical Usage (Ibs/ton)
          C12                             60
          C102                             5       --     18
          02                              --     12.5
          NaOH                            —       20
          Other (S02)                     --       --     50
          Residual C12                  Trace
       Brightness                         —       47     >88
     Four power  boilers  are  used to produce  1.3 million  Ibs of
 steam/hour.  Three burn  coal while the  fourth  burns wood wastes
 (800 tons  per  day).   Fly  ash   from  the three  coal  boilers is
 collected by electrostatic  precipitators while ash  from the  wood
 waste boiler is  collected by a  wet  scrubber.   All  ash  including
 bottom ash  is  landfilled.   Wastewater is used  to  convey some of
 these ashes and is then sewered.

      Raw water to the mill  is supplied from two  sources  including
 river water "and  wells.    Portions  of  the total  (30 MGD) receive
 treatment with either sand  filtration or lime  softening prior to
 use in specific parts of  the mill.   Residues from  both  processes
 are sewered.  The general mill sewer system  is  shown schematically
 in Figure  III-9.   Identification codes  and flow  rates  for  each
 sample location are provided.

-------
                      -17-
I

o ^* ^ *••
s|lll
Scomza
*




1

— .
"S
E
T-
s




A
•o
i»:
c
„ Z
ts
*•— o
*R z

ov= 3 i- •
CM en o j • ^
CM . -r,-O CO 0
00 0 0 = «-5
•""sSw jo
U-.
I
c
«
*u

*
j>
'
U
cc

c
I1

"*]
t
V







r . ^

' i!
•^ ^ Q ^

o
o
•3L
a.
6
Z
r <
w>
CO
i
Z
CM
6
z

d
Ecx
*^
(4.0 mgd)
— 5 ~
o S ^>
co J E

0 | S
u a —
o 9
-.T" ' ' e>
** i, E
O
J f c~
« o 6 • —
I* I °*l
» 1 > 285
25 S s I S
So m co o u.





• 9
°!~
ta W
•g o E
r = 6
o2-

                                 0 = 0
                                 Z c E

                                 °I2

                                 CM 4. o>


                                 all
                             — c o
                            to'o a'"

                            ills
                            Not. 21,22,23,24 PM
                                                            O
                                                           •f-i
                                                           JJ
                                                            m
                                                            s
                                                            a;

                                                            u
                                                           CO



                                                            tu
                                                           -P
                                                            w
                                                                       Q)
                                                                       S
                                                                       a>
                                                                       CO

                                                                       u
                                                                       OS

                                                                       D
                                                                       CM

-------
                                -18-
    The wastewater  treatment system  consists of primary  clarifi-
cation followed by a 10-acre aerated stabilization basin  (ASB)  and
a 7-acre activated  sludge  (AST)  system.  Excess  solids  from  the
two secondary clarifiers are returned to both the primary clarifier
and the sludge  thickener.   Thickened secondary  sludge  and primary
sludge are  combined  prior  to  dewatering.    Dewatered  solids  are
utilized commercially and/or sent to a landfill.  Nearly 2 MGD of
the secondary effluent is  recycled back into the mill  and used in
the woodwaste boiler scrubber.  The remaining portion is discharged
to a river.

    The wastewater  treatment  plant  is shown   schematically  in
Figure 111-10.   Identification  codes and flow  rates  at  the  time
of sampling  are  noted  next  to  each  sample  location.   Typical
operating conditions   and performance  are  shown  in Tables  III-8
and III-9.   These data  reflect average operating  conditions  for
both winter  and summer months.
                                                            2 mgd
                                                            Recycle
                                                Secondary
                                                 Clarlflers
            Primary
            Clarifier
                                                            Final
                                                           Effluent
                                                         (DE026013
                                                          (28 mgd)
                (DE026011)
             Combined Dewatered
        Sludge (800 Tons/day * 27% Solids)
   FIGURE  111-10.    Mill C Wastewater Treatment  Plant Schematic

-------
                              -19-



                          TABLE III-8

     MILL C WASTEWATER TREATMENT PLANT OPERATING PARAMETERS


    Parameter                                          Value
    Flow (MGD)                                           28
    Residence Time (days)                                 1.5
    Mixed Liquor Suspended Solids  (mg/L)              2400
    Return Sludge Recycle (%)                            50
    Aeration Horsepower  (HP/million gallons)             38
No
                          TABLE III-9

       MILL C WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter

BOD5 Loading  (Ibs/day)                   100,000-150,000
8005 Removal  (%)                                      97
Suspended Solids Loading  (Ibs/day)               409,000
Suspended Solids Removal  (%)                          96
Primary Sludge Production  (wet tons/day)            2500
   Consistency  (%)                                     8
Waste Activated Sludge Production  (tons/day)        5800
   Consistency  (%)                                     0.6
Combined Dewatered Sludge
   Production (wet tons/day)                         800
   Consistency  (%)                                    27%


 significant differences between winter  and  summer  operations,

-------
                                 -20-
D.  Mill  D

    Mill  0  is an  integrated bleached  kraft  mill with  a capacity
for 1105  tons  per  day of  paper  products.   Major  products  are
newsprint and telephone directory paper.  Six batch digestors  are
used to  pulp  softwood  chips.   Pulping  capacity  exists  for  460
tons per  day bleached  kraft  (425  tons per day unbleached kraft).
In additional there  is capacity  for  830  tons  per day  groundwood
production.

     The  bleach plant  consists  of two lines, each utilizing  a  CEH
sequence.   The  bleach   plant  is   shown  schematically   in  Figure
III-ll.   Sample identification  codes  and  flow rates  of both pulp
and washer  filtrates  are listed  next  to  each sampling location.
Mominal operating   conditions and chemical   usages  are  listed  in
Table  111-10.  The relatively high hypochlorite use  in the 3 bleach
line hypochlorite  stage is  related to high caustic  carryover from
an undersized E-stage  washer.  Chlorine use  on  the  B bleach line
was computed  from  tank car  inventories.
A Side
   •(DF024409)

          • A »
                                                              250 Tons/day
                                                                (DF24410)
                          |(DF0244I2)
                          1 1.42 mgd
                                   T-(DF024413)
(DF024414)
 1.42 mgd
        B Side
                                                              (DF024411)
                                                              120 Tons/day
          (DF24409)
                           
-------
                            -21-
                        TABLE 111-10

MILL D BLEACH PLANT OPERATING CONDITIONS AND CHEMICAL USAGES
  SOFTWOOD LINE A

  _ Parameter _

  Throughput (dry tons/hour)
  Residence Time (hours)
  PH
  Temperature (°F)
  Chemical Usage (Ibs/ton)
Bleaching Stage
     NaOH
     NaOCl
     Monoethanolamine
     Residual Cl2
  Semi-bleached Brightness
c
13.3
0.91
2.3
67.1
0
0
0.25
2.0
—
E
13.3
0.30
10.5
0
46
0
0
—
—
H
13.3
1.16
8.5
0
0
90
0.14
14.9
69
  SOFTWOOD LINE B

  _ Parameter _

  Throughput (dry tons/hour)
  Residence Time (hours)
  PH
  Temperature (°F)
  Chemical Usage (Ibs/ton)
Bleaching Stage
     NaOH
     NaOCl
     Monoethanolamine
     Residual Cl2
  Semi-bleached Brightness
C
5.8
2.0
76. 5
0
0
—
4.0
—
E
5.8
0.5
0
53
0
0
—
—
H
5.8
2.5
0
0
227
0.39
9.9
69
  NOTE:   Brownstock pulp permanganate number for
         both bleach lines is typically 24.5.

-------
                                  -2.2-
       Power  boilers at the mill burn gas and approximately 600 tons
  per  day  of bark to produce  550,000  Ibs per hour of  steam.   Black
  liquor  is  burned  in a  recovery boiler.   Fly  ash  from  the bark
  boiler  is  collected  with  a  'nechanical  dust collector  and  a  wet
  scrubber.   Both  fly  ash   and   bottom  ash  are  landfilled.   The
  scrubber water  is sewered.

       Raw  water  to the  mill is takan  from a  nearby  lake  and from
  wells.   Water  from  both sources is  chlorinated prior  to  use  in
  the  mill.   Approximately  22 MGD  are  used  in  the   process.   The
  general  mill sewer  is shown in Figure 111-12.   This  figure provides
  identification  codes and  flow  rates associated with each  sample
  location.   These flow values represent measurements  or  estimates
  where flow is not routinely monitored.
(DF024401)
No. Entry
few Water
10.2 mgd
         (DF024402)
          10.2 mgd

         "(DF024403)
          11.7 mgd
So. Entry
Raw Water
11.7  mgd
3)
<
1

(DF024601)
Qroundwood
'aper Machines
9.60 mgd
i
' i
B
Pulp Mill
^Brownstock 2.8 mgd
Dregs, Old Caust
*(DF024406) 0.7 mgd
r \
t
i
Lime Kiln
Sewer
0.06 mgd
'(DF024406)
Evap. Sewer
" O.il mgd
Recovery
Boiler Sewer
0.1 mgd
leach Plant H Stage
1 (DF024414)
A Side Acid ^ 1.42 mgd
(DF024412) 1.42 mgd
IH Stage
(DF024418)
0.92 mgd
TrJF024416) 0.96 mgd
Caustic Sewer
(DF024413) 2.722 ms
i
{
i t
i
(DF024616)
0.06 mgd
Boiler Sewer
d
' To Wast<
(DF0246
Woodyard
0.6 mgd
          FIGURE 111-12.  Mill D General  Mill  Sewer Schematic

-------
                                 -23-
    The wastewater treatment  system consists of primary clarifi-
cation followed by activated  sludge  with  2  to 3 hours detention
time.  A  dissolved  air  flotation  system  is  used  to  control
suspended  solids prior  to  the  secondary clarifiers.   Waste solids
are returned  to the  lagoon.  Waste  activated  sludge  is returned
to the primary  clarifier.   The  combined  sludge is  dewatered and
sent to   landfill  for  disposal.    Chlorine   (1000   Ibs/day)   is
regularly  used  to  control  secondary  sludge bulking.   The  waste
treatment  plant is shown schematically in  Figure  111-13.  Identi-
fication codes and flow rates at  the  time  of  sampling are noted
next to  each  sample  location.   Typical  operating conditions and
performance  during both winter  and  summer  months  are  shown  in
Tables III-ll and 111-12.
               Primary
               Clarifiers
                             Sludge Recycle
                             10 mgd • 0.6% Solids
    (DF024611)
    18.85 mgd
r
^

Activated
Sludge
Solids Recycle


Dissolved
Air Flotation
*r\.

\

j

\
' ht
(
                            Wasted Sludge
                        Primary Sludge
                          (DF024614)
                          0.46 mgd
                            * 3%
                        Dewatered
                         Sludge
                       *(DF024613)
             Secondary
             Clarifiers
 (DF024616)
  0.4 mgd
  • 0.5%
 (DF024519)
after Chlorlnatlon
                       (DF024512)
                       18.49 mgd
   FIGURE  111-13.   Mill  D  Wastewater Treatment Plant Schematic

-------
                               -24-
                           TABLE III-ll

      MILL D WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
     Parameter                                         Value
     Flow (MGD)                                              20
     Residence Time (days)                                 0.75
     Mixed Liquor Suspended Solids  (mg/L)            1200-1500
     Sludge Age                                           2-2.5  days
     Return Sludge Recycle (%)                               50
     Aeration Horsepower  (HP/million gallons)                30
     Primary Sludge Production  (gal/day)                600,000
        Consistency (%)                                   2-2.5
     Waste Activated Sludge Production  (gal/day)        400,000
        Consistency (%)                                    0.50
                           TABLE 111-12

        MILL D WASTEWATER TREATMENT PLANT PERFORMANCE DATA


Parameter                               Winter            Summer
BOD5 Loading (Ibs/day)               15,000-30,000      15,000-30,000
BODs Removal (%)                         85-90              90-93
Suspended Solids Loading (Ibs/day)  100,000-200,000    100,000-200,000
Suspended Solids Removal (%)             90-98              95-99
Combined Dewatered
Dry Sludge Production (tons/day)         50-100             50-100
   Consistency  (%)                       15-18              15-18

-------
                                 -25-
 E.  Mill E
                                        »
     Mill E  is  an  integrated bleached  kraft mill  with  a capacity
 for 1330 tons  per day  of  miscellaneous papers.   Major products
 include bond, business  form paper,  carbonizing, envelope, ledger,
 offset paper, coated publication paper, and  tablet.  Two continuous
 Kamyr digestors are  used  to pulp both  hardwood and softwood chips
 with a typical mix  of  30%  hardwood and 70%  softwood.   The kraft
 pulp capacity  is  1200  tons per day with  an  additional  130 tons
 per day groundwood production.

      The bleach plant  consists  of  two lines both  with a CDEOH/D
 sequence.   One  of  the  lines  alternately  bleaches  hardwood  and
 softwood pulp.  The  bleach  plant is shown  schematically in Figure
 111-14.  Sample identification codes and  flow rates of both pulp and
 washer filtrates  are  listed  next  to  each  sampling  location.
 Nominal operating  conditions  and  chemical  usages are  listed  in
 Table 111-13.
    A Side
(RQ186364)


CD
*

7 ^

i
t

\


4(RQ186369)
* 3 mgd


E0
'
k
1
Y ^

^


i
>

t(R0186370)
T 1.8 mgd

	 1
H/D
4
L

*T ^

^ •

— • — w
(R0186366)
600 Dry Tons/Day
J[R0186371)
* 1.0 mgd
    B Side
                +£5:
(RQ186366)
            D
                                              H/D
                                                             (RQ186367)
                                                             600 Dry Ton8/Day
                  f(RQ186372)
                    1.1 mgd
 (R0186373)
X 1.6 mgd
WRQ186374)
^ 0.76 mgd
          FIGURE 111-14.  Mill  E  Bleaching Line Schematics

-------
                               -26-
                           TABLE 111-13
       Parameter
LINE A - SOFTWOOD

Throughput (tons/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
   Cl2
   C102
   NaOH
   02
   NaOCl
   Residual Cl2  (gm/L)
Brightness

LINE B - HARDWOOD

Throughput (tons/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
   C102
   NaOH
   02
   NaOCl
   Residual C12  (gm/L)
Brightness

LINE B - SOFTWOOD

Throughput  (tons/hours)
Residence Time  (hours)
PH
Temperature (°F)
Chemical Usage  (Ibs/ton)
   C12
   C102
   NaOH
   02
   NaOCl
   Residual Cl2  (gm/L)
Brightness
AT ING CONDITIONS AND CHEMICAL USAGE:
Bleaching Stage
/-i
25
0.67
1.8
110
120
3.3
—
—
—
0.019
—
CD
25
0.33
1.80
130
80.4
2.03
—
—
—
0.022
—
CD
21
0.33
1.80
130
80.4
2.03
—
—
—
0.022
— —
E0
25
1.7
10.7
160
_ _
	
81
7.85
2.97
—
—
Eo
25
1.50
11.2
155
_ _
—
116.5
4.7
—
—
—
E0
21
1.50
11.2
155
_ _ .
	
116.5
4.7
— —
— —
— —
H
25
0.20
9.4
185
— —
	
2.65
—
17.2
0.0
66.3
H
25
0.20
10.1
185
~ _
—
0.35
—
24.6
0.0
64.5
H
21
0.20
10.1
185
-_ -_
	
0.35
—
24.6
0.0
66.1
D
25
1.5-2.0
6.7
180
— _
11.17
2.71
—
—
0.06
84.2
D
25
1.5-2.0
7.0
180
_• «
14.9
4.05
—
—
0.0
85.8
D
21
1.5-2.0
7.0
180
— —
14.9
4.05
—
— —
0.09
84.8

-------
    The  power
bone dry tons
steam per  hour
                                 -27-
boiler  at  the mill  burns oil  and  approximately  250
 per  day of  bark  to produce  1.1 million pounds  of
    Both bottom and  fly ash  are  sewered directly.
    Raw  water to  the  mill  is  taken  from  a nearby river/  treated
with alum  flocculation, sand filtration, and chlorination  prior to
use in  the mill.  Residues  from  the alum flocculation  are  sewered.
Approximately 38  MGD  of  treated  water  are  used  in  the  process.
The general  mill  sewer is  shown  schematically  in Figure  111-15.
This figure   also  provides  identification  codes  and  flow  rates
associated with each sample location.  These flow  values represent
measurements or estimates  when  flow is not  routinely monitored.
River
Water
(RQ1-86366)
38 mgd
Treated Water
• fr{RG1-8635$)
34.6 mgd
      Water
      Treatment
      Purge
      0.9 mgd  *
 A-B Side
 General
 Sewer
 (RQ1-86361)
 4.2 mgd
Combined
Paper Machines
(RQ1-86379)
            A-B Side Recaust.
            Evap, Power
            (RQ1-86362)
            2.6 mgd
Otis Mill
(RQ1-86380)
2.6 mgd
                       A Side Eo (RQ1-86370)
                       B Side Eo (RQ1-86373)

                       A Side D (RQ1-86371)
                       B Side 0 (RQ1-86374)
                             * To WTP
                             (RQ1-86386)
                               37 mgd
           FIGURE  111-15.  Mill  E  Sewer System  Schematic

-------
                               -28-
    The wastewater treatment system  consists  of primary clarifi-
cation followed  by  an  activated   sludge   system   with  1.1  day
aeration time.  The  acid  sewer  bypasses primary treatment  and is
put directly  into  the  aeration   lagoon.   Secondary  sludge  is
gravity thickened prior  to  dewatering  with the primary sludge on
sludge presses.  Overflow from  the gravity thickener is recycled
to the primary clarifier.

    The wastewater treatment plant  is shown schematically in Figure
111-16.  Identification codes and flow rates at the time of sampling
are noted next to each sample location.  Typical operating condi-
tions and performance  during both  winter  and  summer  months are
shown in Tables 111-14 and 111-15.
                           TABLE 111-14

      MILL E  WASTEWATER  TREATMENT  PLANT  OPERATING  PARAMETERS
     Parameter                                          Value
     Flow (MGD)                                          40
     Residence Time (days)                                1.2
     Mixed Liquor Suspended Solids (mg/L)             1300-1400
     Return Sludge Recycle (%)                           53
     Aeration Horsepower  (HP/million gallons)            44
                             TABLE 111-15

        MILL E WASTEWATER TREATMENT PLANT PERFORMANCE DATA
   Parameter

   BODs Loading (Ibs/day)                        80,000-120,000
   BODs Removal (%)                                  93-94
   Suspended Solids Loading (Ibs/day)              430,000
   Suspended Solids Removal (%)                      93-95
   Secondary Sludge Production (dry tons/day)           35
   Combined Sludge Production  (dry tons/day)           200

-------
                                 -29-
                 Comblned
                 Acid Sewer
                 (RQ1-86368)
                 4.03 mgd
 Influent
 (RQ1-86386)
   37 mgd
                                                               Effluent
                                                               To River
(RQ1-86388)
  41 mgd
                                         (RQ1-86397)
                                          0.43 mgd
                              (RQ1-86387)
                            90 Dry Tons/Day
FIGURE 111-16.   Mill  E Wastewater Treatment Plant Schematic

-------
                                -30-
IV.   FIELD PROGRAM

     The field program for  this  study was conducted  according  to
 the schedule shown below:

                 Mill A            June 24-25,  1986
                 Mill B        September 8-10,  1986
                 Mill C         October 15-18,  1986
                 Mill D          December 2-3,  1986
                 Mill E         January 13-15,  1987

 In  addition, preliminary grab samples were collected  from  Mill A
 in  March 1986 for analytical  methods development and  prescreening
 of  selected samples including wood chips,  unbleached  and bleached
 pulps,  selected  untreated  wastewaters,  paper machine  additives,
 wastewater sludges,  and  treated  process  wastewater  effluents.

 A.   Sampling Plan

     The study design called  for sampling  all  mill inputs thought
 to  be significant;  intermediate  process materials and  untreated
 process wastewaters; and  mill  exports  including  bleached  pulps,
 wastewater sludges,  and  treated  process  wastewater  effluents.
 Table IV-1 presents the  detailed sampling plan  for  Mill A.  Similar
 plans were  developed  for  each mill after  site  reconnaissance
 visits  to review process  water  treatment  systems, process  opera-
 tions,  sewerage systems, and  wastewater treatment systems.

     Based upon the results of the  reconnaissance visits, specific
 sampling locations were selected  to  determine mass flow rates  of
 process waters, wastewaters,  and process materials.  The sampling
 plans were reviewed in detail by USEPA,  NCASI, and mill personnel
 prior to  implementation.   Arrangements  were made  to  acquire pulp
 mill, bleach  plant,  and  wastewater  treatment  system  operating
 logs during each  sampling  survey.   Note  that primary  flow moni-
 toring  devices  have  not  been  installed  on  most  internal  plant
 process wastewater  streams.   Accordingly, crude  measurements  or
 best engineering  estimates  of flow were  developed   for  these
 streams.  This  is  particularly  common  for the  individual  bleach
 plant pulp  washing  stages between  chemical   applications.   Mass
 flow rates of pulps and  final treated  process wastewater effluents
 were generally determined with primary monitoring devices and are
 considered to  be  more  accurate.    Also,  the  determination  of
 chemical applications  in  the  bleach plants  from the  operating
 logs was  found  to  be difficult due  to  differences in  reporting,
 solution strength  measurement  methods,  and  mill-specific  data
 recording procedures.

-------
                                             -31-
                                          TABLE IV-1
                               MILL A - DETAILED SAMPLING PLAN
 SAMPLE
 NUMBER
DE020801
DE020802
DE020803
DE020804
DE020805
SAMPLE DESCRIPTION

A. Background Samples

Treated River Water
Water Treatment Precip. Sludge
Water Treatment Sandfilter Sludge
Softwood Chips
Hardwood Chips
          B. Pulping Process

DE020806  Combined Pulping & Recaust WWs


          C. Chemical Recovery Plant

DE020807  Combined Process Wastewater
DE020808  Lime Mud

          D. Bleach Plant

DE020901  Unbleached Softwood Pulp
DE020902  Bleached Softwood Pulp
DE020903  Unbleached Hardwood Pulp
DE020904  Hypo Hardwood Pulp
DE020905  Peroxide Hardwood Pulp

          Softwood Bleach Line
DE020906  S-l Washer, C Stage
DE020907  S-2 Washer, Eo Stage
DE020908  S-3 Washer, H Stage

          Hardwood Bleach Lines
DE020909  K-6 Washer, C Stage
DE020910  K-4 Washer, EQ Stage (Hypo line)
DE020911  K-5 Washer, H Stage (Hypo line)
DE020912  K-2 Washer, Eo Stage (Per line)
DE020913  K-3 Washer, H Stage (Per Line)
DE020914  K-l Washer, H Stage (Per Line)
DE020915  Combined Process Wastewater
DE020809  Hypo Solution
DE020810  Caustic Solution
 SAMPLE
 NUMBER   SAMPLE DESCRIPTION

          E. Paper Machines

DE020811  Combined Process WW Process Additives
DE020812  Alum
DE020813  Clay-1
DE020814  Clay-2
DE020916  Dye-1
DE020917  Dye-2
DE020815  Resin Size Emulsion
DE020816  High Brightness Filter
DE020817  Slimicide
DE020822  Soda Ash
DE020823  Sodium Thiosulfate
DE021001  White Water - Clean
DE021002  White Water - Dirty

          F. Utilities, Wastewater Treatment

DE020818  Powerhouse Wastewater
DE020918  Bottom Ash
DE020919  Fly Ash
DE020819  WWTP Primary Sludge
DE020820  WWTP Secondary Sludge
DE020920  WWTP Composite Sludge
DE020921  Combined Untreated Wastewater
DE020922  Final Wastewater Effluent
DE020821  Landfill Leachate

          G. Other

DE020923  Sludge - not from Mill A
DE020824  Thiosulfate & H2S04 Reagent Blank

-------
                               -32-
    The sampling plan for each mill  called  for  24-hour composite
sampling of mill  inputs,  intermediates, and  exports,  except  for
paper machine additives (alum, clays, dyes,  slimicides)  and,  for
some mills, power boiler  ashes and  landfill leachates.  Discrete
grab samples  of  those materials  were  collected during  or  imme-
diately after the 24-hour  sampling  period.    At most  mills  where
multiple dyes are used,  samples   were collected  of at  least  two
dyes used at  the  time of  the survey and of  one or two dyes most
heavily used  throughout the  prior year.   For four  of the mills,
final process wastewater effluent sampling was delayed to account
for the  estimated  time-of-travel  or   residence  time  of  the
wastewater through the  respective wastewater treatment  systems.
Mill-specific field  sampling is described in Section IV.C.

B.  Sample Collection, Sample Handling,  and  Sample Custody

    Attachment B  presents  the field  protocols  followed  for  the
five-mill study.  Precleaned sample collection devices and sample
containers (one  gallon  or  one  quart  glass  bottles)   were  used
throughout the  study.   The   cleaning  procedures  are  outlined  in
Attachment B.  For liquid samples   (treated process water, untreated
and treated  wastewaters,  liquid  or  slurry sludges,  and  dilute
process additive  solutions)  one   gallon  samples  were  collected.
For solids and semi-solids (wood   chips,  clays, dewatered sludges,
ashes, and pulps) and concentrated  liquid additives (slimicides,
dyes, and certain paper  machine additives)  one quart samples were
collected.  The  pulp samples  were  partially  dewatered in  the
field at the  time of collection  by  manually squeezing individual
grab samples  used to make up the 24-hour composite samples.  The
analytical data for  solid and semi-solid samples including liquid
sludges were determined  on a dry   weight  basis.  All other samples
were analyzed on  a  wet  weight basis.   At most  mills, individual
or combined paper machine wastewaters were  sampled at convenient
sewer locations and  combined on a   flow-proportioned  basis  with
other paper  machine   wastewaters  to form   one  composite  paper
machine wastewater sample from the mill.

    The 24-hour  composite samples  were  manually  collected  and
comprised of  eight discrete  grab samples obtained  at approximate
three-hour intervals.

    All samples were  iced  during  the  collection period and secured
in locked ice chests or in ice chests secured with custody seals
or tape.  With  few exceptions, individual  or multiple ice chests
were specifically assigned   to a sampling  location  to  minimize
chances of  sampling   errors.  Wastewater   samples  suspected  of
containing chlorine   were  checked for total   residual  chlorine at
the time of collection.   Total residual  chlorine  was neutralized

-------
                               -33-
with a  slight excess  of  sodium  thiosulfate  in  solution  or  in
crystalline form  at  the  time  of  collection.   Also,  samples
collected for chlorinated  phenolics  were adjusted to pH  <2 with
6M sulfuric acid upon collection for sample preservation.

C.  Site Specific Sampling

    The sampling  at each  mill  was  conducted  according  to  the
sampling plans and protocols described above and in Attachment B.
Unique sampling  and deviations  from the  sampling  protocols  at
each mill are described below:

1.  Mill A

    Sample Number DE020818 - Due to minimal wastewater flows, the
powerhouse wastewater was grab sampled.

    Sample Number DE020821 -  The  landfill   leachate  and  runoff
sample was a grab sample vs. a 24-hour composite sample since the
leachate and runoff collected in a pond  with long retention time.
The wastewaters  are  discharged  on an  intermittent basis  to  the
wastewater treatment facilities.

    Sample Number DE020922 - The final effluent 24-hour composite
sample was  collected concurrently  with  samples  from  the  mill.
Hence, the estimated  residence  time  in  the  wastewater treatment
system was not taken into account in the sampling program as was the
case for the other four mills included in the study.

2.  Mill B

    Sample Number 86374621 - The first aliquots  for the individual
24-hour field  composite samples  from the  newsprint machine  #3
(station E-2A)  and  forms  bond  machine  (station  E-2B)  were  not
taken due to sampling error.

    Sample Number 86374646 -  The  landfill leachate  sample  was a
short term composite sample  vs.  a  24-hour composite sample since
the discharge flow  rate  was  minimal  and  the discharge was direct
rather than to the wastewater treatment  system.

3.  Mill C

    Sample Number DE026006 - Only one aliquot of D-stage filtrate
was collected during  the first  12 hours  of the survey  due to a
plugged sample port.  Sampling  resumed as normal  for the balance
of the survey.   The D-stage  filtrate was not  sewered during the
survey.

-------
                               -34-
    Sample Number DE026011 - Due to minimal wastewater volume and
remote location, the wastewater sludge landfill leachate was grab
sampled.

    Sample Numbers  DE026013  and  DE026206  -  24-Hour composite
samples of  secondary  wastewater effluent  were collected  during
the 24-hour sampling  period for the  mill  (0-24 hours) and  on a
delayed basis  (36-72  hours)  to account  for  residence time  in
the wastewater  treatment  facilities.   The  0-24-hour  sample was
collected to characterize  about 2 MGD of treated effluent returned
to the .mill during the survey period.

4.  Mill  D

    No significant changes from the sampling protocols.

5.  Mill  E

    Sample Number RG1-86357 - A two gallon concentrated sample of
river intake water filter  backwash  was  obtained by decanting one
gallon samples from six separate filter  backwashes.

    Sample Numbers RG1-86367, 72, 73, and 74 -  Due  to production
scheduling at the mill,  the B bleach line was sampled for a 4-hour
period after the 24-hour sampling period for the mill and after a
change from softwood  to  hardwood  production.  Precautions  were
taken in  the  field  to  insure hardwood pulp was being  sampled on
this line.  However,  based  upon  a  review  of  process operating
logs, the short-term bleached  pulp  composite  sample obtained was
comprised of  undetermined  amounts  of both  softwood and hardwood
pulps.

    Sample Numbers  RG1-86380/92  -  An   untreated  paper machine
wastewater from a nonintegrated paper mill  located  near Mill  E was
sampled as  it entered  the Mill E  wastewater  treatment  system.

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                               -35-
V.  ANALYTICAL PROGRAM

A.  Polychlorinated Dibenzo-p-Dioxins  (PCDDs) and Polychlorinated
    Dibenzofurans (PCDFs)

1.  Compounds Selected for Analyses

    Analyses of preliminary samples from two mills indicated that
2378-TCDD and 2378-TCDF  are the principal PCDDs  and  PCDFs found
in various pulp and paper mill matrices.  Samples from other pulp
and paper  mills  analyzed  by  USEPA   reveal  similar  patterns.3

    Tables V-l to  V-3 present data for  six mills for isomer specific
determinations of 2378-TCDD,  data  for the determination of 2378-
TCDF plus possible co-eluting  isomers, and  data for higher chlori-
nated PCDDs  and  PCDFs.   Each of  these mills process  primarily
virgin fiber.  Mills A and  E  (Tables   V-l  and V-2)  are  among the
five mills included in the cooperative study.  Mill 1 (Table V-l)
and Mills 2,  3, and 4  (Table  V-3)  are other  bleached kraft mills
not included in this study.   Data for  Mill E were developed using
procedures previously  demonstrated  to  be  isomer  specific  for
2378-TCDF.  Also  summarized  are the  2378-TCDD  toxic  equivalents
computed to the extent possible for all detected  PCDDs and PCDFs.
Very few  of  the  higher   congener  measurements  were  made  using
procedures which have been demonstrated to be isomer specific for
the 2378-substituted  isomer.   Accordingly/  the   results  must  be
qualified as  possibly  reflecting  the  presence  of  co-eluting
isomers.  Nevertheless,  conservative   calculations  of  the  toxic
equivalents (TEQs) were made assuming  the concentrations reported
for the 2378-substituted  isomers  were all the most toxic isomer.

    Note that the  analyses  were  completed  by three laboratories
(Dow Chemical (Table V-l);  Wright State  University  (Table V-2);
and USEPA-ERL Duluth (Table V-3)) using different sample cleanup,
extraction, and analytical  protocols.  Accordingly,  the  results
may not be fully comparable.   Nonetheless,  the data are consistent
in the relative absence of the higher  chlorinated  PCDDs and PCDFs.

    The 2378-TCDF  concentrations  measured  as   part  of  a  full
congener analysis for Mill A and Mill  1 (Table V-l) were shown to
be substantially  correct  based  upon  split  sample analyses using
procedures which  were isomer  specific  for  this compound.   It
should also be noted that only  the  2378-substituted  isomers were
quantitated in  the  Mill  A  and Mill   I analyses.  However,  the
comparatively low relative  toxicity  equivalency  factors  for the
higher  congener  non-2378-substituted isomers  indicate  that this
data limitation does not  substantially alter the conclusion that
virtually all the TEQs  are associated with 2378-TCDD and 2378-TCDF.

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                                    -36-
                                 TA3LE V-l

           PCDDs and PCDFs IN BLEACHED KRAFT  PAPER MILL MATRICES
          USEPA/PAPER INDUSTRY COOPERATIVE  DIOXIN  SCREENING STUDY
                           DOW CHEMICAL ANALYSES
PCDDS

2378-TCDD
12378-PeCDD
123789-HxCDD
123678-HxCDD
123478-HxCDD
1234678-HpCDD
OCDD
   Mill A
 Bleachery
Wastewaters9

  150 ppq
    6 (6)
   ND (20)c
   ND (15)
   ND (15)
   45 (10)
  220 (40)
  Mill A
   Final
 Effluent9

  73 ppq
  ND (7)
  ND (20)
  ND (15)
  ND (15)
  30 (15)
 220 (30)
  Mill A
Wastewater
  Sludgeb

  17 ppt
  ND (1)
  ND (7)
  ND (7)
  ND (7)
  ND (6)
  59 (9)
  Mill 1
 Combined
Wastewater
  Sludgeb

  240 ppt
   25
    6  (3)
}   9  (5)

  150
 1400
        Notes
PCDFs

2378-TCDF
23478-PeCDF
12378-PeCDF
234678-HxCDF
123789-HxCDF
123678-HxCDF }
123478-HxCDF
1234789-HpCDF
1234678-HpCDF
OCDF

SAMPLE TEQf

% TEQ from
 2378-TCDD &
 2378-TCDF
 2500 ppq
   23  (3)
   27  (3)
   ND  (5)
   ND  (7)
    9  (2)

   ND  (10)
   10  (5)
   30  (15)

  410 ppq

   98%
1000 ppq
  16 (3)
  16 (2)
  ND (5)
  ND (5)
   5 (3)

  ND (10)
   7 (7)
  20 (10)

 180 ppq

  98%
 300 ppt
   3 (1)
   3 (1)
   2 (2)
  ND (2)
   1 (1)

  ND (3)
   2 (2)
   5 (5)

  48 ppt

  99%
 2300 ppt
   53
  140
    3  (1)
   <4
   20
    5
   11
   43
(2)
  500 ppt

   94%
          d
          d
          d
          d
          d,e
          d
NOTES;   (a) Concentrations  in liquid samples determined on the basis  of the
            total weight of the samples.
         (b) Concentrations in  sludge samples determined on dry weight  basis.
         (c) ND  -  Not detected at stated  detection level; detection  level is
            reported  in  parentheses  (    ).    Detection  level   reported  in
            parentheses  (   )  when  analytical  result is  less  than  10 times
            detection level.
         (d) Data may reflect presence of  co-eluting  isomers.
         (e) Maximum possible concentration.
         (f) Sample TEQ computed  assuming  isomer-specific  analyses for  listed
            compounds.  Sample  TEC  computed  by  USEPA  (see  Reference  2).

-------
                          -37-
                       TABLE V-2
 PCDDs and PCDFs IN BLEACHED KRAFT PAPER MILL MATRICES
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING  STUDY
            WRIGHT STATE UNIVBRSITY ANALYSES
 PCDDS

 2378-TCDD
 12378-PeCDD
 123789-HxCDD
 123678-HxCDD
 123478-HxCDD
 1234678-HpCDD
 OCDD
       Mill E
     Bleachery
    Wastewaters
      970
       ND
       ND
       ND
       ND
      130
     1800
ppq
(70)
(70)
(30)
(30)
          Mill E
           Final
         Effluent
 80
 ND
 ND
 ND
 ND
 80
990
ppq
(12)
(100)
(50)
(120)
               Mill E
              Combined
             Wastewater
               Sludge
190
 12
 ND
 ND
 ND
 26
298
ppt

(13)
(23)
(1.9)
 PCDFs
 2378-TCDF
 23478-PeCDF
 12378-PeCDF
 234678-HxCDF
 123789-HxCDF
 123678-HxCDF
 123478-HxCDF
 1234789-HpCDF
 1234678-HpCDF
 OCDF

 SAMPLE TEQ
 % TEQ from
  2378-TCDD &
  2378-TCDF
4600 ppq
ND (20)
ND (90)
ND (870)
ND (130)
ND (150)
ND (70)
ND (40)
ND (10)
70
360 ppq
ND (15)
ND (5)
ND (410)
ND (450)
ND (340)
ND (130)
ND (90)
ND (20)
86
     1400 ppq
    (1500)C

      >99%
      (96%)C
         120 ppq
         (150)C

         >99%
         (78%)C
                                 760
                                  ND
                                  ND
                                  ND
                                  ND
                                  ND
                                  ND
                                  ND
                                  ND
                                  ND
                           PPt
                            (12)
                            (19)
                            (68)
                            (29)
                            (19)
                            (11)
                            (4)
                            (2)
                            (9)
              270 ppt
             (280)c

               98%
              (96%)C
 NOTES:  (a)
         (b)
         (c)
ND - Not.detected at stated detection
level; detection level is reported  in
parenthesis (  ) .
Data for 2378-TCDD, 2378-TCDF, OCDD, OCDF
are isomer specific.  Data for other com-
pounds may reflect the presence of  co-eluting
isoraers.
Sample TEQ and percentage attributable  to
2378-TCDD and 2378-TCDF shown in  (  ) were
computed assuming all compounds present at
stated analytical detection levels.

-------
                          -38-
                       TABLE V-3

           PCDDs and PCDFs; IN BLEACHED KRAFT
             PAPER MILL WASTEWATER SLUDGES
               USEPA-ERL DULUTH ANALYSES
2378-TCDD
TCDD-Other
12378-PeCDD
PeCDD-Other
123678-HxCDD
HxCDD-Other
1234678-HpCDD
1234679-HpCDD
OCDD

2378-TCDF
TCDF-Other
12378-PeCDF
PeCDF-Other
123678-HxCDF
HxCDF-Other
HpCDF-Total
OCDF

SAMPLE TEQ

% TEQ from
 2378-TCDD &
 2378-TCDF
                   Mill 2
                  Combined
                 Wastewater
                   Sludge
               Mill 3
              Combined
             Wastewater
               Sludge
    ppt
    (10!
    (5)
    (5)
 150
  ND
  ND
  ND
  17
  62
 110
  82
1860
880 ppt
640
 29
140
  5
 30
  5
 53

260 ppt

 93%
37
ND
ND
ND
2
21
1380
1240
14000
200
310
2
15
31
240
360
310
PPt
(5)
(5)
(5)





ppt







                              Mill 4
                             Combined
                            Wastewater
                              Sludge
                 61 ppt

                 94%
 53
 ND
 ND
 ND
  2
 10
 33
 29
710

280
220
 ND
 ND
 ND
 ND
 22
 ND
PPt
(1)
(5)
(5)
(2)
                                  ppt

                                  (5)
                                  (5)
                                  (5)
                                  (5)

                                  (20)
 81 ppt

>99%
NOTES:  (a) ND - Not detected at stated detection  level;
            detection level is reported in parentheses

        (b) Data for 2378-TCDD, OCDD, and OCDF are
            isomer specific.  Data for other  2378-
            substituted compounds may reflect the
            presence of co-eluting isomers.
        (c) Mills 2, 3, and 4 were not among  the
            five mills included in this study.

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                               -39-
    Note that for  Mill  E  (Table V-2) ,  TEQs  were  computed in two
ways:   (1) assuming that compounds not detected were present at the
stated analytical  detection  level;  and  (2)  that compounds  not
detected were not present, i.e., concentration of  zero.  This was
done because of  the relatively  high  analytical  detection levels
observed for  several higher  chlorinated  2378-substituted  PCDDs
and PCDFs in the bleachery wastewater and final effluent samples.
For the bleachery  wastewater there is  no significant difference
in the proportion of the TEQ associated with 2378-TCDD  and 2378-TCDF
with either of the methods described above.  For the final effluent
only 78%  of the TEQ  would  be  associated  wath 2378-TCDD  and
2378-TCDF, if it were  assumed  that all  of the higher chlorinated
compounds not detected  were present  at  the stated  analytical
detection levels.   However,  this is unlikely  given  the  findings
in wastewater sludge from that mill.  The conservative calculations
have the tendency to overstate  the  TEQs associated  with the higher
congeners.  Despite this bias,  the 2378-TCDD and 2378-TCDF concen-
trations for  the  remaining  mills  clearly  represent the  major
portion of  the  total PCDD/PCDF  toxic  equivalents (TEQ).   Based
upon these data,  the principal  focus  of  the  analytical  program
for this  study  was  directed   at  isomer-specific  analyses  for
2378-TCDD and 2378-TCDF.

    Each of the mills listed in  Tables V-l to V-3  and each of the
five mills included  in  this  study are  reported to produce virgin
hardwood or  softwood pulps.   Extraneous  sources of  fiber  that
might include wood  treated  with chemical  preservatives  are  not
used at these mills. Hence,  the  introduction of higher chlorinated
dioxins and furans associated with pentachlorophenol is not likely.

2.  Preliminary Sampling - March 1986

    As part of the  analytical  methods development for this study
preliminary grab samples of selected matrices were collected from
Mill A  in  March 1986.   The analytical  results   for  the  process
samples are presented in Table V-4, while the results for wastewater
and sludge samples  and  process  additives are presented in Tables
V-5 and V-6,  respectively.   The  sample preparation, sample extract
processing, and  GC/MS  analytical  methods  used  for  analyses  of
these samples were not the final methods  selected for  the five-mill
study.  The data for 2378-TCDF  were not isomer-specific  and only
total homologue data were developed for  penta-octa CDDs and CDFs.
In some cases, the  analytical  detection  levels attained  were not
consistent with the study objectives.  Finally, since the samples
were grab  samples,  the representativeness  of  the  results  with
respect to mass-  flow  rates is  questionable.  Nonetheless,  the
results provide some insight to  the formation of   PCDDs and PCDFs
in this bleached  kraft  pulp and paper  mill  and  to  the  relative
distribution of  2378-TCDD  and  2378-TCDF  versus   other  PCDDs  and
PCDFs.

-------
                               -40-
    In Table  V-4,   2378-TCDD  and  2378-TCDF  were  not   found  in
softwood chips, weak liquor, or  recovery  system  mud,  all samples
obtained prior  to  pulp  bleaching;  neither  were  TCDDs,  PeCDDs,
HxCDDs, or  TCDFs,  PeCDFs,  HxCDFs, HpCDFs,  or OCDF at  detection
levels in the  0.5  to 12 ppt  range.   Total  HpCDDs and  OCDD were
found in the softwood chips (37  and 154 ppt, respectively)  and in
the recovery mud (3.3 and 10.7 opt, respectively).  The brownstock
pulp contained  only OCDD  at 1.2 ppt  while  the bleached  pulp
contained 2378-TCDD and 2378-TCDF plus possible co-eluting isomers
at 8 and  70 ppt, respectively.   Other  TCDDs and  TCDFs  were not
found at  significantly  higher levels  in  the bleached  pulp, and
penta-hepta CDDs and CDFs  and OCDF were  not found at  detection
levels of less  than  1  ppt.   OCDD was found  in  the bleached pulp
at nearly 1 ppt. These  data  indicate  that 2378-TCDD and 2378-TCDF
plus possible  co-eluting isomecs are  formed  in  the bleaching of
softwood pulp  and these  compounds are preferentially  formed over
higher chlorinated  PCDDs and PCDFs.

    The wastewater   and   sludge   results  presented  in  Table V-5
show similar trends.   Wastewater samples obtained  prior to pulp
bleaching show  no detectable  PCDDs and  PCDFs at detection levels
in the 0.01 to  0.02 ppt  range, except  for  OCDD at 0.04 ppt.  The
combined untreated  bleach plant  wastewaters  contained 1.1 ppt of
2378-TCDD and   3.9   ppt  of   2378-TCDF  plus   possible  co-eluting
isomers.  While no  other TCDDs  were found,  about  3 ppt of  TCDFs
other than  2378-TCDF were  found.   Considerably  lower  levels of
2378-TCDD (0.09 ppt)  and 2378-TCDF plus possible co-eluting isomers
(0.45 ppt)  were  detected   in  the  paper  machine  wastewaters.
Penta-octa CDDs  and  CDFs were not analyzed  in  the bleach  plant
and paper machine wastewaters.   The  treated final process waste-
water effluent  contained both 2378-TCDD  (0.25 ppt)  and  2378-TCDF
plus possible  co-eluting isomers (1.0 ppt).   Higher  chlorinated
PCDDs and PCDFs were not  found   in  the  treated  effluent  in the
0.01 to 0.05 ppt range.  The combined wastewater treatment sludge
sample contained about 65 ppt of 2378-TCDD (average of two analyses)
and 280 ppt of  2378-TCDF plus  possible co-eluting  isomers.  Except
for OCDD, higher chlorinated PCDDs and PCDFs were not detected in
the sludge.

    TCDDs and  TCDFs  were not detected  in  samples  of slimicide,
alum, clays, and a yellow dye at detection levels of less  than 1 ppt
(Table V-6).   However  2378-TCDD  and  other TCDDs  were found in a
sample of blue dye  at   3.4  ppt  and 53 ppt,  respectively.    TCDFs
were not found  in the blue  dye.

    The distribution of PCDDs arid PCDFs in these  samples were also
considered  in  the  decision  to  focus  the  analytical  program on
2378-TrCDD and  2378-TCDF.

-------
J
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                               -44-
3.  Analytical Methods for 2378--TCDD and 2378-TCDF

    As noted above,  in the initial phase of the assessment of paper
mill process samples and waste products, attention was focused on
accurate quantitative measurement of 2,3,7,8-tetrachlorodibenzo-p-
dioxin (2378-TCDD)   and   2, 3 , 7 ,- 8-tetrachlorodibenzof uran  (2378-
TCDF).  Target detection  limits  of 1-2  parts per trillion (ppt)
for these isomers in solid media were established,  while the target
limits for  these  isomers  in  aqueous media were  set  at 0.001 to
0.010 ppt  (1-10  parts per  quadrillion  (ppq) ) .    Analyses  of  the
preliminary samples  at Wright  State   University  indicated  that
achieving these  detection   levels  was  not  practical   using  the
traditionally applied  sample  extraction and  cleanup techniques.
Moreover, an extensive  evaluation  of the separation capabilities
of the  several   capillary  gas chromatography  columns  which  are
usually employed in such analyses  (DB-5, SP-2330,  SP-2340), using
all 38 TCDF  isomers,  revealed that 2378-TCDF co-elutes  with  one
or more  of  the  other  TCDF  isomers  on  all of  these  columns.
Therefore, 2378-TCDF  could  not be uniquely determined  by using
any of these columns.  Accordingly, Wright State,  in consultation
with USEPA and NCASI, undertook the development  and validation of
sample extract cleanup procedures which utilized  a  multiple silica,
alumina, and carbon  column 1iquid-chromatographic  cleanup sequence
which has  the capacity to   remove larger  quantities   of  matrix
constituents and  other chemical  residues.   These  methods  also
utilize modified alumina column elution procedures, in which the
strength of  the  eluting   solvent   mixtures  is   more  critically
adjusted in order to optimize separation of  2378-TCDD and 2378-TCDF
from other  extraneous  chemicals in the  sample  extract.  Finally,
gas chromatographic  studies were  accomplished  which  led  to  the
development of  a hybrid phase DB-225/DB-5 capillary  GC  column,
which was  demonstrated  to  completely resolve 2378-TCDF (<10% to
<25% valley)  from  the  other  37  TCDF  isomers.    This  column  was
applied routinely  for  definitive  2378-TCDF  analyses.  A  brief
summary of the overall analytical procedures applied to determine
2378-TCDD and  2378-TCDF  in the  samples  characterized in  this
study follows.   The  final  analytical   protocol   is  presented  as
Attachment C.

a.  Sample preparation

    Sludge samples  were mixed thoroughly to achieve  uniformity
and two  aliquots were  withdrawn.   One aliquot was subjected to
oven drying  at  105°C until  the sample  attained  constant weight.
This aliquot  was then discarded.   The  percent  solids determined
on this basis  was  used for determining  the  concentration  of the
analytes in  the  second  aliquot,   which was  the  portion  of  the
sample actually  analyzed for 2378-TCDD and 2378-TCDF.   The second

-------
                               -45-
sample aliquot  was  dried on  a  stainlass steel  screen  which was
supported within a  desiccator.   The dried sample was homogenized
in a laboratory blender  and  an  aliquot was removed for analysis.

    Wood chip  samples  were  reduced to a  particle  size  of  1 cm
diameter or less using  a  laboratory mill.   The  pulverized  wood was
then dried, homogenized, and subsampled in the same .manner as the
sludge samples just described.

    Ash samples were prepared in  the same manner as sludge  samples,
except that that they were dried in a shallow  flat dish placed in
a desiccator.

    Pulp samples were  manually  compressed to  removed  the  bulk of
water contained therein  and the  sample  was  broken up  to  small
pieces (2  cm  or   less  in  diameter)  which  were  then  dried,
homogenized, and  subsampled  in  the  same manner  as the sludge
samples.

    Slurries (secondary sludge and  similar materials) were stirred
to suspend particulate matter and an aliquot was  removed for total
suspended solids determination  (Standard Methods  for  the Exami-
nation of Water  and Wastewater, 17th  Edition,  APHA,  AWWA,  WPCF,
1986, Method 209C) .  The remainder of the sample was  allowed to
settle, under refrigeration,  and the  supernatant was  removed and
filtered through a  tared Gelman Type A/E  filter.  The solids thus
recovered were  dried,  homogenized  and  subsampled,  in the  same
manner as described for  sludge samples.

    Water and  wastewater samples  were agitated  in  the   original
sample vessel  to  resuspend  solids contained  therein,   and  the
sample was split into four portions, each portion being placed in
a new  sample bottle.   One of the  split  samples  was  spiked  with
isotopically labelled   C-, 2-2378-TCDD and TCDF internal standards
in an acetone solution and the  sample  was stirred vigorously for
15 minutes to disperse the spiking  standards.   The aqueous sample
was then  filtered  through a Whatman  42  filter  and  the   filtrate
was retained for analysis.   The  filter and  solids recovered  were
dried in  a  desiccator  to  constant weight and  the solids  were
retained for analysis.

    Exceptional samples  which were too wet to  dry efficiently in
a desiccator but  could  not  be filtered were  first  air  dried
at ambient temperature,  then desiccated.

-------
                               -46-
b.  Extraction of 2378-TCDD and 2378-TCDF from  the sample matrices

    Methylene chloride  was  added  to   internal-standard   spiked
aqueous filtrates  (1 liter, typically) and the sample was  stirred
for 16  hours.   The  aqueous  and  organic phases were  allowed  to
separate and  the  organic phas;e  was  removed  and   retained   for
analysis.  The  aqueous  sample was  reextracted sequentially  with
two additional  portions  of  methylene   chloride  and  those  were
pooled with  the  original extract.   This  extract   solution   was
concentrated and combined with the benzeneracetone solvent  in  the
Soxhlet apparatus  used  to  extract  the  solid  portion  of  each
filtered aqueous sample,  as described below.

    Portions (typically  7-10  grams)  of  the  solid  samples  (dried
sludges, ash, wood chips, pulp, solids from water and wastewater)
were placed  in  a Soxhlet apparatus,  spiked  with 13c-j2-2378-TCDD
and TCDF internal  standards,  and  extracted  with a 50:50 solution
of benzene:acetone  for  a period  of  16 hours.   Extracts  were
concentrated to  a  volume of about  15  mL using a  Snyder column.
These extracts were cleaned up as described below.

c.  Preliminary  fractionation  of  sample extracts  to  separate
    2378-TCDD and 2378-TCDF from other extract constituents

    Organic extracts prepared  as  described  above  were subjected
to a  series  of  sequential  washes  with  20%  aqueous  potassium
hydroxide, concentrated sulfuric acid and double-distilled  water,
discarding the  aqueous  portions  and retaining  the  organic phase
in each case.

    Each washed  organic extract  was  subjected to a  sequence  of
liquid chromatographic column separations, including, (a) passage
through a composite column of silica gel, base-modified and acid-
modified silica gel, eluting tVie column with hexane and retaining
the eluate;  (b)  passage  through  a Woelm basic alumina column,
eluting sequentially  with 3%  methylene  chloride-in-hexane,   20%
methylene chloride-in-hexane and 50% methylene chloride-in-hexane,
retaining only  the  last  eluate  fraction; (c)  passage  through a
second basic  alumina  column,   as  just   described;  (d)  passage
through a carbon/celite column, eluting with  hexane, 50% methylene
chloride/50% cyclohexane, then with  50% benzene/50% ethyl acetate,
and finally reverse eluting with toluene, retaining only the last
eluate fraction; and  (e)  passage through a  third basic alumina
column, just as described earlier.   The  final  eluate  fraction
collected was concentrated just to dryness,  and was reconstituted
with 10 micro  liters of  tridecane  containing  other  appropriate
standards, prior to GC/MS analysis.

-------
                               -47-
d.  Gas  chroraatographic-mass
    sample extracts
                      spectrometric  (GC/MS)  analyses  of
    Sample extracts prepared  by the procedures  described  in the
foregoing were analyzed by GC/MS utilizing  an appropriate capillary
GC column  (temperature-programmed)  while  the  MS is  operated in
the selected ion monitoring (SIM)  mode, monitoring simultaneously
the ion masses appropriate for detection of 2378-TCDD, 2378-TCDF,
and the  13C12-labelled  internal standards of  these.   Typically,
1 to 5 uL portions of the extract are injected  into the GC.  Sample
extracts were  initially analyzed  using  a  60 meter DB-5 capillary
GC column at a  typical mass spectral  resolution of 1:600 to obtain
data on the concentration of 2378-TCDD and to determine  if 2378-TCDF
or other isomers which  co-elute with  2378-TCDF  are  present.  If
the latter were  detected  in this analysis, then another aliquot
of the  sample  extract  was  analyzed  in a  separate  run,  using  a
newly developed hybrid  column which consists of a 10 meter section
of a 0.25 mm I.D. fused silica open tubular DB-5 capillary column
coupled with a 30 meter section of a 0.25 mm I.D.  DB-225 column.
Again, the  mass  spectrometer  was   operated  at  low  resolution
(typically 1:600) in the  first analysis  with this column.   The
hybrid column uniquely separates 2378-TCDF from the other 37 TCDF
isomers and  therefore  yields  definite data on  the  concentration
of 2378-TCDF in  the extract which  is analyzed.   However, in some
instances compounds are present in  the sample exract  which give
rise to ion masses which, at low mass  resolution (1:600) , interfere
with the  quantitation   of  2378-TCDF.   In  these  instances  the
analysis of the sample extract was repeated, using the DB-5/DB-225
hybrid column,  but  this time  at  a  mass  spectral resolution of
1:6,500 or higher.
    The analytical
in Attachment C.
           procedures summarized here are fully described
4.  Identification and Quantitation of 2378-TCDD and 2378-TCDF

    The following criteria were  established  for positive identi-
fication and quantitation of the target analytes:

   (1)   Mass spectral responses  must be observed  for the following
        ions monitored, i.e;:
                         13,
                            •12
                         13
                       TCDD:
                      -TCDD:
                       TCDF:
                           c12~TCDF:
320,  322, and 257
332 and 334
304,  306, and 241
314 and 316
   (2)
The signal to noise  ratio of the molecular ions (2378-TCDD
-- 320 and 322; 2378-TCDF -- 304 and 306)  must be greater
than 2.5:1  for  the ions  to  be  considered  detectable.

-------
                               -48-
   (3)   The molecular ions for a given analyte should co-maximize
        within no more than plus or minus one scan of each other.

   (4)   The ratio of the  [M]+ to  [M  + 2]+ intensities must be at
        or within ±15%  of  the  theoretically  expected ratio  of
        0.77;  i.e.,   0.65  to  0.,89  for  2378-TCDD and  2378-TCDF.

   (5)   The chromatographic retention  time of the unlabelled 2378-
        TCDD or  2378-TCDF must   be within  five  seconds   of  the
        corresponding l^C-labelled internal  standard.

   (6)   The GC column resolution  must be demonstrated to provide
        a 25%  valley  or less between 2378-TCDD and  its  closest
        eluting isomers  on  the  DB-5  column  or  between 2378-TCDF
        and its closest  eluting  isomers on the DB-5/DB-225 column.

   (7)   If responses are detected for the molecular ions of 2378-
        TCDF on the DB-5  column,  the sample extract  must  be re-
        injected and  reanalyzed  on   the  DB-5/DB-225  column  to
        ensure isomer specific quantitation.

   (8)   No response must  be  seen  at  M/Z = 374,  the  [M]+  ion for
        hexachlorodiphenyl ether, at  the  same  retention  time as
        2378-TCDF.  This ether would give fragment ions identical
        to 2378-TCDF, and hence  cause false  positives.

   (9)   The target percent  recoveries of  the  13c_;i.abeiecl  analogs
        for 2378-TCDD and 2378-TCDF were set  at 40%-120%.

5.  Intra-Laboratory Method Validation Experiments

    This study  was   one  of  the  first  large-scale   attempts  at
quantifying 2378-TCDD and  2378--TCDF on  an  isomer-speci f ic basis,
at ppt  and  ppq levels,  in  pulp and  paper mill matrices.  These
matrices were  expected  to  provide  considerable  difficulties in
cleanup and  isolation   of  the  target analytes  due  to the  high
levels of particulate matter, dissolved organics and other chemi-
cals.   It was  also felt that the  var iabil ity of feedstock, in-plant
processes, chemical application  rates, etc.,  could cause problems
that were specific to samples  from particular mills.  Therefore,
method validation  experiments  were   carried  out  on  selected
matrices.  These  analyses  were  to  characterize  any  inherent
deficiencies in the  analytical  methodology  that  would  result in
inter-mill data comparability  problems.   Since  virtually  all of
the samples were to.be analyzed by a single laboratory  for 2378-TCDD
and 2378-TCDF,  the  primary  goal  was  to  validate   the  method
internally within the scope of the study.

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                               -49-
    Method validation studies were carried out on three distinctly
different matrices  that  are  the  primary exports  from  pulp  and
paper mills.   The  three  matrices  were  bleached  pulp,  wastewater
treatment sludge,  and  treated process  wastewater  effluent.   The
cleanup and the last would be demanding because of the relatively
low target detection limit of 0.010 ppt.  A  restricted study was
carried out  on a  fourth  matrix,  namely an  artificial composite
caustic extraction  stage  effluent made up  of  equal  volumes  of
caustic extraction stage  effluents from the  five mills.   Samples
for each  matrix  from  four  of  the  five mills  surveyed  in  this
screening study  were  analyzed  in duplicate. . Additional  sample
aliquots were spiked with  2378-TCDD and  2378-TCDF at concentration
levels two to three times the native concentrations.   In general,
16 determinations  each were  made  for 2378-TCDD  and  2378-TCDF  in
these selected matrices.   An exception was the caustic extraction
stage wastewater where a composite sample made up of equal volumes
from all five mills was used  for the method validation experiment.
A single sample spike and spike duplicate analytical sequence was
carried out for this composite sample.

    The analytical results obtained,  i.e., concentrations, native
spike recoveries, and relative percent differences in the detected
levels are presented in Tables V-7 to V-10.   Examination of these
results indicate that with  the exception of  one treated process
wastewater, that  gave  an  elevated  recovery,  these  experiments
were an  unqualified  success.   These  data  indicate  that  the
analytical method  is relatively insensitive  to  the  variations  in
sample composition  or  chemical loading  that exist from  mill  to
mill due  to  variations  in  manufacturing processes.   While  not
every sample matrix has undergone this  type  of  method  validation
study, these  data  provide  experimental  documentation  of  the
overall method performance for the matrices  tested.

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                                       -50-


                                     TABLE  V-7

                            METHOD  VALIDATION EXPERIMENT

                                BLEACHED  KRAFT  PULPS
Pulp 1 (DE020902)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 2 (86374612)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 3 (DF024411)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 4 (RG1-86367)
Duplicate
Matrix Spike
Spike Duplicate
Concentration
(ppt.pg/gm)
15.2
16.3
47.5
51.7
10.2
11.0
37.5
38.0
3.89
3.99
15.9
15.8
55.7
46.7
161
171
2378-TCDD
% Spike
RPD Recovery
7
105
9 118
8
99
1 102
3
110
1 109
18
92
6 100
Concentration
(ppt.pg/gm)
333
1064
912
54.3
64.4
211
203
7.68
7.9
21.5
21.6
181
183
575
559
2378-TCDF
% Spike
RPD Recovery

121
15 96
17
112
4 107
3
84
0 84
1
92
3 87
NOTE:   (1)  RPD - Relative Percent  Difference.
       (2)  Each analysis  (original,  duplicate, matrix spike, and matrix spike
           duplicate)  was conducted  on  a  separate aliquot of unprocessed sample.

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                                        -51-


                                      TABLE  V-8

                             METHOD  VALIDATION EXPERIMENT

                             WASTEWATER  TREATMENT  SLUDGES
Sludge 1 (DE026011)
Duplicate
Matrix Spike
Spike Duplicate
Sludge 2 (R61-86387)
Duplicate
Matrix Spike
Spike Dupl icate
Sludge 3 (DF024606)
Duplicate
Matrix Spike
Spike Duplicate
Sludge 4 (DE020920)
Duplicate
Matrix Spike
Spike Duplicate
Concentration
(ppt,pg/gm)
3.37
3.27
13.0
11.8
193
168
552
576
19.2
17.4
71.2
64.0
37.4
35.8
119
127
2378-TCDD
% Spike
RPD Recovery
3
97
10 86
14
88
4 95
10
106
11 91
4
104
7 115
Concentration
(ppt.pg/gm)
42.6
34.5
142
148
879
670
2641
3023
35.7
31.9
129
125
624
732
2023
1883
2378-TCDF
% Spike
RPD Recovery
21
104
4 111
27
99
13 119
11
95
3 91
16
113
7 101
NOTES:   (1)  RPD - Relative  Percent  Difference.
        (2)  Each analysis  (original,  duplicate, matrix  spike, and matrix spike
            duplicate)  was  conducted  on  a  separate aliquot of unprocessed sample.

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                                        -52-


                                      TABLE V-9

                             METHOD VALIDATION EXPERIMENT

                              TREATED PROCESS WASTEWATER


Effluent 1 (86374645)
Dupl icate
Matrix Spike
Spike Duplicate
Effluent 2 (DE026006)
Dupl icate
Matrix Spike
Spike Duplicate
Effluent 3 (DF024512)
Dupl icate
Matrix Spike
Spike Dupl icate
Effluent 4 (RG1-86388)
Dupl icate
Matrix Spike
Spike Duplicate
2378-TCDD
Concentration % Spike
(ppt,pg/gm) RPD Recovery
0.0157
0.0145 8
0.0550 95
(2)
ND(0.0034)
ND(0.0042)
0.0156 158
0.0125 22 125
ND(0.0075)
ND(0.0072)
0.0203 115
0.0178 13 101
0.0881
0.0953 8
0.538 112
(2)
2378-TCDF
Concentration % Spike
(ppt,pg/gm) RPD Recovery
0.133
0.110 19
0.376 97
(2)
0.0085
0.0140 49
0.0279 84
0.0365 27 126
ND(0.0069)
ND(0.0066)
0.0187 106
0.0253 30 143
0.447
0.441 1
2.140 85
(2)
NOTES:   (1)  RPD - Relative  Percent  Difference.
        (2)  Not analyzed  due  to  insufficient  sample volume.
        (3)  Each analysis (original, duplicate, matrix spike, and matrix spike
            duplicate)  was  conducted on  a  separate aliquot of unprocessed sample.

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                                         -53-



                                       TABLE  V-10

                              METHOD VALIDATION EXPERIMENT

                  COMPOSITE CAUSTIC EXTRACTION  STAGE  WASTEWATER  SAMPLE
   Sample

   Matrix Spike

   Spike Duplicate
Concentration
(ppt,pg/gm)
961
2774
3010
2378-TCDD
RPD


8
% Spike
Recovery
87
94
2378-TCDF
Concentration
(ppt.p'g/gm)
7080
20,312
23,301
RPD


14
% Spike
Recovery
85
99
NOTE:  (1)  RPD - Relative Percent  Difference.
       (2)  Sample consisted  of a composite  of  equal  volumes
           of the caustic extraction  stage  samples  collected
           at each of the five mills.   Sample  was not  run  in
           duplicate.
       (3)  Each analysis  (original, matrix  spike, and  matrix
           spike duplicate)  was conducted on a separate
           aliquot of the composite sample.

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                               -54-
6.  Inter-Laboratory Method Comparison

    A limited  inter-laboratory  method  comparison  study  was at-
tempted involving Dow Chemical and Brehm Laboratory, Wright  State
University (WSU).  At the outset of the study, two wastewater and
two sludge samples were  analyzed  by both laboratories.  The data
and the  relative  percent difference  (RPD)  are  presented  below:
 Sample
 Number

DE020915
Wastewater
2378-TCDD
2378-TCDF
                               Concentrations (ppt)
 Dow*

0.150
2.50
                                            WSU
                         Range
 Mean

0.296
 NA**
RPD
 65
DE020922
Wastewater

DE020920
Sludge

DE020923
Sludge
2378-TCDD    0.073   (0.111-0.150)   0.124     52
2378-TCDF    1.00         ~        2.18      74

2378-TCDD    17.0    (35.8-37.4)     36.6      73
2378-TCDF    300     (624-732)       678       77

2378-TCDD    240     (317-470)       394       49
2378-TCDF    2300    (3270-4190)     3730      47
 * The Dow Chemical analytical results for 2378-TCDF
   may reflect the presence of co-eluting isomers.

** NA - Sample consumed in analytical method development
        experiments.
    The Dow  Chemical  results  confirm  the presence  of 2378-TCDD
and 2378-TCDF  in  these  samples.   However,  the  mean RPD  of 62%
indicates notable  differences  in   reported  concentrations  when
compared to  the high  degree  of  precision  achieved  for  intra-
laboratory and  field  duplicate  samples.  The  bias  observed  in
the data  is  consistent  in  both direction and  magnitude.    These
differences can  be attributed  to  variations  in  extraction and
cleanup procedures  and  to  the fact  that different calibration
standards were  used.    Additional   inter-laboratory method  com-
parisons have  not  been  conducted   as  part  of  this  study.   The
above data clearly indicate the need for further inter-laboratory
studies involving these atypical sample matrices.

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                               -55-
B.  Chlorinated Phenolics

    Selected water  and  wastewater samples  were  analyzed for the
following chlorinated  phenolics  using  NCASI  GC/MS  analytical
methods  (Technical Bulletin No. 498, July 1986):
                        Chloroguaiacols

                        4,5-Dichloroguaiacol
                        3,4,5-Trichloroguaiacol
                        4,5,6-Trichloroguaiacol
                        Tetrachloroguaiacol
                             Chlorovanillins

                             5-Chiorovan ill in
                             6-Chlorovanillin
                             5,6-Dichlorovanillin
Chlorophenols

2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
1,4/2,5-Dichlorophenol
3,4-Dichlorophenol
2,5-Dichlorophenol
2,3-Dichlorophenol
2,4,5-Tr ichlorophenol
Pentachlorophenol

    A revised  quantitation  procedure  (May   1987)  incorporating
stable isotope  internal  standards  was  used  in  the  analysis  of
samples from Mills  C,  D,  and E.  All analyses  were completed by
NCASI at  its  West  Coast  Regional  Center  located  at  Corvallis,
Oregon.  The NCASI  methods are  fully described  in Attachment D.

C.  Total Suspended Solids and Biochemical Oxygen Demand

    Selected water and wastewater samples were analyzed for total
suspended solids  and  five-day biochemical oxygen  demand  by mill
laboratories for  four  mills  and  by a local  water  authority for
one mill.   The  analytical  methods  used  were those  contained  in
Standard Methods for the  Examination  of  Water  and Wastewater,
15th Edition,  1980
Analysis of  Water
(APHA,  AWWA, WPCF)
and  Wastes,  EPA
USEPA, EMSL-Cincinnati, Ohio,
                                       ;  or,  Methods for Chemical
                                       600/4-79-020,  March 1979,

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                                -56-
VI.   QUALITY ASSURANCE

 A.   2378-TCDD and 2378-TCDF

 1.   Quality Assurance Objectives

     Prior to  undertaking   the   five-mill  screening  study,  data
 quality objectives for precision, accuracy,  and completeness were
 established.  The primary  goal  was to provide  reliable  measure-
 ments of the concentrations of  2378-TCDD and 2378-TCDF at low ppt
 levels in  solids  and  low  ppq  levels  in  liquids.  The  approach
 included the isotope dilution analytical methodology  used in the
 National Dioxin  Study.   An  isotopically  labelled analogue  (l^c
 labelled) for each of  the  target compounds  was  added  as  early as
 possible in the sample preparation process.   This labelled compound
 would then be present  throughout the  entire extraction,  cleanup,
 and instrumental  analysis.   Any  losses of the unlabelled naturally
 occurring TCDD or TCDF would be;  mimicked  by the labelled TCDD or
 TCDF.  Therefore, operational problems  would be  compensated  for
 and final  recoveries  of the  labelled analogues  would  serve  as
 indicators of overall method efficiencies.

     In this  discussion,  2378-TCDD and   2378-TCDF  results  are
 evaluated as two  separate  analyses  on  the  same sample  even though
 the sample  extraction, multi-column  cleanup,  and  concentration
 steps were  common to  both  compounds.   The  only divergence  in
 analytical methodology occurs  at  the  gas  chromatographic  stage
 where capillary columns of different  polarities  were  utilized to
 ensure isomer  specificity   for   both   2378-TCDD  and   2378-TCDF.

 a.   Laboratory precision

     As noted  in  the  analytical  methods  section, a  considerable
 amount of  sample  processing,  i.e., drying,  blending,  filtering,
 splitting, etc.,   takes  place before  the  extraction and  cleanup
 stages.  Therefore,   documenting  laboratory   precision   was  of
 paramount importance.  This  was done by  carrying  out replicate
 analyses of sample aliquots  and  calculating the relative percent
 difference (RPD).  In  cases where multiple determinations  were
 made, the  percent relative standard  deviation  (% RSD)  was  cal-
 culated.  Duplicate   aliquots  of  samples  were  also spiked  with
 2378-TCDD and 2378-TCDF and the  precision  evaluated by comparison
 of these  concentrations.   A QA  objective  of precision  £50%  RPD
 was established for  this study.

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                               -57-
b.  Field precision

    Field precision targets were not established prior to initia-
ting this screening study due  to the  wide  range of matrix types,
variability of  solids  content, and  the collection of  both  grab
and multi-hour composite samples.  However,  a  selected  number of
field duplicate  samples for  each  type  of  sample  matrix  were
collected and analyzed to provide an indication of field sampling
precision.

c.  Accuracy

    The accuracy  of  the  analytical   process   was  evaluated  by
analyzing samples spiked with known amounts of 2378-TCDD and 2378-
TCDF.  Subsequently, percent  recoveries of  the spiked  compounds
were calculated.  This  was done  in  addition to  calculating  the
percent recoveries of the labelled dioxin and furan to provide an
estimate of the accuracy of the analytical  system.   Since  valid
measurements of accuracy require reasonable spike levels, samples
were analyzed  once,  to determine the  native  concentration,  and
then reextracted and reanalyzed after  spiking  at a level  of  2 to
3 times the native concentrations.

d.  Completeness

    A target  of  80%-100%   completeness  was established  at  the
beginning of the study.  This was the  percentage of sample analyses
that met all  other  QA  objectives.  Since  a  substantially larger
number of samples, particularly background and chemical additives,
were collected than were essential to characterize mill operations,
completeness is a  measure of the percentage of the samples analyzed
deemed critical by  the project  manager  that  were subjected  to
analysis.

e.  Internal standard recovery

    One of  the  quality assurance   targets  established  at  the
beginning of the  screening  study  was  that the  recoveries of  the
isotopically labeled internal  standards should  be in the range of
40%-120%.  As mentioned in  the  analytical  protocol,  the internal
standards 13C-, 2-2378-TCDD,   13C12-2378-TCDF,  and  37C14~1278-TCDF
are added to the samples before sample processing, carried through
the entire extraction and cleanup process, and  finally quantified
against 13C12~1234~TCDD and    C14-1278-TCDF added  prior to  in-
jection on the GC/MS.

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                               -58-
2.  Quality Assurance Results for 2378-TCDD and 2378-TCDF

    Table VI-1 provides  a  tabulated summary  of  how well  the  QA
objectives were .met  in the course  of the  study.   As indicated  in
the previous section concerning  the methods validation experiments
(V.A.5), three matrices  believed to be the most  environmentally
significant were  selected   for   extensive  laboratory  duplicate,
spike and spike duplicate analyses.  In addition,  a similar group
of analyses  were  carried out on a five-mill  caustic  extraction
stage composite sample.   These results  are presented in detail  in
Tables V-7 to V-10.

    In the course  of carrying out the analytical  portion  of the
study, it  was  noted that certain  samples had  internal  standard
recoveries of less than  40%,  primarily  for the 2378-TCDF internal
standard.  For the  majority  of  these  instances,   the  recoveries
were in  the  30%-40% range  and   gave acceptable  signal  to  noise
(S/N) ratios.   In  addition,   the samples  in  which  2378-TCDD  or
2378-TCDF were not detected,  had  detection limits that were judged
acceptable for the purposes  of the study.

    In order to better  assess any possible  impact that internal
standard recoveries  less  than 40%  may have  on  data  quality  or
usability, leading chemists  in the  field of dioxin/furan analyses,
in both  the public  and  private  sectors,  were   polled.   These
reviewers were  in  general  agreement that  internal  standard  re-
coveries of  less  than 40%  could  produce  usable   data.   Several
commented that the analytical system would  have to meet criteria
regarding adequate S/N,  correct  isotope  ratios, and correct mass
measurements.  The  possible  impact  of  decreased   S/N would  be
questionable extraction  or  cleanup efficiency, elevated detection
limits, and decreasing precision.

    Careful examination  of  the  analytical data acquired  in this
study showed  11  samples that   had  pairs  of  positive  results
with internal  standard  recoveries  bracketing  the  40%  criterion.
Calculation of the relative  percent difference (RPD)  between the
two concentrations for each  sample resulted in RPDs less than 50%
for 10 of  the  11  samples.   The one outlier  had  an RPD of 62%.
The mean  RPD for  the  11 samples  was  20%.   These  data  clearly
suggest that internal standard  recoveries  of  between 10% and 40%
do not significantly impact quantisation of  the target analytes in
this study.   Accordingly,   for   purposes  of  the  mass  balance
calculations, the mean of the duplicate results, including results
with low  internal  standard  recoveries, was used  to characterize
the sample, provided all other QA criteria were met.

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                              -59-
                             TABLE VI-1
                     QUALITY ASSURANCE SUMiMARY
Laboratory Precision as RPD

  Quality Assurance Objectives
  Number of Determinations^
  Range (mean)
  Percent Meeting QA Objectives
 2378-TCDD

  < 50
    35
 1-138 (15)
    97
 2378-TCDF

  < 50
    33
  0-62 (16)
    97
Field Precision as RPD

  Quality Assurance Objectives
  Number of Determinations
  Range (mean)
    NA
     8
  4-19 (14)
    NA
     9
  0-99 (22)
Accuracy as % Spike Recovery

  Quality Assurance Objectives
  Number of Determinations^
  Range (mean)
  Percent Meeting QA Objectives
50-150%
    35
66-160 (103)
    97
50-150%
    35
58-153 (102)
    97
Completeness

  Quality Assurance Objectives      80-100%
  Number of Determinations             133
  Percent Meeting QA Objectives         95%
                80-100%
                   133
                    95%
NOTE:  (1) The number of determinations for laboratory precision
           and accuracy include those from  intralaboratory method
           validation experiments  (Section  V.A.5).    Thus,  the
           percents meeting  QA  objectives are  weighted  toward
           the mill  exports  (bleached pulp,  treated  wastewater
           effluent, and wastewater  sludge).   Refer  to the text
           for discussion of other sample  matrices.

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                               -60-
    Analysis of  the  field duplicates  indicated excellent  field
sampling reproducibility in the great majority of the cases.  Two
dioxin field duplicate pairs ancl one furan pair gave inconclusive
results as one  analysis  gave a positive  result and the  other  a
nondetect.  An  evaluation  of  these results and  their  use within
the scope of this study are presented Section VII.

    QA results on a matrix-specific basis are presented below for
the main matrices of interest.

a.  Bleached and unbleached pulps

    Bleached pulp  was  one of  the  matrices  selected  for intra-
laboratory method validation experiments.  Bleached  pulp samples
from four of the five mills were analyzed in  duplicate before and
after spiking  with  2378-TCDD  and  2378-TCDF   (see  Table  V-7).
Fifteen of  the  sixteen determinations  gave  RPDs  less  than  18,
with one  analysis  being  rejected  due  to a  high peak  ratio  for
m/m+2 for  2378-TCDF  in   the  unspiked  sample.   This  indicates
excellent precision  in laboratory  operations  as  these  samples
were dried, blended, homogenized,, and subsampled prior to analysis.
All spike  recoveries  ranged   between   84%  and  121%  indicating
acceptable accuracy.  Spike recoveries were comparable (81%-108%)
with those  for  unbleached pulp.    When  field  duplicates  were
analyzed for  both  the bleached  and unbleached  pulps,  the  RPDs
ranged from 0 to 33.  Clearly, the pulp matrix is one that can be
accommodated by  the  field  and laboratory protocols  and the data
generated are of high quality.

b.  Bleach plant wastewaters

    Since caustic extraction stage filtrates were determined to be
critical process samples,  with high levels of organic materials
and high  pH,  a composite  sample  was prepared  by  blending  equal
amounts of the  E-stage samples  from all five mills.   This sample
was analyzed  in  duplicate  after  spiking with twice the estimated
concentrations of 2378-TCDD and 2378-TCDF.  The  results presented
in Table V-10 indicate good precision and accuracy.  One additional
laboratory duplicate  and  two  field  duplicate  determinations  for
actual field  samples  had  RPDs  of  0 to  5.  Note  that  many of the
initial analyses for  caustic  extraction stage  filtrates had very
low internal  standard recoveries  and/or  high  detection limits.
Reanalyses using medium  or high  resolution  were conducted  on  a
number of these samples to confirm  the  initial results or improve
detection limits.

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                               -61-
    The chlorination stage  samples  had  considerable variation in
both spike recoveries and RPDs.  Four sample spikes gave recoveries
ranging from 94% to  160%.   The one  sample  spike recovery of 160%
is out  of  the  QA  range of 50-150%.   It  is probable  that this
high recovery  is due to sample inhomogeneity  rather  than method
inaccuracies as the  same sample also gave a high RPD of 138.  The
five laboratory duplicates covered an RPD range of 3 to 138.  The
two field duplicate pairs also gave  anomalous  results  with 2378-
TCDF RPDs covering a range from 13 to 99 and 2378-TCDD giving one
positive result and  one nondetect  in  each case.   These samples
were not subjected to additional cleanup and analysis with a view
to lowering  the levels  of   interferring  compounds and  possibly
confirming the presence of 2378-TCDD.  While these analytical data
point to problems  in field  and laboratory precision  for chlori-
nation stage wastewaters, they were judged not so significant as to
render the data unusable.

    In contrast, analyses of D-stage and H-stage wastewaters gave
good QC results, with  one elevated  recovery of 153% for a matrix
spike of 2378-TCDF as  the  only outlier.   The  other three matrix
spike results ranged from 99%  to  124%  recovery.   The  same sample
that was  used   for matrix  spikes was  also analyzed  as  a  field
duplicate, gave acceptable results for 2378-TCDD, and a positive at
0.0272 ppt and  an  ND  at  0.0056 ppt  for 2378-TCDF.  This  is no
clear reason for the discrepancy  in  the  2378-TCDF  results.  One
additional laboratory duplicate gave an  RPD of  12 for  2378-TCDF.

c.  Wastewater  treatment sludges

    Composite sludges  from  four  of the  five mills  were analyzed
as part of the  method  validation experiments and  gave excellent
results for  all sixteen precision  and  accuracy  determinations.
These results are  presented  in detail  in  Table V-8.  One composite
sludge was  analyzed   in quadruplicate   using  both  the  routine
protocol and  a modified procedure  being  developed for  isomer-
specific determinations of  all  2378-substituted  PCDDs  and PCDFs.
The results gave a  9% RSD for 2378-TCDD and a 12% RSD for 2378-TCDF.
These results demonstrate good sample homogenization  and  a high
degree of  analytical  precision.    One   additional  matrix  spike
experiment on a primary sludge gave  a  90%  recovery  for 2378-TCDD
and 95% recovery for 2378-TCDF.

d.  Treated wastewaters

    Since these wastewaters  are discharged into streams and rivers,
they are of particular environmental significance.  Every attempt
was made  to  achieve the  lowest  possible  detection  limits.   A
method validation  study was  undertaken  to  determine  if  any mill-

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                               -62-
specific processing could affect the analytical method performance.
Laboratory duplicates and matrix  spike  analyses  were  carried out
on samples from four mills.   Matrix spike duplicate results could
only be  obtained  on samples  from two  mills  due to  the  lack of
sufficient sample volume from tne other two mills.  These results
are presented in detail in Table  V-9  and  indicate good precision
and accuracy  with  one  outlier,  i.e.,  a  recovery of  158%  for  a
2378-TCDD matrix spike,  slightly  above the  upper  bound  of the
acceptable range of 50% to 150%.  The duplicate analyses for this
sample (DE026006)  resulted in  no detectable 2378-TCDD at detection
levels of 0.003 and  0.004 ppt,  respectively;  and the spike level
was about 0.010 ppt.   Given  that  2378-TCDD  might be  present in
this sample  at  less than detectable  levels,  the computation  of
percent spike  recovery may   be  influenced  by  trace levels  of
native 2378-TCDD present.   In retrospect, slightly  higher spike
levels (e.g.,  0.015  or  0.020  ppt)   should  have  been  chosen.
Samples from  three  mills  were  run   in  triplicate  with  results
ranging from  0  to  18%  RSD.   One sample  run  in  triplicate for
2378-TCDF gave  an   RSD of  12?.    Overall  this  indicates  good
laboratory precision  in  splitting  the  effluent  samples  into
multiple aliquots and in carrying out the analyses.

B.  Chlorinated Phenolics

    Since chlorinated  phenols are  known  to be  produced  in the
bleaching process,   it  was  thought  that  chlorination  in  the
bleaching stage could be  followed by cyclization forming chlori-
nated dibenzodioxin  and  dibenzofuran  products.   In  order  to
determine the amounts and  species  of chlorinated phenols produced,
selected background, bleach  plant,  and wastewater samples  from
all five mills were  analyzed  for  chlorinated phenols, vanillins,
and guaiacols.

    The analytical methodology underwent slight alterations in the
course of this survey in order  to utilize procedures more comparable
with the  isotope  dilution  quarititation used  for  2378-TCDD and
2378-TCDF.   The samples from  Mill A were acetytlated, extracted,
and quantitated  against  3,4,5--tr ichlorophenol   as  the  internal
standard.  Two stable labelled internal  standards, namely ^3-2,4-
dichlorophenol and    Cg-pentacnlorophenol,  were  added  to  the
samples from Mill  B prior  to derivatization.  The  samples from the
last three  mills  were  treated  in a  similar  fashion  except for
 he inclusion  of   two  additional  deuterium  labelled  compounds,
 H4-chlorophenol and 2H2-2,4,5-trichlorophenol.

     Table VI-2 provides  a  summary  of the results  obtained for
duplicate and spike samples analyzed from each of the five mills.
Overall, the  data  obtained   met   established  quality  assurance
objectives.

-------
                                 -63-


                              TABLE VI-2

         QUALITY ASSURANCE SUMMARY FOR CHLORINATED PHENOLICS


                   Mill:     A        B        C        D
Precision as RPD

  QA Objectives              £40      £40      £40      £40      £40
  No. of determinations       24        8       18       22        1
  Range                     0-70     2-53     1-93     3-40      5.4
  Mean                        13       16       18       16        5
  % meeting QA objectives     96       88       94      100      100

Accuracy as % Recovery

  QA Objectives           60-140   60-140   60-140   60-140    60-140
  No. of determinations       65       28       42       42        14
  Range                   52-149   82-127   71-122   63-125     66-98
  Mean                        93      108       99       99        85
  % meeting QA objectives     95      100      100      100       100

Completeness

  QA Objectives           80-100   80-100   80-100   80-100    80-100
  No. of determinations       98      126      112      112       154
  % meeting QA objectives     96       99       99      100       100
NOTE:  (1)  For Mill A, the quality assurance summary includes one
           sample analyzed by GC/EC.  The data for Mill A do not
           include spike recoveries for spike levels less than twice
           the background.

-------
                                 -64-
VII.   RESULTS AND DISCUSSION

      Attachment E contains the master  sample lists for  the  field
  surveys conducted at  each of the five mills.   All samples collected
  at  each mill are identified  by a unique sample number and a  brief
  description.  For those samples analyzed, the following information
  is  displayed:   2378-TCDD  and  2378-TCDF concentrations  in  ppt;
  ratio of monitored molecular  ion clusters  for  identification  of
  2378-TCDD and  2378-TCDF;  percent  recoveries  of  the  internal
  standards used to  quantitate  2378-TCDD and  2378-TCDF;  and,  for
  those samples where both  2378-TCDD and  2378-TCDF  were found, the
  2378-TCDF/2378-TCDD ratio.  Where detectable  quantities  of  2378-
  TCDD or 2378-TCDF were not  found,  the  analytical  detection  level
  is  presented with the percent  recovery of  the respective internal
  standard.  Positive findings are  reported  for  only those samples
  where criteria established  for   identification  of 2378-TCDD  and
  2378-TCDF were achieved (i.e.,  2378-TCDD,  320/322  ratio  (0.65  to
  0.89); 2378-TCDF,  304/306  ratio  (0.65-0.89)).   For  reference
  purposes, the date of the laboratory report  for each analysis  is
  also presented.

      The following  protocols   were  followed  to   establish  the
  2378-TCDD and  2378-TCDF  concentrations used  in  this  report  for
  mass balance calculations:

      1.  For  samples  with no  detectable levels  of  2378-TCDD  or
          2378-TCDF, concentrations of zero  were assigned.

      2.  For samples with multiple analyses  (blind  or known  field
          duplicates and laboratory duplicates), the mean values  of
          the multiple  analyses  were  used   to  characterize  the
          samples, with nondetects counted as zero.

      There were three field duplicate sample pairs  where duplicate
  2378-TCDD analyses yielded  a  nondetect  and  a  positive  finding.
  For one of  those  pairs  (Mill  D,  sample numbers DF024511/604) the
  positive finding was used in  the mass  balance calculations  based
  upon consideration  of  findings  in  tributary  streams  and  the
  2378-TCDF/2378-TCDD ratio characteristic of  that  mill  (see Sec-
  tion VILA) .  There was reasonably good agreement between 2378-TCDF
  analyses for this sample pair.  For the second  sample  pair (Mill B,
  sample numbers 86374613/73), the average of the 2378-TCDD results
  was used  based  upon consideration  of  the  2378-TCDF/2378-TCDD
  ratio characteristic of  that  mill.   The 2378-TCDF  analyses were
  in good  agreement.   For  the  third sample  pair  (Mill  D,  sample
  numbers DF024412/605),  agreements  between   the   field  duplicate
  analyses and the laboratory  duplicate analyses for sample DF024605
  were poor,  as  was  agreement  for  the  corresponding  2378-TCDF
  analyses.   Lacking any suitable  criteria  to  evaluate these data,

-------
                               -65-
all results  were  averaged  to  characterize  this  stream.   The
resulting 2378-TCDF/2378-TCDD  ratio  fell  in  the  mid-range  of
other samples from Mill D.   Finally,  there was one field duplicate
sample pair  (Mill  C  sample numbers  DE026003/013)  where analyses
for 2378-TCDF  yield  a  nondetect  and  a  positive  finding.  The
average value  of  these  analyses  was  assigned to this  sample.
This had no  impact  on mass balance  calculations  since there was
no discharge  of  wastewater  to  the mill   wastewater  treatment
system from this source during the survey.   Aside from these four
sample pairs,  agreement  between  analyses   of  field  duplicate
samples and  agreement  between laboratory  duplicate  analyses for
the remaining 28 sample pairs was considered good (generally within
±15%).  The  impact  on  mass  balance calculations  would  not  be
significant had  either  of  the duplicate  analytical  results been
used for the remaining samples.

    The data contained  in  Attachment E  are presented as received
from the laboratory with no editing of significant figures.  These
data were used  with  the mass flow rates  of pulps,  untreated and
treated wastewaters,  and  sludges and ashes  to  compute  the mass
flow rates of 2378-TCDD and 2378-TCDF for each mill.  The concen-
tration data, mass  flow data,  and  mass  flow rates  of 2378-TCDD
and 2378-TCDF are presented by mill for each sample in Attachment F.
The mass flows  of process  waters,   treated  and untreated waste-
waters, pulps, and sludges and ashes were obtained for the survey
periods from primary measurement devices  or  from best engineering
estimates by  mill  personnel.   As  noted  earlier,  the  mass flow
rates of treated process water,  treated  effluents, pulps and, to a
lesser extent,  sludges  are  considered   to  be  fairly  accurate.
However, in most cases,  the mass flow rates of untreated wastewater
streams, particularly  bleach  plant  filtrates,  can  only be  char-
acterized as  reasonable  estimates.   The  mass flow data  were not
edited as to significant figures for the  calculation of mass flow
rates of 2378-TCDD  and 2378-TCDF.   For  purposes  of reporting in
this section,  the  computed mass  flow   rates  of  2378-TCDD  and
2378-TCDF were  generally  rounded  to   two   significant  figures.

A.  Observation on 2378-TCDF/2378-TCDD Ratio

    In the course  of  obtaining and  reviewing analytical  results
from the  laboratory  over  a  period  of  several months,  certain
trends in the data began to  emerge.  Among  these was the observation
that the ratio of the concentration  of 2378-TCDF to that of 2378-
TCDD for samples where both were detected appeared to be somewhat
uniform within  mills   or  within  bleach  lines.    The  data  for
individual bleach lines for all five mills are  presented in Table
VII-1.  These  data demonstrate  considerable  variations  in  the
mean 2378-TCDF/2378-TCDD  ratio across  the  seven bleach  lines.
However, for the softwood bleach lines at  Mills A, B, D,  and  E, and

-------
                             -66-
                         TABLE VII-1

                  2378-TCDF/2378-TCDD RATIO
                     BLEACH LINE SUMMARY
       MILL:

Softwood Lines

Bleached Pulp
Filtrates
B
     Range
     Mean
       MILL:

Hardwood Lines

Bleached Pulp
Filtrates
     Range
     Mean


c
Eo
H}
H

16



21.1
16.0
17.9
16.9


.0-21.1
18.0

Hypochlor








9.7
C 14.4
E0 ND
H ND


9.7-14.
—

5.4
CD 2.9 C
E 4.7 E
H 4.4 H
H 6.9
D 4.5
2.9-6.9
4.8
A
ite Peroxide
16.8
C 14.4
E0 7.0
H 4.2
H 7.0
P — —
4 4.2-16.8
9.9
A B
ND 2.0 5.4
1.8 C 3.3 C/D 3.9
1.8 E 1.8 E 4. 5
1.6 H 1.8 D 5.2


1.6-3.3 3.9-5.4
2.0 4.8
C E

ND 3.6
C/D ND C/D 4.9
E0 ND E0 3.9
D ND D 4.8


3.6-4.9
4.3
NOTES;  (1) ND - 2378-TCDD not detected.
        (2) Mill D - A and B softwood bleach lines with combined
            E-stage filtrates.
        (3) Mill A - Hardwood bleach lines - common C and
            E0-stages; separate E0-stage washers and filtrates.

-------
                               -67-
for the hardwood bleach line at Mill  E,  the ratios were remarkably
uniform.  The ranges  of ratios computed  for  the hardwood bleach
lines at  Mill  A  and  the  softwood  bleach  line at  Mill B  were
somewhat larger.   The  2378-TCDF/2378-TCDD  ratio  could  not  be
computed for Mill  C  because 2378-TCDD was  not detected  in the
bleached hardwood pulp  or  bleach  plant  filtrates from that  mill.

    Table VII-2  presents  2378-TCDF/2378-TCDD  ratios   for  paper
machine wastewaters, combined untreated wastewaters, final efflu-
ents, wastewater  sludges,  and  landfill leachates  for  the  five
mills.  The  characteristic  high  ratio for  the softwood  bleach
line at Mill  A  was in  evidence  for  all other  samples  at  Mill A
except for the  landfill  leachate.   In  similar manner, the bleach
line ratios observed at Mills D and E were also observed in other
samples from those mills with  little variation.   For Mill B, the
final effluent and secondary wastewater  treatment sludge exhibited
somewhat higher  ratios  than  the bleach plant  samples,  while the
ratio for  the  primary  wastewater  treatment  sludge  was more  in
line with the bleach plant ratio.  This possibly suggests prefer-
ential partitioning of  2378-TCDF  in  biological solids at Mill B.
The limited data preclude a more definitive statement.

    Factors accounting for the differences in 2378-TCDF/2378-TCDD
ratios across bleach  lines and  across  mills have not been deter-
mined nor has the  possible process significance been formulated.
Controlled laboratory  or bench scale  research studies  would be
necessary to provide  insight into  the  mechanisms  of  formation of
2378-TCDD and 2378-TCDF.

B.  Background Samples

1.  Treated Intake Process Waters and Residuals

    Table VII-3  presents  analytical  results  for  the  treated
intake process waters  at the  five mills.  Intake process waters are
obtained from surface waters at three mills and  from  a combination
of surface water and ground water at  two mills.   In each case, the
untreated intake  process waters  are  treated  by  coagulation and
sedimentation or  filtration followed  by chlorination   (residual
chlorine about  1  mg/L)  prior to use in  the pulp and papermaking
processes.  The  samples  obtained  were after  chlorination  but
prior to any uses.  The data indicate  no 2378-TCDD  or 2378-TCDF
contamination of  treated intake process  waters at  or  below the
desired analytical detection level of 0.01 ppt.

    For Mill  E,  a  concentrated  sample  of  river   water  filter
backwash was obtained and analyzed.   The  solids  in this  sample
are comprised principally  of river  sediment  and coagulants used

-------
                                       -68-
                                    TABLE VII-2

                             2378-TCDbV2378-TCDD RATIO
                                    MILL SUMMARY
Bleached Pulp
MILL:
B
          D
Softwood Line
Hardwood Line
         16.0-17.9   2.9-6.9
          4.2-14.4
              ND
         E
Softwood
Hardwood
Bleach Plant Filtrates
21.1 5.4
9.7, 15.8

— ND, 2.0 5.4
ND — 3.6

       1.6-3.3    3.9-5.2
                  3.9-4.9
Paper Machine Wastewaters
               9.3
  ND
18.6
 ND   3.3, 3.5
Combined Untreated Wastewaters
              14.1
  ND
  ND
2.1
4.7
Final Effluents
              17.6
 8.1
  ND
 ND
4.7
Wastewater Sludges

Pr imary
Secondary
Combined
              1(5.3       5.3
              15.4       9.1
              18.5
             6.7
            11.6
           1.8
           2.2
           1.9
           4.3
           4.2
Landfill Leachates
               4.4
  ND
  ND
 ND
 ND
     Number
     Range
     Mean
     Std. Dev.
              17         9
          4.2-21.1   2.9-9.1
              13.3       5.7
               5.3       2.0
             3        11         14
        6.7-18.6   1.6-3.3    3.3-5.4
            12.3       2.0         4.4
                       0.5         0.6
NOTE:  ND - 2378-TCDD not detected.

-------
                           -69-


                      TABLE VII-3



                      MILL  INPUTS

             TREATED  INTAKE PROCESS  WATERS



 [Concentrations in parts per trillion  (ppt)  or pg/gm.]



                      2378-TCDD            2378-TCDF

     MILL A           ND  (0.005)           NO (0.011)



     MILL B           ND  (0.007)           ND (0.010)



     MILL C           ND  (0.005)           ND (0.007)



     MILL D           ND  (0.005)           ND (0.005)



     MILL E           ND  (0.006)           ND (0.007)
NOTE:  ND - Not detected; analytical  detection level in
       parentheses  (  ).

-------
                               -70-
for water treatment prior  to chlorination.  There are two bleached
kraft pulp and  paper mills located upstream from Mill E.  2378-TCDD
was not found in the solids fraction of the Mill E filter backwash
at a detection  level  of 1.8 ppt.   2378-TCDF  was found  at  about
8 ppt.    However,  due to  low  recovery of the internal  standard
for the  2378-TCDF  analysis  (13%),  quantitation at  that  level is
questionable.  A second  analysis of a much smaller mass of remaining
solid filter residue confirmed the  presence of 2378-TCDF;  however,
quantitation is  again  questionable because  of the  low mass of
sample analyzed.   Nonetheless,  these  data indicate  2378-TCDF is
present in the  river  system  upstream of  Mill E.  The source or
sources cannot  be  identified  from  this information, nor  can the
amount removed  in  the Mill E water treatment  process  or  the mass
amount contributed  to  the Mill  E  wastewater treatment  system.
Based upon  the results obtained  for major  wastewater  flows at
Mill E,  the  amount  of  2378-TCDF  contributed  to the  wastewater
treatment system from  the  river water filter backwash  system is
believed to  be  a   relatively  small  fraction of  the  untreated
process wastewater loading.

2.  Kraft Pulping Process

    Seven unbleached kraft (brownstock)  pulps from the five mills
were analyzed for 2378-TCDD and 2378-TCDF.  The data are displayed
in Table VII-4.  2378-TCDD was not detected in any of the unbleached
pulps at  detection levels ranging from  0.3 to  about  1.0 ppt.
2378-TCDF was  not  found in the  unbleached pulps  from Mills  A, C,
and D at detection levels less  than 0.3 ppt.

    2378-TCDF was found in the  unbleached softwood pulp at Mill B
at 1.5 ppt  and in  the unbleached  softwood and hardwood  pulps at
Mill E at  1.1  and  2.3 ppt,  respectively.  These  findings may be
accounted for by reuse of paper machine white waters for brownstock
pulp washing or dilution  at both mills.   As  shown later  (Section
VII.D.I, Table VII-16),  paper machine white waters contain 0.11 ppt
and 0.17 ppt of  2378-TCDF at Mills B and E,  respectively.   It is
theorized that  the 2378-TCDF  is  transferred  to  the  brownstock
pulp during  pulp  washing  and  dilution.  The  mass  amounts  of
2378-TCDF found  in the brownstock pulps at  Mills  B  and  E  are
substantially less than the masis amounts contained in the respec-
tive paper  machine  white  waters  discharged  to  the  wastewater
treatment systems.  This suggesits that the 2378-TCDF found  in the
brownstock pulps may be accounted for by the volume of paper machine
white waters reused at these  mills.  Representatives from Mills C
and D report no reuse or recycle of paper machine white waters to
the respective  pulping  processes,  while  reuse  of  paper  machine
white waters for brownstock pulp dilution is  practiced at Mill A.
More detailed mass balance studies  would be necessary to determine

-------
                          -71-
                      TABLE VII-4


                 UNBLEACHED KRAFT PULPS


 [Concentrations in parts per trillion  (ppt)  or  pg/gm.]


                     2378-TCDD            2378-TCDF

     MILL A

      Softwood       ND  (0.74)            ND  (0.27)
      Hardwood       ND  (0.31)            ND  (0.23)


     MILL B

      Softwood       ND  (0.95)               1.5


     MILL C

      Hardwood       ND  (0.56)            ND  (0.16)


     MILL D

      Softwood       ND  (0.70)            ND  (0.20)


     MILL E

      Softwood       ND  (0.44)               1.1
      Hardwood       ND  (0.98)               2.3
NOTE:  ND - Not detected; analytical detection  level  in
       parentheses  (  ).

-------
                               -72-
the extent to which the brownstock  pulp findings can be attributed
to this practice.  The 2378-TCDF data and the 2378-TCDF/2378-TCDD
ratio for other  mill  streams  also  suggest  that  the  brownstock
pulps at Mills B and E may contain 2378-TCDD at less than detectable
levels.

    Based upon the negative 237&-TCDD findings and the intermittent
and relatively low  level  contamination  of unbleached  pulps  with
2378-TCDF, analyses of  pulping process and chemical  recovery system
wastewaters and lime muds were not conducted  in order to conserve
analytical resources.  Analyses  of  preliminary  samples  from Mill A
(Section V.A.2)   indicate  no  detectable  levels  of  2378-TCDD  or
2378-TCDF in pulping process  wastewaters  or lime rnud at that mill.

C.  Bleach Plant Findings

1.  Bleach Plant Chemical Applications

    As noted earlier,  bleach plant  process  operating  logs  were
obtained from the  respective  mills during the  weeks  of the field
surveys.  The data  for  the 24-hour  sampling  periods  were reduced
and are  presented  in   Table  VII-5   for  each  bleach  line.   A
significant finding  from  this e;xercise  is that interpretation of
the process operating logs from different mills  is not straight-
forward.  Mill personnel  sometimes  record  data  entries  on  log
sheets that are  different than  called  for by the headings on the
logs (e.g., % valve  opening vs. gpm  of  chemical  solution); NaOCl
solution strength and flow may not be  monitored  routinely; and mass
flow rates  of  chlorine may  not be  monitored  with  a  reasonable
degree of accuracy.  In many  ccises,  these practices  have evolved
over a  number  of years.  They  are the  reported  process control
information most  useful  for  bleach  plant   operators.   However,
these practices  created  considerable  difficulty  in determining
reasonably accurate  chemical  application rates  for  the sampling
periods for this  study.   Accordingly,  it  is  strongly recommended
that further mill scale research or monitoring efforts be proceeded
by a thorough  review of existing  bleach plant process operating
monitoring systems and data reporting procedures.

    Notwithstanding, the data reported on Table VII-5 are believed
to be  fair  representations  of  chemical applications  during the
survey periods for most of the fi^e mills.  Data  for Mill D are rough
engineering estimates  of  typical  chemical usages determined from
inventories over  a  monthly period  encompassing the field program
for that  mill.   Deficiencies  in monitoring  equipment   in  the
bleach plant  precluded  collection  of  more  reliable  chemical
application rate  data  for  the survey period.  Data for the other
mills were  developed in large  measure  directly  from  the bleach
plant operating  logs with adjustments suggested by mill personnel

-------
                                        -73-
                                    TABLE VII-5

                         BLEACH PLANT CHEMICAL APPLICATIONS
                       (Ibs/ton of Air Dried Unbleached Pulp)
Mill A - Softwood Bleach Line  (June 24-25, 1986)


C12
NaOH
02
NaOCl
PH
PN:
Mill A -

C12
NaOH
02
NaOCl
H202
PH
PN:
Mill B -


Unbleached
Pulp





19.0/19.6/20.
Hardwood Bleach
Unbleached
Pulp






11.6/11.8/12.
Softwood Bleach
Unbleached
Pulp

C
64/75/89



1.8/1.9
3 CEK:
Line (June
C
55/66/73




2.5/2.8
2 CEK:

E0 H H

25/29/32

91.4 76.9
10.3/10.8 8.6/8.8 8.3/8.6
2.9/3.0/3.2
24-25, 1986)

E_ _i 	 N 14 J. 	 N LI HP


22/23/24

61.3 69.5
NA
9.7/10.7 8.2/9.4 8.3/9.3 7.7/8.7
2.7/2.9/3.0
Line (September 8-9, 1986)

Cn

E H H D
C12 50/82/117
C102
NaOH
NaOCl
pH
PN:
NOTES:




11.1/19.6/26.
0/0.6/1.


NA
4 CEK:
(1) Mi nimun/ Average/Maximum
5 8.6/11/12
38/54/72
19/33/52 0/2.7/4.4
10.2/10.7 8.5/8.9 NA 1.9/2.6
2.2/4.6/5.9
( Ibs/ton) .
        (2) pH - Minimum/Maximum standard units.
        (3) PN - Permanganate number or K number for unbleached
                 kraft pulp - minimum/average/maximum.
        (4) NA - Data not available.
        (5) NM - Not measured.
        (6) CEK - Caustic extraction stage pulp permanganate
                  number or K number - minimum/average/maximum.

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                                        -74-
                              TABLE VII-5 (continued)

                         BLEACH PLANT CHEMICAL APPLICATIONS
                       (Ibs/ton of Air Dried Unbleached Pulp)
Mill C - Hardwood Bleach Line (October 15-16, 1985)
            Unbleached
               Pulp            Cn            En          D
   C12                        42/50/65
   C102                    3.7/4.3/5.0               14/15/17
   NaOH                                   15/19/22
   02                                     12/12/14
   pH                          1.5/1.9   10.5/11.6       MA
   PN:    12.9A3.7/14.4         CEK:  2.1/2.3/2.5
Mill D - Softwood Bleach Line - A (December 2-3, 1986)
             Unbleached
                Pulp          C     	E	      H
   C12                        69
   NaOH                                   46
   NaOCl                                            89
   pH                        2.3    9.5A0.6   7.8/9.1

   Pf-J:     22.0/24.3/26.9         CEK:    NM
Mill D - Softwood Bleach Line - B (December 2-3, 1986)
             Unbleached
                Pulp           C         E          H
   C12                        73
   NaOH                                     53
   NaOCl                                             226
   pH                       2.3/2.4   9.7A0.6   7.5/8.8

   PN:     22.0/24.3/26.9           CEK:    NM
Mill E - Softwood Bleach Line  (January 13-14, 1987)
             Unbleached
           	Pulp	   	CD           EQ	   	H
   C12                      120/147/191"
   C102                             3.4                            12/13/13
   NaOH                                   108/139/187     2.4           2.4
   02                                             7.1
   NaOCl                                                12A9/28
   pH                               1.8     10.5/11.3    8.2/9.9    3.9/9.0

   PN:     10.1/18.8/24.5           CEK:  2.5/3.0/3.3

-------
                                        -75-
                              TABLE VII-5  (continued)

                         BLEACH PLANT CHEMICAL APPLICATIONS
                        (Ibs/ton of Air Dried  Unbleached  Pulp)
Mill E - Hardwood Bleach Line  (January 14, 1987)
Unbleached
Pulp
C12
C102
NaOH
02
NaOCl
PH
Cn
76/93/107
1.8/1.9/2.2
1.8
Eo
90/93/97
4.2
11.4/11.5
H
14/23/38
9.9/10.7
D
13 A 5/16
6.5/7.3
   PN:
11/16.7/22.4
CEK:  2.1/2.8/3.7

-------
                               -76-
in certain  cases.   The permanganate  numbers  for  the  unbleached
kraft pulps fed  to  the chlorination  stages  and the minumum and
maximum pH  values  recorded  at each  stage  of bleaching  are  also
presented in Table VI1-5.

    The bleaching practices  at  the   five  mills cover   a  fairly
broad spectrum of  bleaching  sequences  and chemical  application
rates.  However,  these plants do not  represent  the full  range of
bleaching sequences, bleaching tower  configurations,  or  chemical
application rates in United  States bleached  kraft  pulp and paper
mills.  For the five mills,  first stage  chlorination  rates range
from 50 to  108 Ibs  Cl2/ton of air dried  brownstock pulp, or  2.5%
to 5.4%.  Chlorine dioxide is added  in  the chlorination  stage at
four of  eight  bleach  lines  at  rates   of  0.6  to 4.3  Ibs/ton.
Sodium hydroxide  is applied  from  19 to  139  Ibs/ton  in caustic
extraction  stages.   Oxygen   is  added in  five  of   eight  caustic
extraction  stages.  Sodium hypochlorite  is also applied in two of
eight caustic extraction stages, both with oxygen.  For  the  four
mills with  hypochlorite stages,  the  range  of  sodium hypochlorite
application rates is 19 to 227 Ibs/ton.  These  data are  used and
discussed in subsequent sections.

2.  Unbleached and Bleached Kraft Pulps

    The unbleached  pulp  2378-TCDD  and 2378-TCDF data  from Table
VII-4 are presented in  Table  VI1-6 with the corresponding bleached
pulp data for the five mills.  Nine samples of bleached pulp were
collected vs. seven  samples  of unbleached pulp.   At  Mill  A, the
unbleached  hardwood  pulp  is bleached   using   CEOHH  and  CEOHHP
bleaching sequences.   At Mill D, the  unbleached softwood pulp is
bleached in parallel CEH sequences.

    These data clearly show the1 effect   of  bleaching  kraft pulps
on the formation of 2378-TCDD arid 2378-TCDF.  2378-TCDD was found
in seven of nine bleached pulps at concentrations ranging  from 3 to
51 ppt and  2378-TCDF  was  found in eight of nine  pulps at levels
ranging from 8  to 330 ppt.   The median and  mean   concentrations
are presented below with nondetects counted as  zero:


                           2378-TCDD      2378-TCDF

               Median         5 ppt         50 ppt

               Mean          13 ppt         93 ppt


    There does not  appear  to be  a  clear relationship between the
type of  wood  pulp processed and the  concentrations of  2378-TCDD
or 2378-TCDF found  in  the fully bleached pulps.  At the outset of

-------
                                    -77-
                                TABLE  VI1-6
                   UNBLEACHED AND BLEACHED  KRAFT PULPS
                 [Concentrations  in  parts  per  trillion (ppt)  or pg/gm.]
                       2378-TCDD
MILL A

 Softwood
 Hardwood
MILL B
 Softwood
MILL C
 Hardwood
MILL D

 Softwood A
 Softwood B
MILL E

 Softwood
 Hardwood
Unbleached Pulp  Bleached Pul]
   ND (0.74)
   NO (0.31)
   ND (0.95)
   ND (0.56)
   ND (0.70)
   ND (0.70)
   ND (0.44)
   ND (0.98)
16
(4.9(H)
 3.0(P)
11
ND (0.62)
ND(1.0)
3.9
26
51
                                           2378-TCDF
           Unbleached Pulp  Bleached  Pulp
ND (0.27)
ND (0.23)
1.5
ND (0.16)
ND (0.20)
ND (0.20)
1.1
2.3
330
(47(H)
 50(P)
 61
 15
ND(1.2)
7.8
140
180
NOTES:  (1) ND - Not detected; analytical  detection level
                 in parentheses  (   ).

        (2) Mill A - H = Bleached pulp  from  CEOHH sequence.
                     P = Bleached pulp  from  CEOHHP sequence.
                     Unbleached  kraft hardwood  pulp is
                     processed in common C and  Eo stages.

        (3) Mill D - A common unbleached kraft  pulp is supplied
                     to both bleach  lines  at Mill D.

        (4) Mill E - The hardwood line  bleached pulp  sample  con-
                     tained an unknown  amount of softwood pulp.

-------
                               -78-
this study, it was hypothesized  that  bleaching  of softwood pulps
may result in higher levels of 2378-TCDD and 2378-TCDF based upon
the higher lignin content typically found in softwoods.  However,
the data displayed in Table VII--6 do not support that hypothesis.
Note that although precautions were taken  in the  field to insure
that hardwood pulp  was  sampled  on the B  bleach  line at  Mill  E
after a  change  over  from  softwood pulp  bleaching,  a review  of
process operating  logs  indicates  the  pulp  sample designated  as
hardwood contains  undetermined  amounts  of  both  hardwood  and
softwood pulp.   The  relatively high concentrations  of 2378-TCDD
and 2378-TCDF in that sample  and  the  uncertainty  surrounding its
actual composition confuses this  analysis.   Variables  other than
the general wood type  furnished  to the  bleach  plant  would appear
to have more influence on the formation of 2378-TCDD and 2378-TCDF.
It should be  noted that  the results presented  in  Table VII-6 may
not account  for  either  sampling  or process variability  and  it
would be  inappropriate  to generalize  further  on  the effect  of
wood species  with this  limited  data   base.   This  question  is
examined further in Section VII.C. 5. in the context: of the relative
amounts of lignin removed during  bleaching.

    The pulp  samples  were squeezed  during  collection  to remove
any loose water  in the pulp mat  and  the pulps were  analyzed  on
dry weight basis.  Hence, the  2378-TCDD  and 2378-TCDF concentra-
tions reflect findings on  the bleached  pulp carried  over to the
paper machine areas.  The next section  presents the  findings for
bleach plant filtrates (wastewaters).

3 .  Bleach Plant Wastewaters

    The bleach plant  sampling  plan for each mill was  focused  on
the collection of  wastewater  sstmples as close  to  the individual
bleaching stages as possible.   In every mill, seal tank overflows
or seal  tank  contents were sampled  following  each  stage  in the
respective bleaching  sequence.    While  sampling  in  this  manner
yielded analytical results  for 2378-TCDD and  2378-TCDF  close  to
process, the computation of mass  discharges was confounded by the
overall lack of  primary  flow  measuring  devices  on these streams.
In some cases, these flows were not continuous.  For every bleach
line, best engineering estimates  by mill  personnel  served as the
basis for the wastewater flow rates from each pulp washing stage.
For Mill A, the  estimates ,were refined  after the  field survey by
mill personnel through supplemental field  testing.   Although the
accuracy of  the  flow estimates  could  not  easily be  verified  at
most mills, they are considered reasonable for computing the mass
discharges of 2378-TCDD  and  2378-TCDF  in  these  streams.   Often
the mills  relied upon prior  special  study situations  in which
water balances  were   estimated  for the  bleach plant  and other
process areas.

-------
                               -79-
    The computation of mass flow rates of 2378-TCDD and 2378-TCDF
from the bleacheries  is  also  affected by the  reliability  of the
analytical results.   As  described  in Section  VI,  the  analytical
results are considered to be highly reliable with few exceptions.
Analyses of  field  duplicate   samples and  duplicate  laboratory
analyses for bleach plant  samples yielded  agreement  within ±15%
and recovery of  labeled  spiked compounds were within acceptable
ranges.  Data  for  two C-stage samples  with  duplicate  field  or
laboratory analyses (Mill B - 86374613/73; Mill D - DF024412/605)
did not  yield  good  agreement  as  discussed  above.   These data
suggest the possibility of field sampling problems  (e.g., collec-
tion of nonrepresentative duplicate samples) or laboratory-related
issues (e.g., nonhomogeneity of sample aliquots analyzed) .  Analy-
tical difficulties peculiar to C-stage filtrates may be possible.

    As described  earlier,  the  analytical  results  for 2378-TCDD
and 2378-TCDF  presented  in Attachment E  were combined  with the
wastewater flow  estimates  and  pulp  production rates  to compute
the mass  flow  rates   of  2378-TCDD  and  2378-TCDF presented  in
Attachment F.   While   the  data contained  in  Attachment F were
generated with a  computer program to more  than  two  significant
figures, the resultant mass flow rates are considered accurate at
most to only two significant figures.

    Table VII-7 presents a  summary of the bleach line wastewater
data for  2378-TCDD and  2378-TCDF.   2378-TCDD  was detected  in
bleach line wastewaters from four of  five mills, Mill C being the
exception.  2378-TCDF  was  found in every bleach  line  wastewater
sampled.  Although  2378-TCDD  was  not found  in the bleached pulp
or in bleach line wastewaters  from Mill C, it is probably present
at less  than  analytical  detection levels  since  it was  found  in
combined paper machine wastewaters  and  wastewater  sludges from
that mill.  (Another possible  source of 2378-TCDD  in the wastewater
sludge at Mill C is purchased  bleached softwood pulp from outside
sources.) Generally the highest concentrations  and mass discharges
of 2378-TCDD and 2378-TCDF were found in caustic extraction stage
(E or Eo) wastewaters  with  lesser amounts in hypochlorite (H, H/D)
and chlorination stage wastewaters (C, CD, and C/D) .

    Individual bleach line summaries  are  presented  in Tables VII-8
to VI1-12.   The  summaries  include concentrations  and estimated
mass loadings of  2378-TCDD and 2378-TCDF in unbleached and bleached
kraft pulps and individual  bleach line wastewaters.  The estimated
total daily bleach line generation rates of 2378-TCDD and 2378-TCDF
were determined  as  the  sum of the mass  flow rates  in bleached
kraft pulps  and  bleach  line   wastewaters  (bleaching  stage fil-
trates) .  The  relatively  minor amounts  of  2378-TCDF  found  in
unbleached kraft pulps at  Mills B  and E  were not discounted from
the bleached pulp  results  for purposes  of  estimating  the amount

-------








































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                               -87-
of 2378-TCDF  produced  in  bleach  lines  at  those mills.   Also,
recycle of paper machine white waters practiced at some mills was
not taken into account in these calculations owing to the relatively
low-level contamination  found  in paper machine  wastewaters  (see
Section D below).  The practice of recirculating white waters may
be intermittent  depending  upon  the availability  of  warm process
water for pulp transport or dilution.

    The wastewater data  for  the  softwood  bleach line at  Mill  A
(Table VII-8), the softwood  and hardwood lines  at  Mill  E  (Table
VII-12), and, to  a lesser  extent, the softwood  lines at  Mills  B
and D (Tables VII-9 and VII-11)  show similar patterns in that the
greatest amounts of 2378-TCDD and 2378-TCDF were found in caustic
extraction stage  effluents.   That  trend  is  not evident  in  the
hardwood bleach  line  at Mill  A.   At  Mill  C 2378-TCDD  was  not
detected in bleach line wastewaters.   The  2378-TCDF data at  Mill C
show an even  distribution  in Co-stage and  Eo-stage  wastewaters.
As noted  above,  the  C-stage and  H-stage wastewaters  generally
contain significantly less  2378-TCDD and 2378-TCDF than the E-stage
wastewaters.

    The bleach plant wastewater data do not clearly distinguish the
point or points of dioxin formation in the bleacheries.   However,
these data indicate formation in the C stages and possibly  in the
E stages.  It is  not possible with these data  to determine whether
2378-TCDD and 2378-TCDF  are  formed in the highly acidic  C stage
and extracted from the pulp  in  the  E  stage,  or,  whether there is
additional formation  in  the  highly  alkaline  environment  of the  E
stage.  The data also suggest formation of 2378-TCDD and 2378-TCDF
in subsequent  bleaching  stages.   This  point  is  particularly
evident from the  Mill D data which show that 2378-TCDD and 2378-TCDF
can be found  in the final hypochlorite bleaching stage.   Rigorous
mass balance  studies  around each  bleaching stage  in  several
bleach lines  are necessary  to  fully investigate  this  question.
Recent data from other researchers where inter-stage pulp samples
were collected  in  bleach  lines  suggests  that  2378-TCDD  and
2378-TCDF formation  is   concentrated  in  the chlorine  stage.4'5

4.  Distributions of 2378-TCDD and 2378-TCDF

    Total bleach  line exports  of  2378-TCDD  and 2378-TCDF  are
presented in  Table VII-13  with  the distribution  between pulp and
wastewater from each line.   Within each bleach line the distribu-
tions of  2378-TCDD  and 2378-TCDF agree  within  4%,  which  is
substantially less than  the  sampling  and  analytical error  and
uncertainty in  wastewater   flow  measurements expected   in  this
study.  These data  indicate  the partitioning  of  2378-TCDD  and
2378-TCDF between  bleached  pulp  and  wastewaters within  bleach
lines is essentially the same.  There is considerable variability

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                               -89-
in the  distributions between  pulp  and  wastewaters  across  the
eight bleach lines.  There  is  no  obvious  pattern  associated with
the type of  pulp bleached or the degree of application of bleaching
chemicals.  Factors  accounting  for   these  differences  are  not
known, but  may be related  to  the efficiency of  chemical  mixing
within the  bleaching reactors, bleach  tower  pH  or  temperature,
the efficiency of pulp washing  between  bleaching  stages,  or some
mechanism associated with the chemical or physical characteristics
of the partially bleached pulps.

5.  Formation of 2378-TCDD and 2378-TCDF

    The rates of  formation of 2378-TCDD  and 2378-TCDF for the five
mills are presented  in Table VII-14 computed as follows:

    1.  From  individual  bleach  line exports  -  the  sum   of  the
        bleached pulp  and  bleach  line wastewater  loadings  was
        divided by  the  respective brownstock pulp  inputs  to the
        respective bleach lines; and

    2.  From total mill  exports  - the sum of  the bleached pulp,
        treated wastewater  effluent,  and  wastewater  sludge load-
        ings was divided  by the sum of brownstock pulp inputs to the
        bleach lines.

    This method  of  presenting  the  data  was  initially  selected
because it  was  hypothesized that the major  source of  2378-TCDD
and 2378-TCDF was the bleaching process.  Thus, reducing the data
based upon  the  brownstock  pulp  entering  the  bleach plant  was
considered  logical.

    For Mills A,  B,  and C  the  rates of formation computed from
the total mill exports fall within the  range  or  are  close to the
rates computed from the  individual bleach line exports.  The rates
of formation computed from  the  total  mill  exports at  Mills D and
E are  less  than  those computed  from the   individual  bleach line
exports.  Agreement  between the rates of  formation  computed from
bleach line and total mill exports is considered reasonably good.
The extent to which  formation of 2378-TCDD and 2378-TCDF determined
for the bleach lines at the five  mills and from  the  total mill
exports is representative of long-term average conditions at these
mills is not known.   The  extent to which the data  from these mills
are representative of the industry is also not known.

    Although the scope of this study was limited to screening for
sources of  dioxins  at  five bleached  kraft pulp  and  paper mills,
there were  several hypotheses that developed during the course of
the study regarding  the formation of 2378-TCDD and 2378-TCDF.  At
the outset, the principal  hypothesis  was  that  bleaching  of kraft

-------
                                -90-
                            TABLE VII-14

                FORMATION OF 2378-TCDD AND 2378-TCDF

        [10-8 Ibs/ton (kg/kkg)  of brownstock pulp bleached]
MILL

 A - Softwood
 A - Hardwood
From Bleach Line Exports

 2378-TCDD   2378-TCDF
   20
    0.9
360
 11
            From Total Mill Exports

             2378-TCDD   2378-TCDF
7.2
130
 B - Softwood
    2.6
 13
3.0
 19
 C - Hardwood
     ND
  3.2
0.14
  4.7
D
D
E
E
- Softwood A
- Softwood B
- Softwood
- Hardwood
1.4
5.7
13
20
2.6
12
63
76
                                                0.76
                                                11
                                             1.5
                                            51
MEDIAN!

MEAN
    4.1(2.0)

    8.0(4.0)
 12.5(6.3)

 68  (34)
3.0(1.5)

4.4(2.2)
 19(9.5)

 41(21)
NOTES:   (1)  ND - 2378-TCDD not detected.
         (2)  Bleach line exports  include bleached pulp and
             bleach line wastewater streams discharged from
             the process at each  bleach line.
         (3)  Paper mill exports include bleached pulp from
             all bleach lines, treated wastewater effluent,
             and combined wastewater sludge.   The formation
             of 2378-TCDD and 2378-TCDF was computed on  a
             production weighted  basis for mills with
             multiple bleach lines.
         (4)  The Mill E hardwood  line bleached pulp sample
             contained an unknown amount of softwood pulp.

-------
                               -91-
pulps with chlorine and chlorine derivatives would, in some manner,
give rise  to   formation  of  2378-TCDD and  2378-TCDF.    This  was
clearly indicated  by the  results  from  preliminary sampling  at
Mill A (Section V)  and was  confirmed  by the data from  full-scale
sampling at  the  five  mills.   With  that  hypothesis  confirmed,
attention was  directed at  using the  available  data and  recorded
process information  to explore other  relevant  hypotheses  beyond
the principal one noted above.  The data obtained from this limited
study are clearly not sufficient  to establish  any of the following
hypotheses.  However, some useful  insights can be gained from the
analyses presented below:

a.  Bleaching  softwood vs. hardwood kraft pulps

    As noted  earlier,  it was  theorized that bleaching  softwood
kraft pulps might result  in higher rates of  formation of 2378-TCDD
and 2378-TCDF  than  bleaching  of hardwood kraft  pulps  due  to the
higher lignin  content of  softwoods.   The data presented  in Table
VII-14 do not  indicate a  clear trend  with  respect to wood types.
While the  formation rates  for  2378-TCDD for  all  of the  softwood
bleach lines are  higher  than  those for the hardwood bleach lines
at Mills A  and C,  the hardwood  bleach line  at  Mill  E generated
2378-TCDD at  a rate  equivalent  to  the  highest  softwood  bleach
line (Mill  A) .   (Note the  bleached pulp  sampled at  the  Mill  E
hardwood bleach line  on  a  short-term  basis  was a combination of
hardwood and  softwood pulps  resulting  from  a  process  change.)
For 2378-TCDF, the  softwood bleach line  at  Mill A generated more
2378-TCDF per  ton  of  brownstock  pulp  bleached than did any other
bleach line.   (The 2378-TCDF/2378-TCDD ratio  for  this bleach line
was the highest  among all bleach  lines sampled).   The  softwood
and hardwood bleach lines  at Mill  E  also  generated considerably
more 2378-TCDF, as  well  as  2378-TCDD than  all other bleach lines
except the  softwood line at Mill  A.  Analysis of particular wood
species beyond the  general  hardwood/softwood  classifications has
not been attempted here but may prove  to be worthwhile.

    To investigate bleaching of hardwood pulps vs. softwood pulps
further, estimates  of lignin  removal  in   the   chlorination  and
caustic extraction  stages  in  each bleach  line were  made.   The
average CEK number  (permanganate number of the partially bleached
pulp after  caustic extraction)  was  subtracted   from  the average
K-number (permanganate number)  of  the brownstock pulp  for  each
bleach line.   K-CEK for  Mill  D  was not determined since  CEK is
not monitored  at  the bleach lines at Mill D.   The  K-CEK  values
are uniformly  higher  for  partially  bleached  softwood  pulps.

-------
                               -92-
    Figures VII-1 and VII-2  are  plots  of  2378-TCDD and 2378-TCDF
formation for each bleach line vs. the difference in permanganate
number from brownstock pulp  to  partially  bleached pulp after the
caustic extraction stages (K-CEK).  The bleach  lines are designated
by mill and by "h" or "s" for hcirdwood or  softwood, respectively.
These graphs show,  generally,  with increasing  lignin  removal as
estimated by K-CEK,  there is  increasing  formation of  2378-TCDD
and 2378-TCDF.   The data  for the hardwood bleach  line  at  Mill E
(Figure VII-1)  does  not  fall  within  the  general  trend observed
for most of  the  other bleach  lines.   If  more  softwood pulp had
been sampled during  the  short-term, 4-hour  composite  sample at
this line, than  was estimated from a  review of  the  log  sheets,
the actual K-CEK  for  the pulp  sampled would have  been greater,
thus causing  the  plotted  point  for   that  bleach  line to   fall
closer to those for the  softwood  bleach lines  for Mills A and E.
The same type of  change would occur  in  Figure VII-2 for 2378-TCDF.
The limited data  were evaluated  with   a curve  fitting  program to
determine whether any linear, exponential, log, or power functions
might describe the   results.   For  Figure VII-1   (2378-TCDD  vs.
K-CEK), the  r2  value  (coefficient  of determination)  for   each
function was less than 0.5,  indicating the data do not fit any of
the functions.   For  Figure VII-2  (2378-TCDF vs. K-CEK)  the results
were about the same.   Clearly, substantial additional  data   from
other mills are needed to examine these relationships.

    Nonetheless,  these limited  data appear to provide some support
to the hypothesis that bleaching  of kraft  softwood pulps results
in greater formation of 2378-TCDD and  2378-TCDF than bleaching of
kraft hardwood pulps.   Because of  the possible  significance of
the results,  additional  research  into  this  question  through
full-scale sampling at other mills  is  warranted.   Care should be
taken to  insure  that the sampling programs  are  conducted  in a
manner to clearly isolate sampler of  hardwood and softwood pulps
on bleach lines that process both types of pulps.

b.  Degree of chlorination

    The amount of  lignin remaining in the  brownstock  pulp  is a
major determinant of the amount of chlorine required in the first
stage chlorination reactor.   It was also theorized that the gross
amount of  chlorine  applied   to  the pulp  may  have  a  substantial
effect on  the  amounts of 2378-TCDD and  2378-TCDF formed.   The
formation of 2378-TCDD and 2378-TCDF at  the five mills was evaluated
with respect to applications of chlorine and chlorine derivatives
as follows:

    (1) The rate  of  application  of chlorine  and chlorine equiva-
        lents  (Ibs/ton air dried of brownstock pulp) in the first
        stage chlorination reactor.

-------
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-------
                                              -94-
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-------
                               -95-
    (2) The rate of  application  of chlorine and chlorine equiva-
        lents (Ibs/ton air dried  of brownstock  pulp) in the entire
        bleaching sequence.

    The chlorine equivalents  were computed  on the basis  of the
weight percent  composition of chlorine  in  chlorine  dioxide and
sodium hypochlorite  (C12EQWT), and  on the basis  of  the  chlorine
equivalent oxidizing  power  of chlorine dioxide  and  sodium hypo-
chlorite (Cl^EQOX).    Table  VII-15  presents  a  summary  of  the
chemical application  rates derived  as described  above   for  the
chlorination stage at each bleach line and the total for all stages
of bleaching  at  each  bleach line.   The  chlorine dioxide  and
sodium hypochlorite  application  rates presented   in  Table  VII-5
were used to compute  the  chlorine  equivalents presented  in Table
VII-15.  Note that  chemical application data  presented  in Table
VII-15 are  averages  over  the sampling  period  for each  bleach
line.   Reference is made  to Table  VII-5 for  the  range  of values
recorded during  the  surveys.  For the hardwood  bleach  line  at
Mill E,  the  residence  time in  the  bleach  line  was taken  into
account to the extent possible when computing chemical application
rates to  adjust for  the  short-term  (4-hour)   sampling  period.
This was  judged not  necessary at the other bleach  lines  where
24-hour sampling was  conducted and the production grades did not
change during the sampling surveys.  A  two-hour gap in the process
data for the Mill  E  hardwood bleach line  occurred just  prior to
the change  over.   This made  determination  of  actual  chemical
application rates during that period impossible.

    Figures VII-3 and VII-4  are  plots  of  2378-TCDD and  2378-TCDF
formed in each bleach line (Ibs x 10~^/ton  of air dried brownstock
pulp)  vs. the degree of chlorination in the first stage bleaching
tower (Ibs Cl2  applied per ton  of  air  dried  brownstock pulp).
Figures VII-5 and  VII-6  are  similar  plots  of the  formation  of
2378-TCDD and 2378-TCDF vs.  the   equivalent  chlorine  oxidizing
power (C12EQOX)  applied in  the first  stage chlot: ination  reactor,
thus taking into account  the oxidizing power of chlorine dioxide
applied in  the   chlorination  stages   at   certain  bleach  lines.
Plots of the  equivalent  chlorine  applied  in  the C-stages  on  a
weight composition  basis  (C12EQWT) were  also prepared,  but  are
similar to Figures  VII-3  and  VII-4  and  are  not  presented  here.

    The data presented  in  Figures  VII-3  through  VII-6 show  to  a
limited extent,  that  the  bleach  lines   with  higher  rates  of
chlorination in the C stages produce more 2378-TCDD and 2378-TCDF
in the entire  bleach lines.  However, there  are  no quantitative
relationships evident  (r2  values  for  linear,  exponential,  log,
and power functions were  less  than 0.5 for Figures VII-3 through
VII-6).  Note that  these plots  deal with the chemical applications

-------
                                -96-
                            TABLE VI1-15

      CHLORINATION STAGE AND BLEACH LIME CHLORINE APPLICATIONS
               (Ibs/ton of Air Dried Brownstock Pulp)
                 Bleaching    Chlorination Stage      Bleach Line
Mill  Wood Type   Sequence  Cl2  C12EQWT  Cl^EQOX  ClpEQWT  C12EQOX
       Softwood
       Hardwood
CE0HH
CE0H
 J- — >HHP
 75
 66
 66
 75
 66
 66
 75
 66
 66
115
 81
 83
235
125
132
  B    Softwood   CDEHHD
           82
        83
          84
          98
         147
  C    Hardwood   C[}EOD
           50
        51
          61
          55
         130
  D    Softwood   CEH
       Softwood   CEH
           69
           73
        69
        73
          69
          73
          90
         1274
         154
         2894
       Softwood
       Hardwood
CDE0D
CDE0D
148
 93
149
 93
157
 98
157
102
208
156
NOTES:  (1) Cl2     - Chlorine
        (2) C12EQWT - Equivalent chlorine applied based upon the
                      weight percent composition of Cl2 in C102
                      and NaOCl:

                      (C102 x 0.256) and (NaOCl x 0.238)

        (3) C12EQOX - Equivalent chlorine oxidizing power applied
                      based upon oxidizing power of C102 and NaOCl:

                      (C102 x 2.53) and  (NaOCl x 0.952)

                      [Reference 6]

        (4) For the Mill D second softwood bleach line/ H stage
            sodium hypochlorite usage is unusually high due to
            caustic carryover from an undersized caustic washer.
            Mill personnel estimate that roughly one-half of the
            sodium hypochlorite applied may be consumed to neutral-
            ize excess aklalinity.  Accordingly, the following
            chlorine equivalents were estimated for this bleach
            line and used in subsequent analyses:
            C12EQWT - 102 Ibs/ADT
                         CL2EQOX -  181  Ibs/ADT

-------
            -97 -






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                              -101-
in chlorination  stages only  while  the  2378-TCDD  and  2378-TCDF
data are for each  bleach  line  as  a  whole.   Rigorous mass balance
studies around the C  and  E stages at a number  of  mills would be
necessary to determine to what extent there is a direct relationship
between first  stage  chlorination  and formation  of  2378-TCDD and
2378-TCDF.

    Figures VII-7 and  VII-8  are plots of  formation of 2378-TCDD
and 2378-TCDF  vs.  the chlorine  equivalents  (C12EQOX)   for  the
entire bleaching sequence  at  each  mill.  Figure VII-7 shows a much
clearer  relationship  between   the  application  of chlorine  and
chlorine derivatives  and   formation  of  2378-TCDD  (r2   0.60  for
exponential function;  r2  0.72  for  power  function).  The  Mill  E
hardwood line  appears  as  the  only  outlier  in Figure  VII-7.   As
noted earlier,  sampling  at  that  mill was  conducted  for  only  a
short time   after  a  change over  from softwood  to  hardwood pulp
bleaching.   Thus,  the pulp  sample  obtained  was  a  mixture  of
undetermined amounts  of  softwood  and hardwood  pulp.   Also,  the
log sheet for  that line had  a  two-hour  gap  in data just prior to
the change   over,  making   a  determination  of  actual  chemical
application rates  for  the pulp sampled  impossible.  Discounting
data from that  line,  the   r2  values  for  the remaining  data  are
0.87 (linear  function);  0.70  (exponential  function);  0.78  (log
function;,  and  0.80   (power  function).   These  data  suggest  the
possibility of a quantitative  linear relationship between dioxin
formation and  the  rate of  chlorine equivalents  applied  across
entire bleach lines.    In  Figure VII-8,  the  plot  for 2378-TCDF is
somewhat skewed by the data  for the hardwood line  at  Mill  E and
the softwood  line  at  Mill  A.   The  latter  line had  the highest
rate of formation of 2378-TCDF.  Those data do not  fit any of the
above cited functions particularly well (r2 0.45-0.63).

    The data presented earlier  (Tables  VII-8  through  VII-12)  and
in Figures   VII-3  through  VII-8,  indicate  that  although  most  of
the formation of 2378-TCDD and 2378-TCDF may be occurring in the
first stage  of  chlorination,   the  formation of   2378-TCDD  and
2378-TCDF across the  bleach  lines is more  closely  correlated to
the application  of  chlorine  and  chlorine  derivatives  across
entire bleach lines rather than chemical application in the first
stage of chlorination.

-------
                                       -102-
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-------
                              -104-
c.  Chlorine dioxide substitution in chlorination stage

    In a survey of  United  States pulp mills,  it is reported that
C1C>2 is substituted for some fraction of the chlorine in C-stages
at 82 of 95 bleach  lines. 7   The  rates  of application were reported
to be above  10  Ibs/ton  for 16 mills  and below  10  Ibs/ton  for 66
mills.

    Reproduced below  is a  sunmary  of  chlorine dioxide  (C102)
substitution practiced at Mills B, C, and E during the field surveys
at each mill.   Chlorine dioxide  is  not used  at Mills A  and D.
                   C-Stage Chemical Application
                    Ibs/ton Air Dried BS Pulp   Chlorine Dioxide
 Mill  Bleach Line  Chlorine   Chlorine  Dioxide    Substitution
   B   Softwood        84           0.6               1.8%
   C   Hardwood        50           4.3              18.4%
   E   Softwood       147           3.4               5.7%
       Hardwood        93           1.9               5.1%
    Another hypothesis  is  that substantial substitution  of C102
in C-stages would give rise to lower rates of formation of 2378-TCDD
and 2378-TCDF.   The data  from bhis  survey are far too limited to
validate or disprove this  hypothesis.   However,  it is noteworthy
that 2378-TCDD was  not detected in bleached  pulp  or bleach line
wastewaters at Mill  C, with  the  highest  C1C>2  substitution (and
overall lowest  chlorine  usage  in  the  C-stage).   The rates  of
formation of  2378-TCDD  and  2378-TCDF  at Mill  E are substantially
higher than at Mill B despite C1C>2 substitution about three times
greater.  However, chlorination rates at Mill E were both 11% higher
(Mill E hardwood) and 75%  higher (Mill  E softwood)  than at Mill B.
While data  from  other  mills  might  be  helpful  in  reviewing this
question, the impact of C102 substitution on formation of 2378-TCDD
and 2378-TCDF  can  best be   studied  with  controlled  laboratory
experiments.

d.  Oxidative extraction

    Nationally,  out of  95 bleach lines for which data were reported,
49 include  oxygen addition to caustic extraction stages.7  Of the
eight bleach  lines included in this  study,  oxidative extraction is
practiced at  Mill  A (softwood  and hardwood), Mill C  (hardwood),
and Mill E  (softwood and  hardwood).   Sodium hypochlorite is also
added to  the  caustic  extraction  stage at the  Mill  A  softwood
bleach line.   There are  no  discernible  relationships regarding
formation of  2378-TCDD and  2378-TCDF  among  the bleach  lines at

-------
                              -105-
these mills or between those bleach lines with or without oxidative
extraction.  Since  it  appears that  2378-TCDD and  2378-TCDF  are
principally formed  in   the   C-stages,   the   impact  of  different
downstream processes  such  as oxidative extraction  may  be  of
lesser significance  than  chemical  reactions  and  environmental
conditions in the  C-stages.   Here again the impact  of  oxidative
extraction can best be  studied with controlled laboratory or mill
experiments.

e.  Recycle of bleach line filtrates

    For the five mills  included  in  this  study,  recycle  of bleach
line wash  waters  is practiced to a  significant  extent  only at
Mill B.  As shown in Figure III-5, the D-stage filtrate is recycled
to the C-stage  seal  tank and  the first and  second  hypochlorite
stage filtrates  are recycled to  the  E-stage  seal  tank.   The
impact of  this practice  on  formation of  2378-TCDD  and  2378-TCDF
at Mill B is not known,  but thought to be not significant.  It is
possible, however,  that  recycle  of  bleach  line  filtrates  in
certain circumstances  might be significant.  For example, should
minor amounts  of  E-stage   filtrates  be  used   for  shower  water
additions on C-stage washers,  process conditions  at the point of
addition (high pH with free chlorine and potential dioxin precursor
compounds present)  might be conducive to formation  of  2378-TCDD
and 2378-TCDF.   Review  of  data  from  other  mills and  laboratory
scale research  are  needed   to  further  explore  this  question.

    Based upon these analyses, it  is  apparent that  the  formation
of 2378-TCDD and 2378-TCDF is  in some manner related  to the degree
of chlorination  and  lignin  content  of  the  brownstock  pulp.
However, the limited data and  limitations  regarding the accuracy
of chemical  application  data preclude  a more  rigorous analysis
here.  There are undoubtedly other factors that may affect forma-
tion of  2378-TCDD  and 2378-TCDF  in the  bleaching of  kraft pulp.
Following is a limited  list of possible  factors:

    (1)  Process conditions  in the chlorination  stage (pH, tempera-
         ture,  residence time, pulp  consistency,  and viscosity).

    (2)  Presence  of specific precursor compounds  in  unbleached
         pulp that may  be attributable to certain wood species or
         pulping practices.

    (3)  Efficiency  of  brownstock  and   partially bleached  pulp
         washing.

-------
                              -106-
    (4)   Efficiency of chemical mixing with  unbleached or partially
         bleached pulp.
    (5)   Bleach plant filtrate recycle(s)
         vat dilution, or stock dilution.
used for shower  water,
    (6)   Delignification with chemicals other than chlorine prior
         to chlorine bleaching,,

    An analysis of total mill exports of 2378-TCDD and 2378-TCDF is
presented later in  this section.   Total mill exports are comprised
of 2378-TCDD and  2378-TCDF  contained  in bleached  pulp,  treated
wastewater effluent, and wastewater treatment sludges.

-------
                              -107-


D.  Paper Machine Wastewaters, Utility Ashes, and Landfill Leachates

1.  Paper Machine Wastewaters

    Paper machine Wastewaters were  sampled  at each mill at loca-
tions of combined wastewater  flow or  at individual paper machine
wastewater discharges which were  flow-composited  into  one sample
for analysis  after  collection.   Mill  E  receives  paper  machine
Wastewaters from a nearby nonintegrated paper mill for treatment.
The data from  that mill are included in this section.  Paper machine
wastewater flows were obtained from primary flow measuring devices
or from estimates by mill personnel.

    Table VII-16 presents a  summary  of  combined  paper  machine
wastewater concentrations  and mass  flow rates  for  2378-TCDD and
2378-TCDF.  2378-TCDD was detected  in  four  of six combined paper
machine wastewater samples, ranging from 0.053-0.10 ppt.  2378-TCDF
was detected  in  each  combined  paper  machine  wastewater  sample
ranging from 0.015-0.35 ppt.   The  source of 2378-TCDD and 2378-TCDF
in these wastewaters is assumed  to be  the bleached pulp slurry fed
to the  paper  machines.   The  2378-TCDD  and 2378-TCDF  on  fine
particulates or in solution is passed from the pulp slurry to the
wastewaters.  Except  for  Mill C where  2378-TCDD was not detected
in bleach line wastewaters, the concentrations and mass discharges
of 2378-TCDD  and  2378-TCDF  from  paper  machine  wastewaters  are
quite small when  compared to combined  bleach plant wastewaters.
As noted  earlier,  a  possible contributing  source of  2378-TCDD
found in  wastewater  sludges  at Mill C  may  be purchased bleached
softwood pulp used at that mill.

2.  Utility Ashes

    A selected number  of  utility  samples  were analyzed  for 2378-
TCDD and  2378-TCDF.   These data  are  presented in  Attachments  E
and F.  2378-TCDD was  not detected  in fly ash  from Mill  A or in
bottom ash and fly ash at Mill E at detection levels ranging from
0.28-0.66 ppt.  2378-TCDF was not detected  in these  samples at
detection levels ranging  from 0.18-0.35  ppt.  Ash samples  from
the other mills were not analyzed.  At some mills, primary and/or
secondary wastewater  sludges  are  disposed of by  incineration in
hog fuel  boilers.   However,  this  is not practiced  at any  of the
five mills included in this study.

3.  Landfill Leachates

    Landfill leachate samples were collected at four  mills and a
sludge lagoon  effluent  sample  was  collected  at  Mill  D.   The
landfill leachate at Mill  A is a noncontinuous flow and is composed
of sludge landfill  leachate,  landfill  surface runoff,  and ground

-------
                                •-108-
                            TABLF: vii-16
                  COMBINED PAPER MACHINE WASTEWATERS
                  2378-TCDD
2378-TCDF
Mill
A
B
C
D
E
MEAN
MEDIAN
Mass Loading
Concentration Ibs/day
(PPt,pg/gm) (kg/day) x!0-6
0.
ND
0.
ND
0.
0.
0.
0.
021 0.73(0.33)
(0.0051)
011 0.73(0.33)
(0.0060)
053 8.3(3.8)
10a 2.1(0.93)
031 2.0(0.91)
016 0.73(0.33)
Concentration
(PPt,pg/gm)
0.
0.
0.
0.
0.
0.
0.
0.
19
11
20
015
17
35
17
18
Mass Loading
Ibs/day
(kg/day) x!0-6
6.9
6.2
14
1.2
27
7.2
10
7.1
(3.
(2.
(6.
(0.
(12
(3.
(4.
(3.
1)
8)
D
53)
)
3)
5)
2)
NOTES;   (a)   Nonintegrated paper mill wastewater
             discharged to Mill E for treatment.
        (b)   ND - Not detected at stated analytical
             detection level (  ) .

-------
                                -109-
  water.   Leachate wastewater  streams  are returned  for  wastewater
  treatment at Mills  A,  C, and  E.   T,he sludge lagoon  sample from
  Mill D and the  leachate sample  from Mill B are discharged directly
  to surface waters.  Table VII-17 presents a  summary of 2378-TCDD
  and 2378-TCDF  concentrations  and  mass  loadings  for  landfill
  leachates.  The data  show that  only one  sample/  Mill A,  had a
  detectable level of  2378-TCDD  (0.025 ppt).  The  other 2378-TCDD
  results were  not  detected   at detection  levels   ranging  from
  0.003-0.008 ppt.  2378-TCDF  was detected  in  all but  one  sample
  (Mill C).  Positive 2378-TCDF findings ranged from 0.011-0.11 ppt
  for the leachate samples.  The  mass discharges are not significant
  when compared  to  the  untreated  wastewater  loadings  from  other
  pulp and paper mill  sources,  and relatively small  when compared
  to treated process wastewater effluent discharges for those mills
  with detected  levels  of   2378-TCDD  or  2378-TCDF  in  treated
  effluents.
                            TABLE VII-17
                          LANDFILL LEACHATES
                  2378-TCDD
                        2378-TCDF
         Concentration
  Mill    (ppt,pg/gm)

   A        0.025
   B        ND(0.004)a
   C        ND(0.006)
   Dc       ND( 0.003)
   E        ND(0.008)
Mass Loadings
   Ibs/day
(kg/day)xl0-8

  3.8(1.7)
Concentration
 (PPt/pg/gm)

  0.11
  0.011
  ND(0.009)
  0.016
  0.064
Mass Loadings
   Ibs/day
(kg/day)x!0-8

  17(7.5)
    	b

  7.9(3.6)
  3.8(1.7)
NOTES;  (a) ND - Not detected at stated analytical
            detection levels (  ) .
        (b) Flow negligible  at  time  of survey  (est
        (c) Sludge lagoon effluent.
                              <50 gal/day)

-------
                              -110-
E.  Wastewater Treatment System Findings

    A principle objective  of this study was  to  (a)  quantify the
loadings of 2378-TCDD, 2378-TCDF,  and other PCDDs and PCDFs to the
general wastewater sewer;  (b) determine the removal efficiency in
wastewater treatment;  and  (c)  examine  their  distribution  in the
three wastewater treatment  plant export vectors (treated effluents,
combined dewatered sludges, and landfill leachates).

    Because of the prolonged residence time in  wastewater treatment
systems compared  to  the general mill  sewer flows, the wastewater
treatment system  effluents were  sampled  over a  different  time
frame to  account  for the time lag in  wastewater  treatment.   The
specific time lags incorporated into the effluent sampling programs
were as follows:

                      Mill A       None
                      Mill B      -12 hours
                      Mill C       36 hours
                      Mill D      -16 hours
                      Mill E      -24 hours

    The sampling  locations selected  for the  wastewater treatment
systems are  identified  in  Figures III-4,  III-?,  111-10,  111-13,
and 111-16.   In general the  sampling plan  for each mill included
the following locations:

    1.  influent  to  primary  clarifiers  or  treatment  system,
    2.  effluent discharged to receiving stream, and
    3.  dewatered sludge (combined or separate).

    All five of the mills have activated sludge treatment.   Hence,
both primary  and  secondary  sludges  were designated  as  sampling
locations.  Discrete  sampling  of  these  sludges   was  physically
possible at  Mills A, B, and D,,   Mill  B did  not  have a  combined
dewatered sludge  but did  add polymer to the  secondary sludge to
aid dewatering.  The sludge was sampled  prior  to and after polymer
addition.  The sample without polymer was analyzed.

    A number  of  other special  conditions  were   identified  and
incorporated  into the sampling plan.   The  acid  sewer from  the
bleach plants  at  Mills B  and  E bypassed  primary clarification.
The influent to wastewater  treatment  was defined as the sum of the
acid sewer plus the  general  mill sewer.   At  Mill B  a composite

-------
                              -Ill-
sample was generated by  combining  both streams based upon flows.
At Mill  C,  a 2  MGD  portion of  the final  effluent  was recycled
back into the mill  as process  water.   This  particular  flow was
sampled  in  the   same  time   frame  as  the  nill  process  sewers.

    Mill D chlorinated a portion of the secondary sludge recycled
to the  primary  clarifier.   This  sludge  was  sampled  before and
after chlorination.  Mill E  treated the  wastewater  from a nearby
nonintegrated paper mill.   This 2.5 MGD  flow was  also sampled.
Landfill leachates were  sampled from  four  mills  and included in
the mass  balance  for   those  flows  that  were  returned to the
wastewater treatment.

    During and immediately preceeding  the  sampling program, Mill A
was experiencing  upset  conditions  in  the  wastewater  treatment
system which resulted  in  significantly higher effluent suspended
solids discharges.

    The major results of  these  analyses are  noted in  the following
tables.  They are grouped according  to sample type.  The concen-
trations (ppt,  pg/gm)  presented  represent the average of all
analyses (laboratory  duplicates and/or   field  duplicates).   The
mass numbers  (Ibs/day, kg/day)  are  based  upon  the  sewer   flows
and/or sludge tonnages noted in Attachment  F.

1.  Influents to Wastewater Treatment

    The  2378-TCDD and 2378-TCDF results for influents to wastewater
treatment are shown  in Table VII-18.   The data are presented for
actual treatment system influents as monitored during  the sampling
surveys  and as a summary of mass loadings from individual wastewater
sources  at the mills.   Note that in two cases the influent analysis
resulted in  nondetectable  2378-TCDD concentrations  at  low   (ppq)
detection limits.  However,  when  individual  flows  that  make up
this flow were  analyzed, detectable  concentrations  were  found.
It is hypothesized that  dilution  in the  combined  influent   sewer
sample was responsible for  reducing  the  2378-TCDD concentrations
to levels either at or below the established detection limits for
this matrix.  In  further use  of these  values for  mass balance
calculations, the  influent  sample  analysis was  used unless this
analysis resulted  in  a   nondetectable concentration.   In  this
case, the influent mass loading to the wastewater treatment  plant
(WWTP)  was  assumed  equal  to  the  sum  of  the  loading  found  in
tributary process  sewers.   Detection  limits  were  not used  or
assumed  to be equal  to  the  WWTP influent  sample  concentration.
Nondetected  (ND)  concentrations were  treated  as  0.0 ppt  in the
mass balance calculations.

-------
                                       -112-
                                    TABLE VI1-18

                               SUMMARY OF RESULTS FOR
                          INFLUENT TO W'ASTEWATER TREATMENT
                             2378-TCDD
                                            2378-TCDF
Mill A
                  Concentration
                  (ppt or pg/gm)
Influent to WWTP1   0.14
Sum of Sources
Mill B

Influent to WWTP2
Sum of Sources

Mill C

Influent to WWTP
Sum of Sources

Mill D

Influent to WWTP
Sum of Sources

Mill E

Influent to WWTP3
Sum of Sources
ND(0.006)
ND(0.003)
0.028
               Mass Loading
              Ibs/day (kg/day)
              2.3(1.0)xl0-5
              2.8(1.3)xl0-5
              5.3(2.4)xl0-6
              7.2(3.3)xl0-7
4.4(2.0)xl0-6
1.0(Q.47)xl0-5
              2,l(0.95)xl0-4
              I.l(0.52)xl0-4
                   Concentration    Mass Loading
                   (ppt or pg/gm)  Ibs/day(kg/day)
                     1.9
                     0.11
                     0.036
0.063
              3.2(1.5)xl0~4
              4.9(2.2)xl0-4
              3.4(1.5)xl0-5
              2.9(1.3)xl0-5
              9.5(4.3)xl0~6
              3.0(1.4)xl0-5
1.0(0.45)X10-5
2.1(0.97)xl0-5
                                  10.3(4.7)xl0~4
                                   4.8(2.2)xl0~4
NOTES;

(1) Mass loading from influent to WWTP at primary clarifier (DE020921).
    Negligible mass loading from landfill leachate (DE020821)  discharged
    to UNOX system not included.

(2) Synthetic flow weighted sample created from process sewer and acid sewer.

(3) Mass loading includes combined acid sewer  (RG1-86388) which bypasses
    primary treatment and primary treatment influent (RG1-86386/02).

-------
                              -113-
2.   Wastewater Treatment Sludges

    The combined dewatered sludge, primary  sludge,  and secondary
sludge concentrations  and  mass loadings  for  both  2378-TCDD and
2378-TCDF are  shown  in Table  VII-19.   In  all  cases  where  both
primary and secondary sludges were analyzed,  the secondary sludges,
comprised principally of biological solids,  contained much higher
concentrations of 2378-TCDD  and 2378-TCDF  than  primary sludges.
The secondary  sludges,  which  are  lower  in volume  than  primary
sludges, also  contained  the   greater  mass  of  2378-TCDD  and
2378-TCDF.

3.   Treated Process Wastewater Effluents

    The final  treated  effluent concentrations and  mass loadings
for both  2378-TCDD  and 2378-TCDF are presented  in  Table  VII-20.
With few exceptions, the effluent mass loadings are less than the
estimates of  untreated wastewater  loadings  presented in  Table
VII-18.  There  is  no   evidence  to  suggest  that   2378-TCDD  and
2378-TCDF are  destroyed  in   the  wastewater  treatment  systems.
Rather, it appears that any  removal  across  the treatment  systems
is simply  mass  transfer   to   the  wastewater  treatment  sludges
(Table VII-19).  Estimates of  wastewater treatment system removals
(transfer to  sludges)  for 2378-TCDD and  2378-TCDF were  made by
comparing the  treated  effluent  mass  loadings  with  the greater of
the influent mass loadings determined from monitoring  at a central
wastewater collection  point  prior  to treatment, or  the influent
mass loadings  determined   from summing  the  mass   loadings  from
individual bleach plant streams and  other  soures  such as  paper
machine wastewaters (see Table VII-18).  The results are presented
in Table VII-20.   As noted above, 2378-TCDD and 2378-TCDF treatment
system removals constitute mass transfer  from the  wastewaters to
the sludges  rather   than   destruction   or   degradation  to  other
compounds.

    These data  show variable  results  for  the  five  mills.   At
Mill A,  where  effluent  suspended   solids  during  the  sampling
survey were higher than normal, about 15%  of  the  detected  2378-
TCDD and  2378-TCDF  were removed  or  transferred to  the sludges.
The data for Mill B show about  13% removal of  the detected 2378-TCDD
and about a 10% increase in 2378-TCDF across the treatment system.
At Mills C and D,  where untreated wastewater loadings  of 2378-TCDD
and 2378-TCDF  were  relatively low and  effluent  suspended solids
were relatively low,  nearly all of the detected influent 2378-TCDD
and 2378-TCDF were removed across the treatment systems.  Finally
at Mill  E,  with the highest  influent  loadings of  2378-TCDD and
2378-TCDF, treatment  system  removals  were  estimated  at  86%.

-------
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-------
                              -116-
4.   Wastewater Treatment System Mass Balances

    The mass  balances  for the  wastewater treatment  systems are
summarized in Tables  VII-21  and  VII-22  for  2378-TCDD  and 2378-
TCDF, respectively.  The mass balances were based upon the influent
to  the wastewater treatment system, the combined dewatered sludge
(primary plus secondary for Mill B) , and the final treated effluent.
                           TABLE VII-21

   SUMMARY OF WASTEWATER  TREATMENT MASS  BALANCES  FOR 2378-TCDD

                               2378-TCDD Mass
       Mill A1
       Mill B1
       Mill Cl
       Mill D
       Mill E
Input
(Ibs/day)
2.8 xl0-5
5.3 xl0~6
0.72x10-6
4.4 x!0-6
2.1 x!0-4
Exports
(Ibs/day)
3.0xl0~5
9.0xl0-6
1.4xl0-6
2.2xl0-6
6.2xl0-5
% Exports
Accounted for
by Inputs
95%
59%
51%
200%
340%
       NOTES
(D
Influent based upon sum of individual
process sewer mass loadings to wastewater
treatment.
                           TABLE VII-22

   SUMMARY OF  WASTEWATER  TREATMENT  MASS  BALANCES  FOR 2378-TCDF

                               2378-TCDF Mass
       Mill A1
       Mill Bl
       Mill Cl
       Mill D
       Mill E
Input
(Ibs/day)
4.9 xl0-4
3.4 x!0-5
3.1 x!0-5
1.0 x!0~5
1.0 xl0~3
Exports
(Ibs/day)
5.3 xl0~4
7.2 x!0-5
1.9 xl0~5
4.2 x!0~6
2.8 xl0~4
% Exports
Accounted for
by Inputs
92%
47%
160%
240%
370%

       NOTES:  (1) Influent based upon sun of  individual
                   process sewer mass loadings to wastewater
                   treatment,.

-------
                              -117-
    The significance  of  the mass  balance calculations  shown  in
Tables VI1-21 and  VII-22 should  be reviewed  in the  context  of
both the precision in the 2378-TCDD and 2378-TCDF measurements and
the process sewer  flow rates  and  sludge  tonnage values.  Section
VI of this  report  provides  a detailed discussion  of the quality
assurance/quality control results  for each  of  the  major matrices
included in this study.   For the sludge and final treated effluent
matrices, the  measurement  precision  estimates  were  ±15%  and
±20%, respectively.  The  uncertainty associated with the sludge,
effluent, and influent flow rates could  not be quantified.  The
effluent flow estimates,  however,  are  probably  fairly reliable
(<±10%)  since the  mills  are  required  to monitor  flow for  NPDES
reporting purposes.  The sludge tonnage data, however, are likely
the least reliable and could  easily be  in error by  another ±10%
to 15%.

    Furthermore, two of the wastewater treatment influents (Mills B
and C)  and  two  of  the  treated  effluents  (Mills  C and D)  had
nondetectable (ND)  2378-TCDD  concentrations.   Mill  D  also  had  a
nondetected 2378-TCDF concentration  in the  treated effluent.   In
all of these cases,  the  effluent  ND was  treated as 0 ppt for the
purposes of the  mass balance calculations.  The influent masses
for Mills  B and  C  were  computed  from  the sum of  less dilute
internal process flows that entered the  sewers going to primary
treatment.  These  flows   included  both  bleach  plant  and  paper
machine white water  sources.  The large discrepancy at Mill E may
also have been due to the sample  collection timing sequence.   At
this mill,  the   influent  streams  to  wastewater  treatment  were
sampled over  a  0  to 24-hour  period while  the effluent  sample
collection was lagged by 24  hours  to  account   for  the residence
time in  wastewater  treatment  and  collected   during the  24-  to
48-hour time frame.   During  the initial  24-hour period, however,
significant process  changes occurred relating  to the wood species
being bleached.    The hardwood  bleach line  was  sampled over  a
4-hour period after the 24-hour mill composite sample period for the
balance of  the   bleach  plant  and the  internal process  sewers.
During the  24-hour  composite  sampling period  for  the mill, both
softwood and hardwood pulps  were  bleached on the hardwood bleach
line.  The hardwood  bleach line filtrates were  not sampled during
that period.  Thus,  the  data used  for  mass  balances  from  the
short-term composite  samples  obtained on the   hardwood  line  may
not be  representative of effluent  and   sludge conditions during
the 24-hour mill sampling.

    In summary,  the various possible sources of  error  noted above
could easily account for the generally poor mass balance calcula-
tions observed for all five mills.  Given the  low concentrations

-------
                              -118-
and inherent measurement  difficulties  at these  levels,  the  mass
balance calculations for both 2378-TCDD and 2378-TCDF were judged
reasonable.

    As noted  in  Table  VII-19,  the  final  wastewater  effluent
concentrations of 2378-TCDD ranged from ND in two samples (0.003,
0.007 ppt)  to 0.12 ppt; and  2378-TCDF  ranged from ND (0.007 ppt)
to 2.20 ppt.  Because of  the significance of  this  vector,  these
values were  further  examined  in  the context  of a mass  balance
between the final effluent and the concentrations of both isomers
of dioxin and furan in the secondary sludges.

    It was assumed that the 2373-TCDD and 2378-TCDF associated with
the final treated  effluent comes  from  the  unsettled mixed liquor
suspended solids  (MLSS)  and is partitioned primarily to the  solid
phase.  An  estimate   of  the  final  effluent concentration  can,
therefore, be calculated from a knowledge of the effluent suspended
solids and the  secondary  sludge concentrations.  The  results  of
these calculations are  summarized  in  Tables VTI-23  and  VII-24.
Suspended solids levels in the  final effluents  ranged from  14 to
104 ppm (mg/1)  and represented nominal  wastewater treatment  plant
performance at each of the five mills, with the  exception of Mill A
which had higher  than  normal suspended  solids  discharges during
the sampling survey.

    It is  interesting  to  note  that   the  calculated  effluent
2378-TCDD and 2378-TCDF concentrations were lower  than  the measured
concentrations in seven cases but  of similar order  of magnitude.
In three other  cases,  nondetectable concentrations of both  com-
pounds were  observed  and  the  calculated values were  lower  than
the reported  detection  limits  and  also  of  similar  order  of
magnitude.  Within the  limits  of  the  analytical capability  for
these measurements (both GC/MS  and  suspended solids), these  cal-
culations suggest that the  unsettled mixed liquor suspended solids
(MLSS) could be  the  major source  of 2378-TCDD and  2378-TCDF  in
the final treated  effluents.   Furthermore,  since the calculated
concentrations were always lower  than  the  corresponding  measured
values, the liquid phase  must  also contribute  some mass  to  this
export vector.  This observation was judged reasonable based upon
the fact that random experimental  errors in both suspended solids
and 2378-TCDD and  2378-TCDF  measurements would  likely produce a
less biased result with  some calculated  2378-TCDD  and 2378-TCDF
concentrations higher than the measured values.

-------
                              -119-
                           TABLE VII-23

           APPROXIMATION OF TREATED EFFLUENT 2378-TCDD
         CONCENTRATIONS USING SECONDARY SLUDGE ASSUMPTION
   Mill A
   Mill B
   Mill C
   Mill D
   Mill E
           Effluent
          Suspended
            Solids
          	(ppm)

             104
              40
              26
              14
              89
                          Secondary
                            Sludge
                          2378-TCDD
                            (PPt)
                710
                 90
                 11
                 36
                500
             Calculated
              Effluent
              2378-TCDD
             	(PPt)

               0.074
               0.004
               0.0003
               0.0005
               0.045
               Measured
               Effluent
              2378-TCDD
                (PPt)	

              0.12
              0.015
              ND(0.003)
              ND(0.007)
              0.088
Mill
Mill
Mill
Mill
Mill
                           TABLE VII-24

           APPROXIMATION OF TREATED EFFLUENT 2378-TCDF
         CONCENTRATIONS USING SECONDARY SLUDGE ASSUMPTION
        B
        C
        D
        E
 Effluent
Suspended
  Solids
  (ppm)

   104
    40
    26
    14
    89
Secondary
  Sludge
2378-TCDF
  (PPt)	

  10,900
     810
      75
      78
   2,100
Calculated
 Effluent
 2378-TCDF
   (PPt)

  1.1
  0.032
  0.002
  0.0011
  0.188
                                                      Measured
                                                      Effluent
                                                     2378-TCDF
                                                        (ppt)	
2.2
0.12
0.011
ND(0.007)
0.42
5.  Distribution of 2378-TCDD and 2378-TCDF in Wastewater
    Treatment System Effluents and Sludges

    A final  observation  on  the  distribution  of  2378-TCDD and
2378-TCDF in  the  wastewater  treatment plant  export  vectors  is
illustrated in  Table  VII-25.   These  data  indicate   that   both
compounds are distributed  differently in  the  sludge and effluent
vectors from mill to mill but consistently within each  mill.  The
reasons for  these  differences  are   not   understood.   Activated
sludge wastewater  treatment  with  fairly  conventional residence
times, aeration capacity, and  secondary sludge recycles  is provided
at each mill.

-------
                              -120-


                           TABLE VII-25

             DISTRIBUTION OF 2378-TCDD and 2378-TCDF
              IN WASTEWATER TREATMENT EXPORT VECTORS


                     2378-TCDD                 2378-TCDF
              % Effluent    % Sludge    % Effluent    % Sludge

    Mill A       80%           20%         79%           21%
    Mill B       51%           49%         52%           48%
    Mill C       ~0%         -100%         14%           86%
    Mill D       -0%         -100%         -0%         -100%
    Mill E       48%           52%         51%           49%
F.  Pulp and Paper Mill Exports

    For purposes  of  this study,  export  vectors were  defined  as
the final  treated effluent,  clewatered  sludges,   and  the  final
bleached pulp.  At  some mills landfill  leachates  are discharged
separately from the  treated  process  wastewater effluents.   The
mass discharges from  leachates  were not  significant  compared  to
those from other  vectors and thus were  not considered  in  this
analysis.  In one  pathway  or another, these  materials enter the
environment.   Summaries of  the results  for each mill are presented
in Tables VII-26 and VII-27  for  2378-TCDD and 2378-TCDF,  respec-
tively.  The  most  obvious  feature of  the data  shown in  these
tables is the variable distribution of 2378-TCDD and 2378-TCDF in
the three export vectors across  the mills.   The distributions  of
2378-TCDD and 2378-TCDF were consistent within each mill.

    The distributions  in  the  treated  effluents were  apparently
related to the  final  effluent suspended  solids  content  as noted
in Table VII-28.  The data in  this table suggest  a casual relation-
ship between  the  effluent suspended solids  concentration  and the
relative distribution of 2378-TCDD and  2378-TCDF in the wastewater
treatment plant  export  vectors   (treated  effluent,  wastewater
sludge).  Generally, higher suspended solids contents resulted in
a greater fraction of the 2378--TCDD and 2378-TCDF associated with
the effluent rather than the sludge.

-------
   -121-
TABLE VII-26
MASS AND

Mill A
Mill B
Mill C
Mill D
Mill E
MASS AND

Mill A
Mill B
Mill C
Mill D
Mill E
DISTRIBUTION
Dewa tared
Sludges
% of
Total
16
17
-100
-70
28
DISTRIBUTION
Dewatered
Sludges
% of
Total
17
20
35
-69
27
OF 2378-TCDD
Final
Effluent
% of
Total
65
17
-0
-0
26
TABLE VII
OF 2378-TCDF
Final
Effluent
% of
Total
64
23
6
-0
28
IN TOTAL MILL
Bleached
Pulp
% of
Total
19
66
-0
-30
46
-27
IN TOTAL MILL
Bleached
Pulp
% of
Total
19
57
59
-31
45
EXPORT VECTORS

Total Mass in
Export Vectors
Ibs/day (kg/day)
3.7 (1.7)xl0-5
2.6 (1.2) xl0~5
1.4 (0.64) x!0~6
3.2(1.5)xl0~6
I.l(0.51)xl0-4
EXPORT VECTORS

Total Mass in
Export Vectors
Ibs/day (kg/day)
6.6 (3.0) xl0~4
1.7 (0.75) xl0~4
4.7 (2.1) xl0-5
6.1(2.8) x!0~6
5.1(2.3)xl0-4

-------
                              -122-


                           TABLE VI1-28

 FINAL TREATED EFFLUENT TCDD/TCDF  DISTRIBUTION  IN EXPORT VECTORS
           VS. EFFLUENT SUSPENDED SOLIDS CONCENTRATION


              Effluent
             Suspended       % of Total          % of Total
              Solids      TCDD in Effluent    TCDF in Effluent
               (ppm)        Export Vector       Export Vector

   Mill D        15              ~0                  ~0

   Mill C        36              -0                   6

   Mill B        40              17                  23

   Mill E        89              26                  28

   Mill A       104              65                  64
    The total  mass  of  2378-TCDD  and  2378-TCDF  in  the  export
vectors (Tables VII-26 and VII-27) can  be accounted for by those
process sewers related to the bleach plant.  The summaries shown in
Tables VII-29  and  VII-30  illustrate  the  results  of  these  mass
balances.  Note that at Mill C, 2378-TCDD was not detected in any
bleach plant  samples,  although  it  may  be present  at less  than
detectable levels.   The  positive  findings   in  paper  machine
wastewaters at this mill may be due to papermaking with purchased
bleached softwood pulp.

-------
                              -123-
                           TABLE VII-29

                  FRACTION OF  2378-TCDD  FOUND  IN
             TOTAL MILL EXPORT VECTORS ATTRIBUTED  TO
                       BLEACH  PLANT  SOURCES
              2378-TCDD
          from Bleach Plant
           Ibs/day(kg/day)

Mill A    3.5(1.6)X10-5

Mill B    2.3(1.0)x!0-5

Mill C    7.3(3.3)x!0-7(l)

Mill D    1.1(0.50)x!0-5

Mill E    1.7(0.77)xl0~4 (3)
                           2378-TCDD
                       in Export Vectors
                        Ibs/day(kg/day)

                       3.7(1.7)xl0~5

                       2.6(1.2)xl0-5

                       1.4(0.64)xl0-6

                       3.2(1.5)xl0-6 (2)

                       1.2(0.51)xl0~4
 % Accounted
for by Bleach
Plant Sources

     94%

     86%

      0%

    360%

    140%
NOTES;  (1) 2378-TCDD was not   found   in  bleached  pulp or  bleach
            plant wastewater  streams.   This mass  was  found  in
            paper machine wastewaters and may be associated  with
            purchased bleached softwood pulp used for paper making.

        (2) 2378-TCDD was found  in  the  wastewater  treatment plant
            influent and sludge but not in  the effluent.   Hence,
            the effluent ND(0.007)  ppt  was  assumed  to  be 0.0 ppt.
            2378-TCDD was not  found  in  one bleach line  bleached
            pulp ND(1.2).   This  export vector  source  was  also
            assumed to be 0.0 ppt.
(3)  Sampling was
    and softwood
    were assumed
                          not done  at the  same  time on  hardwood
                         bleach  lines but the bleach line  masses
                         to  be additive  to  reflect mix  of total
            mill production during  the  sampling  survey,

-------
                              -124-
                           TABLE VII-30

                  FRACTION OF 2378-TCDF FOUND IN
             TOTAL MILL EXPORT VECTORS ATTRIBUTED TO
                       BLEACH PLANT SOURCES
Mill A

Mill B

Mill C

Mill D

Mill E

NOTES:
      2378-TCDF
  from Bleach  Plant
   Ibs/day(kg/day)

  6.1(2.8)x!0-4

  1.2(0.54)xl0~4

  3.2(1.4)xl0~5

  2.2(1.0)xl0-5

  7.3(3.3)x!0-4 (1)
    2378-TCDF
in Export Vectors
 Ibs/day(kg/day)

 6.6(3.0)x!0-4

 1.7(0.75)x!0™4

 4.7(2.1)x!0-5

 6.1(2.7)X10-6

 5.6(2.5)x!0-4
 % Accounted
for by Bleach
Plant Sources

     92%

     70%

     68%

    360%

    130%
(1)  Sampling was  _n_ot  done at  the same time  on  hardwood
    and  softwood  bleach lines but  the  bleach  line masses
    were assumed   to  be;  additive  to  reflect  total  mill
    production  during  the sampling period.
    The footnotes to the tables  qualify  a  number of the sampling
and calculation assumptions made in  computing the mass balances.
Given the various possible sources of  error discussed earlier  in
this section, it is reasonable to conclude that the 2378-TCDD and
2378-TCDF formed are attributable to bleach plant sources  in each
mill.  The  small  amounts of  2378-TCDF found  in  unbleached pulp
from two mills were not significant.

    As noted earlier in  Section  VII.C.,  the mass formation rates
for both 2378-TCDD and  2378-TCDF  in the bleach plants were  related
in some manner  to  the mass amounts of  equivalent chlorine  (C12EQOX)
applied to  the  brownstock  pulp.    Higher  chlorine  application
rates in the bleach  plant  generally resulted in greater  amounts
of 2378-TCDD  and  2378-TCDF   formed.   Similar correlations  are
presented for  the  total  mill  export  vectors  (pulp,  sludge, and
treated effluent) in Figures  VII-9 and VII-10 for 2378-TCDD and
2378-TCDF, respectively.   The  /-axis represents  the mass of each
isomer found in all  three export  vectors divided by  the brownstock
pulp production.  The  x-axis  represents  the total mass amount  of
chlorine and chlorine derivatives expressed  as equivalent chlorine
(C12EQOX)  used  in all  stages  of bleaching.   The  computations  of

-------
   - 125-













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                              -127-
2378-TCDD and 2378-TCDF formed and chemical use were based upon a
production weighted basis  for mills with  multiple  bleach lines.
Since 2378-TCDD and 2378-TCDF are not  destroyed or  eliminated in
the wastewater  treatment  systems,  these   two  graphs  basically
repeat the correlations  shown in  Figures  VII-7 and VII-8.  This
observation is  consistent  with  the  fact  that  the  formation  of
2378-TCDD and 2378-TCDF is principally attributed to bleach plant
sources.
G.  Chlorinated Phenolics
             of  the  five  mills,  samples  were  taken  at  selected
            bleach plant,  and  WWTP locations  to  be  analyzed for
            phenols,  guaiacols,  and  vanillins.   A  list  of the
            phenolics is  found  in Table VII-31.  Analytical data
for these samples are presented  in Attachment  G along  with several
data summary sheets tabulated by  sample type.
    At each
background,
chlorinated
chlor inated
                           TABLE VII-31
                  CHLORINATED PHENOLIC ANALYTES
Chlorophenols
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
1,4/2,5-Dichlorophenol
3,4-Dichlorophenol
2,5-Dichlorophenol
2,3-Dichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
                        Chloroguaiacols

                        4,5-Dichloroguaiacol
                        3,4,5-Trichloroguaiacol
                        4,5,6-Trichloroguaiacol
                        Tetrachloroguaiacol
C h 1 o r o v a n i 11 i n s

5-Chlorovan ill in
6-Chlorovanil1 in
5,6-Dichlorovanillin
    Table VII-32  presents  chlorinated  phenolics  mass  loading
summaries based  upon  the  analytical  results  for  treated intake
process waters,  WWTP  influents,  and WWTP effluents  for  the  five
mills.  Table VII-33  presents  a  summary of chlorinated phenolics
mass loadings in the bleach plant wastewaters sampled in the five-
mill study.  Tables VII-34 and  VII-35 present wastewater treatment
system and bleach plant mass loadings normalized to production on
the basis of air-dried brownstock pulp.
    The data indicate  that  none
detected in any of the five mill
detection levels  estimated  to
                                 of the chlorinated  phenols  were
                                 treated intake process waters at
                                be  in  the  1  to  3  ppb  range.

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-------
                                    -129-


                                    TABLE VII-33


                  CHLORINATED  PHENOLICS  IN BLEACH  PLANT WASTEWATERS
                          Mass Loadings  - Ibs/day  (kg/day)
              Number: of
               Sources

Sum of Chlorophenols
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
                Range
  ND-0.53(ND-0.24)
0.16-2.3 (0.073-1.3)
  ND-0.06(ND-0.027)
  ND
                           Median
 0.09(0.41)
 0.63(0.29)
 0.02(0.009)
   ND
                    Mean
 0.17(0.077)
 0.92(0.42)
 0.03(0.014)
   ND
Sum of Chloroguaiacols
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
0.09-2.1 ((3.041-0.95)
2.1-26   (0.95-12)
0.40-0.67(0.18-0.30)
  ND-0.18(ND-0.081)
 0.25 (0.11)
16    (7.3)
 0.50 (0.23)
 0.025(0.011)
 0.69(0.31)
13   (5.9)
 0.52(0.24)
 0.06(0.027)
Sum of Chlorovanillins
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
  ND-1.9 (ND-0.86)
0.57-13  (0.26-5.9)
0.20-0.43(0.091-0.19)
  ND-0.01(ND-0.005)
 0.18(0.082)
 5.2 (2.4)
 0.34(0.15)
 0.39 (0.18)
 5.5  (2.5)
 0.33 (0.15)
 0.003(0.0014)
Sum of All Analytes
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
0.13-4.0 (0.059-1.8)
3.1-41   (1.4-19)
0.61-1.1 (0.28-0.50)
  ND-0.18(ND-0.082)
 9.61(0.28)
22   (10)
 0.85(0.39)
 0.03(0.014)
 1.2 (0.54)
20   (9.1)
 0.87(0.39)
 0.06(0.027)

-------
                          -•130-
                       TABLE VII-34

    WWTP MASS LOADINGS - SUM OF CHLORINATED PHENOLICS
   [10-3 Ibs/ton (kg/kkg)  of brownstock pulp bleached]
         Mill
           Influent
           Effluent
           A
           B
           C
           D
           E
              9.4
             15
              9.1
             33
             45
              6.4
              5.6
              0.17
             13
              1.9
         Range
         Mean
         Median
           9.1-45
           22(11)
           15(7.5)
           0.17-6.4
           5.4(2.7)
           5.6(1.3)
 NOTE:  Sum of chlorinated phenolics includes chlorinated
        phenols, chlorinated guaiacols, and chlorinated
        vanillins.
                       TABLE VII-35
BLEACH PLANT MASS LOADINGS - SUM OF CHLORINATED PHENOLICS
              C-STAGE AND E-STAGE FILTRATES
   [10-3 Ibs/ton (kg/kkg) of brownstock pulp bleached]
 Mill

 A-HW
 A-SW
 B-SW
 C-HW
 D-SW-A
 D-SW-B
 E-SW
 E-HW(3)

 Range
 Mean
 Median

 NOTE:   (1)
         (2)

         (3)
   C-Stage

  0.51
  0.81
  3.6
  4.0
  2.1
  4.6
  1.8
  0.55

  0.51-4.6
  2.2 (1.1)
  1.9 (0.95)
E-Stage

 8.8
29
25
34
49(2)
49(2)
46
20
8.8-49
33  (17)
32  (16)
    Sum of
C and E Stages

     9.3
    30
    29
    38
    51
    54
    48
    21

    9.3-54
    35  (17)
    34  (17)
Sum of chlorinated phenolics includes chlorinated
phenols, chlorinated guaiacols, and chlorinated
vanillins.
Common E-stage mass loading allocated equally  to
A and B lines.
The Mill E hardwood bleach line filtrate  samples
were obtained when an undetermined amount of
softwood pulp was being processed on the  line.

-------
                              -131-
    The wastewater treatment plant influent data for chlorophenols
show three chlorophenols were detected at four of the five mills.
with 2,4-dichlorophenol  (and  2,4/2,5-dichlorophenol  coelution)
making up  99%  of the  combined  five-mill  influent  chlorophenols
mass loadings.  Pentachlorophenol  was  detected at one  mill.   Of
the three chlorovanillins analyzed, 6-chlorovani11 in was predomi-
nant and detected at  each  mill,  accounting for about 63%  of  the
combined five-mill chlorovanillin influent mass loading.  Chloro-
guaiacols were  found  at  each  mill  in  more  evenly distributed
patterns than  the  chlorophenols  or chlorovanillins.   From Table
VII-34, the mean of all chlorinated phenolic influent mass loadings
was 22  x  10~3  Ibs/ton  of  air-dried  brownstock pulp  bleached.

    Chlorinated phenolic effluent data presented  in  Table VII-32
show a  similar  distribution between  the various  analytes.   The
overall reduction of the sum of  all chlorinated phenolics across
the wastewater  treatment facilities at the five  mills  was about
82%.  From  Table  VII-34  the mean  of  all chlorinated  phenolic
effluent mass  loadings  was  5.4   x 10~3  Ibs/ton   of  air-dried
brownstock pulp bleached.

    With respect to internal bleach plant  sources of chlorinated
phenolic wastewater streams, the data summarized in Tables VII-33,
VI1-35, and G-10 in Attachment G show that the E-stages accounted
for most of  the mass  loadings  of  chlorinated phenolics  in  the
bleachery samples analyzed  in the  five-mill study.  These findings
are similar to  those  for 2378-TCDD and  2378-TCDF.   (see  Section
VII.C.3).  The  distribution  of  chlorophenols  in  the  E-stage
wastewater streams generally  was  similar  to  that  for the  WWTP
influents.  2-Chlorophenol  was detected in the  E-stage wastewaters
at one mill (Mill E,  A side) in  a trace amount.

    With the limited data correlations were not attempted between
chlorinated phenolics and levels of 2378-TCDD and 2378-TCDF present
in wastewater  treatment system  influents or effluents.   Since
chlorinated phenolics were  only analyzed  on  the  water matrix, an
evaluation of chlorinated phenolics in bleach plant or total mill
exports could  not be  made.   With the  limited  and  incomplete
wastewater data, mass  balance calculations between internal bleach
plant filtrates and  wastewater   treatment  system  influents  were
not attempted.

H.  Total Suspended Solids  and Biochemical Oxygen Demand

    Selected samples were analyzed for total suspended solids (TSS)
and biochemical oxygen  demand (8005).  The TSS and  BOD5 analyses
were conducted  primarily to  determine  whether  there  were  any
abnormal wastewater treatment system operations during the sampling

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                              -132-
events.  Analytical  results  for TSS and 8005  for  the five mills
are presented in Attachment G.   Tables VII-36 and VII-37 summarize
TSS and BOD data for the wastewater treatment plant influents and
effluents.

    The effluent mass  loading data  from  the  five-mill study were
reviewed with respect  to typical   loadings  and  percent removals
presented in  Section  III   (Tables  III-3,  6,   9,   12,  and  15).
Effluent mass  loadings  for  TSS  generally  were  within  typical
ranges with the exception of Mill A.  As noted in  Section VII.E. ,
during and  immediately  preceding  the sampling  period, Mill  A was
experiencing upset conditions in  the wastewater  treatment system
which resulted in higher than normal mass  loadings in the effluent.
Monthly sewer and WWTP operating reports for Mill  A were obtained
for the  sampling  period  and   reviewed.   According  to  Mill   A
personnel, failure  of   the  white  liquor clarifier  and disposal
of lime mud into the primary clarifier resulted in an overload of
solids in  the  wastewater  treatment  system which  took  months to
recover a  suitable  balance  in   the  system.   Based   upon  Mill   A
sewer operating  reports, fiber  losses  during the  sampling period
were about  30%  higher  than the  yearly average prior to the date
of sampling.

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                              -133-
                           TABLE VII-36
WASTEWATER TREATMENT PLANT
TOTAL SUSPENDED SOLIDS SUMMARY
Mill
A
B
C
D
E


Cone .
mg/L
654
—
540
875
680

Influent
Mass Loading
Ibs/day (kg/day)
109,700 (49f800)
52,8001(23,900)
141,900 (64,400)
137,600 (62,400)
210,000 (95,200)

Cone
mg/L
104
40
36
15
89
TABLE VII
Effluent
Mass Loading
Ibs/day (kg/day)
20,100 (9100)
12,800 (5800)
8,900 (4000)
2,200 (1000)
30,500 (13,800)
-37
% Removal
82%
76%
94%
98%
86%

WASTEWATER TREATMENT PLANT
BOD5 SUMMARY
Mill
A
B
C
D
E

Cone.
mg/L
175
--
301
232
340
Influent
Mass Loading Cone.
Ibs/day (kg/day) mg/L
29,300 (13,300) 29
48,100! (21,800) 5
79,100 (35,900) 9
36,500 (16,600) 13
105,000 (47,600) 16
Effluent
Mass Loading
Ibs/day (kg/day)
5,600 (2500)
1,500 (680)
2,200 (1000)
2,000 (910)
5,500 (2500)
% Removal
81%
97%
97%
95%
95%
NOTES:  (1)  Mill B influent mass loadings calculated
            from data from two process sewers.

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                                 -134-


VIII.  FINDINGS AND CONCLUSIONS

   A.  Data Quality and Data Limitations

   1.  The analytical protocol foc 2378-TCDD and 2378-TCDF developed
   for this study  was  found to be  satisfactory for isomer-specific
   determinations of 2378-TCDD  and  2378-TCDF  in selected  pulp  and
   paper mill   sample matrices.   Intra-laboratory method  validation
   experiments for  pulp,  sludge,  and  wastewater  effluent  samples
   indicate the performance of the analytical method with respect to
   precision and spike  recovery is demonstrably uniform.  The method
   performance does  not appear  to  be  sensitive   to  any  specific
   matrix or  chemical  effects which  might  be  associated  with  the
   manufacturing processes  at a given mill.  Limited inter-laboratory
   comparisons incorporating  different  sample  preparation,  cali-
   bration standards, and analytical methods confirmed the presence of
   2378-TCDD and 2378-TCDF in selected samples.   However, a consistent
   bias was observed for quantitation of both  2378-TCDD and 2378-TCDF.

   2.  With few  exceptions, the  data  quality  assurance  objectives
   established for  this study  for 2378-TCDD   and  2378-TCDF  were
   achieved.

      (a)  Laboratory precision expressed  as  relative percent differ-
           ence between duplicate analyses for thirty-five 2378-TCDD
           determinations was 15 percent mean (range 1-138 percent);
           and for thirty-three 2378-TCDF determinations, 16 percent
           mean (range  0-62 percent).

      (b)  Field  precision  for  eight  2378-TCDD determinations  was
           14  percent mean  (range 4-19  percent); and  for  nine 2378-
           TCDF determinations, 22 percent mean  (range 0-99 percent).

      (c)  For  thirty-five  2378-TCDD  determinations,   accuracy  ex-
           pressed as percent  spike recovery  was   103  percent mean
           (range 66-168 percent);   and  for thirty-five  2378-TCDF
           determinations,  102 percent  mean  (range  58-153 percent).

      (d)  Including results from intra-laboratory method validation
           experiments, 97   percent  of  the analyses met the quality
           assurance objectives  for laboratory  precision  and accu-
           racy.  Ninty-five  percent  of   133  determinations  for
           2378-TCDD and for  2378-TCDF resulted in  analytical data
           suitable for project objectives.

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                              -135-
   (e)   Target  analytical  detection  levels  of  1  ppt  for  solid
        samples were achieved for all but one sample for 2378-TCDD
        and all but one sample for 2378-TCDF (different samples).
        Target analytical detection levels of 0.01 ppt for liquid
        samples were achieved for all but three samples for 2378-
        TCDD and  all  but  two samples  for  2378-TCDF (different
        samples) .

3.  Mass  flow calculations  for  2378-TCDD and  2378-TCDF  combine
analytical results with mass  flow rates of solid materials (pulps,
sludges) and  liquids  (waters, wastewaters).  The mass flow rates
for pulps and  final treated   wastewater effluents  are considered
to be accurate  within less than  ±10%  while  mass  flow  rates  for
sludges, within less  than  ±10%  to  15%.   Mass  flow rates  for
internal plant  wastewaters were  generally based  upon best engi-
neering estimates   and  are  considered accurate  to  less  than  ±20%
to 25%.    The  reliability  of  reported  bleach  plant  chemical
application rates   varied  considerably from mill  to  mill,  and in
two cases, were best engineering estimates.  The calculations and
analyses presented  in  this  report should  be  viewed accordingly.

B.  PCDDs and PCDFs Found in Pulp and Paper Mill Matrices

1.  Analyses  of samples obtained at  a number  of  bleached  kraft
pulp and paper mills for polychlorinated dibenzo-p-dioxins (PCDDs)
and polychlorinated  dibenzofurans  (PCDFs)   uniformly show  that
2,3,7,3-tetrachlorodibenzo-p-dioxin  (2378-TCDD) and 2,3,7,8-tetra-
chlorodibenzofuran  (2378-TCDF) are  the  principal PCDDs  and PCDFs
found.   This is particularly evident when the data are considered
in light  of  USEPA's  2378-TCDD  toxic  equivalents approach  for
dealing with mixtures of PCDDs and PCDFs.

2.  Data  for  the  five mills  included in this study show there is
a characteristic  2378-TCDF/2378-TCDD  ratio associated with indi-
vidual  bleach lines and individual mills,  ranging from about 2 to
about 18.  This observation suggests that once  2378-TCDD and 2378-
TCDF are formed,  they are not altered in further processing or in
wastewater treatment.    Factors accounting  for  the differences in
2378-TCDF/ 2378-TCDD ratios across  bleach  lines and  across mills
have not been determined, nor  has  the possible process significance
been formulated.

C.  Sources of 2378-TCDD and  2378-TCDF

1.  2378-TCDD  and 2378-TCDF   are  formed  during  the bleaching  of
kraft hardwood  and softwood  pulps  with  chlorine and  chlorine
derivatives at mills included in this study.

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                              -136-
2.  2378-TCDD  was  not detected  in  seven unbleached  kraft pulps
collected at the five mills  at detection levels ranging fronti 0.3
ppt to  1.0  ppt.   2378-TCDF  was  not  detected  in  four  of seven
unbleached pulps at  detection  Levels  less than 0.3 ppt,  but  was
found in  three pulps collected  at  two  mills at  levels  ranging
from 1.1 to  2.3 ppt.  The positive 2378-TCDF findings in unbleached
pulps may be  attributed  to  reuse  of  contaminated  paper machine
white waters for brownstock pulp washing or dilution.

3.  2378-TCDD was found in seven of nine bleached pulps collected
at the five mills  at  concentrations ranging  from 3 to 51 ppt and
2378-TCDF was  found  in eight  of nine  bleached pulps  at  levels
ranging from 8  to  330 ppt.   The median  and  mean  concentrations
are presented below with nondetects counted as zero:

                           2378-TCDD      2378-TCDF

               Median        5 ppt         50 ppt
               Mean         13 ppt         93 ppt:

4.  2378-TCDD  and  2378-TCDF  were found  in most  untreated  bleach
line filtrates  sampled  from  the five  mills.  Wastewaters  from
caustic extraction  stages  (E  and  Eo)   generally  contained  the
highest concentrations and mass  discharges  from the bleach lines
sampled.

5.  The distributions of  2378-TCDD  and  2378-TCDF  in  bleach line
exports (bleached pulp and  bleach plant  wastewaters)   were found
to be highly variable  from  bleach line to bleach line.  However,
2378-TCDD and  2378-TCDF  were  jparti t ioned similarly  to  bleached
pulps and  bleach  plant   wastewaters  within  each  bleach  line.

6.  2378-TCDD  was  found  in paper machine wastewaters  from three
of five mills and 2378-TCDF was found in paper machine wastewaters
from each mill.  The  levels  of  2378-TCDD and  2378-TCDF found in
paper machine  wastewaters  were  significantly less than  found in
the respective  bleach  plant  wastewaters  at  four of  five  mills.
The source of 2378-TCDD and 2378-TCDF in paper machine wastewaters
at these  mills is  believed  to  be the bleaching operations.   At
one mill, 2378-TCDD was not  detected  in  any  bleach plant sources
but was found  in paper  machine  wastewaters.   Purchased bleached
pulp used at that mill may be ci  possible  source.

7.  2378-TCDD  was  found  in one;  of  five  sludge  landfill leachate
or runoff samples at 0.025 ppt,  while  2378-TCDF was found in four
of five samples at  levels ranging from  0.01 to  0.11 ppt.  2378-TCDD
and 2378-TCDF  were not  detected in  coal-fired power  boiler  ash
samples from  two mills at  detection   levels  less  than  1.0 ppt.

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                              -137-
8.  2378-TCDD and other  TCDDs were detected in a  blue dye collected
during preliminary sampling at Mill  A  at  levels  of 3.4 and 53 opt,
respectively.  2378-TCDF  and   other  TCDFs  were not  detected  in
that sample.

D.  Formation of 2378-TCDD and 2378-TCDF

1.  The  rates  of  formation   of  2378-TCDD  and  2378-TCDF  were
normalized on a production basis to Ibs/ton  (kg/kkg)  of air dried
brownstock pulp.   The   rates  of  formation  computed  from bleach
line exports  (bleached  pulps   and  bleach plant wastewaters)  and
from total  mill  exports   (bleached  pulp,  treated  wastewater
effluents, and combined wastewater sludges)  are summarized below:


                    10-8 Ibs/ton  (kg/kkg) of Brownstock Pulp

                  Bleach Line  Exports       Total Mill Exports
                   (eight bleach  lines)          (five mills)

   2378-TCDD

     Range                ND-20(10)         0.14(0.07)-11(5.5)
     Median                 4.1(2.0)                  3.0(1.5)
     Mean                   8.0(4.0)                  4.4(2.2)

   2378-TCDF

     Range         2.6(1.3)-360(180)        1.5(0.75)-130(65)
     Median                12.5(6.3)                   19(9.5)
     Mean                  68  (34)                    41(21)


    The range  computed   from  bleach  plant  exports  exceeds  that
computed from  total  mill exports because  of the  integration  of
results from mills with multiple bleach  lines in the mill export
calculations.  For  three  out  of  five  mills,  the  calculations
using export vectors  resulted in values  less than  computed from
individual bleach  lines.   The extent  to  which  these data  are
representative of long-term operations at the five mills, or are
representative of the bleached kraft industry  as a  whole is not
known.

2.  Although the  data   from this study are  limited,  the  results
suggest casual relationships  between  the formation  of 2378-TCDD
and 2378-TCDF and (1) the degree of bleaching across bleach  lines as
estimated by the chlorine and chlorine equivalents applied to the
unbleached pulp, and (2) the amount of lignin removed in the pulp
across chlorination and caustic extraction stages as estimated by

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                              -138-
the difference in  permanganate  number (K) and  CEK (permanganate
number after caustic extraction).  Attempts  were  made to develop
statistical correlations  with  the  limited  data.   However,  the
results were generally poor.  Data from  several  additional mills
would be necessary to confirm these relationships.

3.  Bleach lines  processing exclusively softwood pulps had higher
rates of formation  of  2378-TCDD and  2378-TCDF  than  bleach lines
processing exclusively hardwood pulps.  However, bleaching condi-
tions on the  softwood  and hardwood bleach lines  were different,
and thus,  it  is  not possible  to  conclude that the  general  wood
species bleached  is the determinant variable  in formation of 2378-
TCDD and 2378-TCDF.

E.  Wastewater Treatment System Findings

1.  2378-TCDD was found in  treated  wastewater effluents from three
of five mills at  levels  ranging  from  0.015 to  0.12 ppt  and 2378-
TCDF was found in  four of five effluents at  levels from 0.011 to
2.2 ppt.  The mass discharges are summarized below:
                       10~5 Ibs/day (kg/day)

              2378-TCDD                     2378-TCDF
         Range
    Median
      ND-3.0(1.4)     0.46(0.21)
          Range
                   ND-42(19)
           Median
                      3.7(1.7)
2.  2378-TCDD and
sludges collected
levels:
2378-TCDF
from each
were  found
of the  five
in wastewater
 mills  at the
treatment
following
Primary Sludges
Secondary Sludges
Combined Sludges
2378-T

17
11
3.
Range
- 24
-710
3-180

ppt
ppt
ppt
CDD
Med
19
89
37

ian
ppt
ppt
ppt
2378-TCDF
Range
32-
75-10,
34-
380
900
760
ppt
ppt
ppt
Med
100
810
330
ian
ppt
ppt
ppt
3.  Mass  balance calculations  around  the wastewater  treatment
systems for three mills showed that about 50% to 80% of the 2378-
TCDD and  401  to 60%  of  the  2378-TCDF found  in  treatment system
exports (treated  effluent,  wastewater  sludge)  can  be  accounted
for by  treatment system  inputs.   For  two  mills  the  treatment

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                              -139-
system input loadings  exceeded  the export loadings  by more than
200%.  The poor mass balances are  attributed to uncertainties in
sludge, influent,  and  effluent  flow  rates,  the  sequencing  of
sampling at certain mills, and,  to some extent, analytical varia-
bility associated with trace level analyses near method detection
1imits.

4.  There  is no  evidence  to  suggest  that  2378-TCDD and 2378-TCDF
are destroyed  in  wastewater  treatment  systems.  Rather, they are
transferred, to varying degrees, to wastewater treatment sludges.
At two mills,  about 10%  to  15% of  the 2378-TCDD and 2378-TCDF
contained  in untreated wastewater  streams  was transferred to the
sludges in the wastewater  treatment systems, while at  the remaining
three mills  more  than 80%  transfer  to   sludges  is  indicated.

5.  The distributions of 2378-TCDD and 2378-TCDF between wastewater
treatment exports (treated effluents and wastewater sludges) were
highly variable from mill  to mill.   However, the partitioning of
2378-TCDD and  2378-TCDF between  treated effluents and wastewater
sludges was consistent within each mill.  Mills with higher total
suspended solids  in  effluents had  higher  levels of 2378-TCDD and
2378-TCDF partitioned  to  the effluent  rather than to the sludge.

F.  Pulp and Paper Mill Exports

1.  The distributions  of  2378-TCDD and 2378-TCDF  among pulp and
paper mill exports  (bleached pulp,  treated effluents, wastewater
sludges)  were  highly  variable   from  mill   to  mill,  but  the
partitioning of  2378-TCDD   and  2378-TCDF  to  the  exports  was
consistent within each mill.

2.  Mass balance  calculations indicate  that  bleach plant sources
accounted for  about  90%  to  140% of  2378-TCDD measured  in mill
exports at  three mills   and more  than  300%  at  another  mill.
2378-TCDD was  not detected  at bleach plant  sources  at one mill.
For 2378-TCDF, bleach plant  sources were found to account for 70%
to 130% of the amount measured in mill exports at four mills, and
more than  300%  in the  last mill.  The  poor  mass  balance results
at some mills  are attributed to  uncertainties in mass flow rates
of wastewater, sludge, and pulp, and,  to  some extent, analytical
variability associated  with  trace  level  analyses  near  method
detection limits.

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                              -140-


G.  Chlorinated Phenolics

1.  For this study,  chlorinated  phenolics  include selected chlori-
nated phenols, chlorinated  guaiacols,  and chlorinated vanillins.
Chlorinated phenolics  were  formed  in  the  bleaching  process  at
each of the  five mills.   These compounds  were not  detected  in
treated intake process  waters  but  were  found  in  bleach  plant
filtrates and wastewater treatment  system  influents and effluents.
Chlorinated phenolics were  distributed  differently  at each mill.

2.  Wastewaters from caustic  extraction stage (E and Eo)  washers
accounted for most of the chlorinated phenolics.  This finding is
similar to  findings for 2378-TCDD  and 2378-TCDF in  bleach line
filtrates.

3.  The  amounts  of  chlorinated  phenolics  found  in  C-stage  and
E-stage filtrates  were  normalized  to  Ibs/ton  (kg/kkg)   of air-
dried brownstock pulp and are sjmmarized below:


        10~3 Ibs/ton (kg/kkg) of Air-Dried Brownstock Pulp

                                      Sum of C-Stage and
         Sum of Chlorinated            E-Stage Filtrates
         	Phenolics	          (eight bleach lines)

               Range                    9.3-54  (4.2-24)
               Mean                         35  (17)
               Median                       34  (17)


4.  With  the  limited data  available,  correlations  between  the
presence of chlorinated phenolics  and  2378-TCDD or  2378-TCDF in
wastewater treatment  system  influents  or  effluents  were  not
attempted.  Because chlorinated phenolics were  analyzed  only for
the water  matrix,  an evaluation  of total  chlorinated phenolics
exports from  bleach plants  (i,,e.,  pulp  and  wastewaters)  could
not be  made.   With  the  limited and  incomplete wastewater data
available, mass  balance  calculations  between  internal  bleach
plant filtrates and wastewater treatment  system  influents were
not attempted.

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                              -141-
                            REFERENCES
1.
2.
3.
4.
United  States  Environmental  Protection Agency  (USEPA),  The
National Dioxin Study,  Tiers, 3, 5f 6, and 1,  EPA 440/4-87-
003, Office of  Water Regulations and  Standards,  Washington,
D.C., February 1987.

United States Environmental Protection  Agency  (USEPA), Interim
Procedures for  Estimating Risks Associated with Exposures to
Mixtures of Chlorinated  Dibenzo-p-Dioxins  and Dibenzofurans
    (CDDs and CDFs) , EPA  625/3-87/012,
    Washington, D.C., October 1986.
                                     Risk  Assessment  Forum,
Memorandum  -  PCDD/PCDF  Determination  in  Pulp/Paper  Mill
Sludge, from  Douglas  W.  Kuehl,  Research  Chemist,  USEPA,
Duluth, Minnesota  (to  Howard  Zar,  USEPA, Chicago, Illinois),
April 14, 1986.
Consolidated  Papers,
Environmental Studies
November 25,  1987.
   Inc.,  "Dioxin/Furan
                           Report
             Wisconsin
In-Mill
Rapids,
Source and
Wisconsin,
5.
6.


7.
Swanson,  S.E.,  C.
Emissions of PCDDs
Rappe,  K.P.  Kringstad, and
and PCDFs  from the Swedish
     J. Malmstrom,
     Pulp  and  Paper
Industry, Presentation at  Seventh International Symposium on
Chlorinated Dioxins and Related Compounds, Las Vegas, Nevada,
October 1987.

White, G.C., Handbook of Chlorination, Van Nostrand Reinhold,
New York, New York, 1972.

Duley,  M.  and  Freeman,  M. ,  Pulp and  Paper,  San  Francisco,
California, July 1987.

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                              -142-
                             GLOSSARY


A.  Chemical Terminology, Abbreviations, Units

    BOD--Biochemical oxygen  demand   is  a  measure of  biological
decomposition of organic matter in a water sample.  It  is determined
by measuring the oxygen required by microorganisms to oxidize the
organic contaminants of a  water  sample  under standard laboratory
conditions.  The standard  conditions  include incubation  for five
days at  20°C.   BOD^-Biochemiccil  oxygen  demand,  measured  after
five-days.

    CDDs—Chlorinated dibenzo-p-dioxins;   chemical  family  con-
sisting of eight homologues  (monochlorinated through octachlori-
nated)  and 75 congeners.  PCDDs-Polychlorinated dibenzo-p-dioxins.

    2378-TCDD—2,3,7,8-Tetrachlorodibenzo-p-dioxin.

    TCDDs--Tetrachlorodibenzo-p-diox ins; homologue comprised of 22
isomers of TCDOs.

    PeCDDs--Pentachlorodibenzo-p-diox ins; homologue comprised of 14
isomers of PeCDDs.

    HxCDD_s--Hexachlorod ibenzo-p-d iox ins; homologue comprised of 10
isomers of HxCDDs.

    HpCDDs--Heptachlorodibenzo-p-dioxins; homologue comprised of 2
isomers of HpCDDs.

    OCDD--Octachlorodibenzo-p-cl iox in; homologue  consisting  of  a
single isomer.

    CDFs—Chlorinated dibenzofurans ;  chemical  family  consisting
of eight homologues (monochlorinated through octachlorinated) and
135 congeners.  PCDFs-Polychlorinated dibenzofurans.

    2378-TCDF--2,3,7,8-Tetrachlorodibenzofuran.

    TCDFs--Tetrachlorodibenzofurans; homologue  comprised   of  38
isomers of TCDFs.

    PeCDFs--Pentachlorodibenzofurans; homologue  comprised  of  28
isomers of PeCDFs.

    HxCDFs--Hexachlorodibenzofurans; homologue  comprised   of  16
isomers of HxCDFs.

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                              -143-
    HpCDFs--Heptachlorodibenzofurans; homologue  comprised  of  4
isomers of HpCDFs.

    OCDF--Octachlorodibenzofuran; homologue consisting of a
single isomer.

    Congener--Any one  particular  member   of  the  same  chemical
family; e.g., there  are 75  congeners  of  chlorinated dibenzo-p-
dioxins.  A  specific  congener  is  denoted  by  unique  chemical
notation.  For  example,   2,3,7,8-tetrachlorodibenzofuran  is  re-
ferred to as 2,3,7,8-TCDF or, in this report, ,2378-TCDF.

    GC_--Gas chromatograph.

    GC/MS--Gas chromatography/mass spectrometry.

    Homologue--A group  of  structurally   related  chemicals  that
have the  same  degree  of  chlorination.   For  example,  there  are
eight homologues of CDDs , monochlorinated through octochlorinated .

    Isomer—Substances that belong  to  the  same  homologous class.
For example, there are  22  isomers that constitute the homologues
of TCDDs.

    ppm--Parts per million  (equal  to milligrams  per  liter,  mg/1,
when the  specific gravity is one  for  aqueous  samples;  and  equal
to micrograms per gram, ug/gm, for solid  samples).

    ppb--Parts per billion  (equal  to micrograms  per  liter,  ug/1,
when the  specific gravity is one  for  aqueous  samples;  and  equal
to nanograms per gram, ng/gm, for solid samples).

    ppt--Parts per trillion  (equal  to  nanograms  per  liter,  ng/1,
when the  specific gravity is one  for  aqueous  samples;  and  equal
to picograms per gram, pg/gm, for solid samples).

    ppq—Parts per quadrillion (equal to picograms per liter, pg/1,
when the  specific gravity is one  for  aqueous  samples;  and  equal
to femtograms per gram, fg/gm, for solid  samples).

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                              -144-
B.  Pulp and Paper Industry Terms

    Active Chlor ine--That portion  of chlorine  in  chemical  com-
pounds available  to  c3o  useful work  in  the chlorination  of  mill
water supply and  in  the  bleaching of pulp.   (See also Available
Chlorine)

    Additives—Chemicals or  any  other  materials  added  to  pulp
stock slurry to impart special physical  and visual properties to
the paper  sheet  or  board  made  from  it.   (See  Paper Additive)

    Air Dr ied--Reference to puljp  and  paper when dried artificially
with the use of heated air in appropriate type dryers.

    Air Dry (AD)--Refers to weight of moisture-free pulp or paper
plus 10%  moisture based  on  a traditional  assumption  that  this
amount of moisture  exists when  they come  into  equilibrium  with
the atmosphere, which in actuality is dependent on the conditions
of the atmosphere  to which  it  is  exposed.   Air-dried  weight is
determined by dividing the oven-dried weight  by  a factor of 3.9.

    Alkali Extraction—The second  stage  in   a  pulp  bleaching
sequence where the first stage is chlorination (in which chlorine
is added and allowed  to react with the pulp slurry) .  The resulting
chlorinated fiber  residuals and other alkali-soluble constituents
are then dissolved in the second or "alkali" extraction  stage; also,
caustic extraction stage, or "E"-stage.
    Alum- -A papermaking chemical , A12 (804) 3 '14^0, A12 (SO^) 3 "1 8H20
or a mixture  of these hydrates, commonly  used  for precipitating
rosin size  onto  the  pulp  fibers   to  impart  water-resistant
properties (when used for water treatment) to the paper made from
it.  Also called aluminum sulfate or papermaker's alum.

    Available Chlorine--A term used  in  rating  chlorinated lime,
hypochlor i tes , chlorine  dioxide,   and  other  chlorine  derived
chemicals (usually  used in  water  treatment  and  pulp  bleaching
operations)  as  to their  total  oxidizing  power;  C12-EQOX,  as used
in this report.  (See also Active Chlorine)

    Back wash ing- -The operation  of  cleaning   a  rapid   sand  or
mechanical filter by  reversing  the  flow of water  or liquid that
is being filtered.

    Bark--The rind   covering  of  stems,  branches,  and roots  of
trees and plants.  Technically, all tissues of woody plants which
are outside the cambium layer.

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                              -145-
    Bark Boiler--A furnace designed especially to burn  bark  as a
fuel"^  It is usually equipped with Dutch ovens.

    Batch Digester—A cooking  vessel,  usually  pressurized,  in
which predetermined, specific amounts of wood and cooking liquors
are heated  so  that  the  wood conversion to pulp  is  completed and
removed before  the  cycle  repeats, as  opposed  to  a  continuous
d igester.

    Batch System—A pulp  and  paper   manufacturing  unit  process
consisting of  a  series  of  operating  units which processes  pre-
determined specific amounts  of materials  and  carries  the process
to completion before starting another cycle.

    Black Liquor--Liquor from  the  digester to  the  point of its
incineration in the recovery  furnace of a sulfate chemical recovery
process.  It  contains  dissolved  organic  wood  substances  and
residual active alkali compounds from the cook.

    Black  Liquor  Evaporators--Multiple-effeet   combination  of
steam pressure  and  vacuum  vessels   in   which  black  liquor  is
concentrated.  They are arranged in such a way as to minimize the
amount of steam used to  carry on  the process of water evaporation.

    Black Liquor Recovery Boiler—A boiler   designed   especially
to recover  heat  by burning  concentrated  black liquor  (from the
cooking of  wood  by  the  sulfate process)  and  to use the heat for
steam generation.

    Black Liquor Recovery Furnace--A furnace or combustion chamber
especially designed to  recover desirable chemicals from burning
concentrated spent black liquor  from  the  cooking of  wood  by the
sulfate process.

    Bleach--(1) A chemical used to purify and whiten pulp.    It is
usually of the oxidizing or reducing type, such as chlorine-based
solution, oxygen,  and   similar   chemicals.    (2)   The  process  of
purifying and  whitening pulp by chemically treating  it to  alter
the coloring matter and  to  impart a higher brightness to the  pulp.

    Bleach Plant--That portion of a pulp mill where  the bleaching
process is performed.   It  usually  adjoins the brownstock washing
operation but  sometimes  is  contained  in a  separate  building.
Occasionally, this  area  is  referred  to  as   a  bleachery or the
bleaching plant.   It  also  refers  to  the  area where hypochlorite
bleach solutions are prepared.

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                              -146-
    Bleach Tower--A tall, cylindrical retention chest where pulp,
mixed with the bleaching agent, is retained the required time for
the bleaching action  to be completed  in  a continuous  system of
pulp bleaching.    An  upflow-type  is  used  when  bleaching  low
consistency pulp,  and  a  downflow-type  is  used  when  bleaching
medium and higher consistency  palp.   Also referred to as bleaching
tower.

    Bleach Washer--A filter (washer)  located after a bleach tower
in the bleaching  sequence  of  pulp where the pulp  is  washed free
of the residual  bleaching agent and the products of the bleaching
action.

    Bleached Pulp--Pulp that  has been  purified  or whitened  by
chemical treatment  to  alter coloring matter  and has  taken  on  a
higher brightness characteristic.

    Bleaching--The process  of purifying  and  whitening pulp  by
chemical treatment to remove or change existing coloring material
so that the pulp takes on a higher brightness characteristic.  It
is usually carried out  in a single stage or a sequence of several
stages.  Chlorine,  peroxides, calcium  hypochlorite,  carbon di-
oxide, and,  lately,   oxygen  are  most  generally  used  to  bleach
chemical pulps.    For  groundwood  pulp,  sulfur dioxide  and  sodium
peroxide are used.

    Bleaching Agent--A variety of chemicals used in the bleaching
of wood pulp such as chlorine  (Cl2), sodium hypochlorite (NaOCl),
calcium hypochlorite [Ca(OCl)2],  chlorine diox ide (C1C>2) , peroxide
(H2^2) • sodium chlorite (NaClC>2) ,  oxygen  (02) ,  and  others.  Also
referred to as bleaching chemical.

    Bleaching Stage—One of the  unit process  operations in which
one of  the  bleaching  chemicals  is  added   in  the  sequence  of  a
continuous system of bleaching pulp.

    Bone Dry  (B.D.) — (1) A descriptive term for  the moisture-free
conditions of pulp  and paper.   See  Oven Dry  (O.D.).   (2)  Refers
to air containing absolutely  no vapor.

    Caustic Extraction—A stage in the  pulp bleaching sequence (E)
that normally follows the  chlorination stages  to  remove alkali-
soluble,  chlorinated   lignins.   (See  Alkaline  Extraction  and
Extraction Stage)

    Caustic Extracted K. No.  (CEK)--A measure of the bleachability
of pulp tested  immediately  after  the caustic  extraction stage in
a pulp bleaching process.   (See Permanganate Number and K Number)

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                              -147-
    Causticizing--Convert ing green liquor to  white  liquor by the
use of slaked  lime [Ca(OH)2l which reacts with  the sodium carbonate
(Na2CC>3) in  the green  liquor  to form  active  sodium  hydroxide
(NaOH) in the white liquor.  Also called recausticizing.

    Cellulose--The chief substance  in  the  cell walls  of plants
used in  pulp  manufacturing.   It  is  the fibrous substance  that
remains after the  nonfibrous  portions,  such  as lignin  and  some
carbohydrates, are  removed  during  the  cooking  and  bleaching
operations of a pulp mill.
                                              t
    Chemical Pulp--The mass of fibers  resulting  from the reduction
of wood  or  other fibrous  raw  material  into  its  component parts
during the cooking phases  with  various chemical liquors, in such
processes as sulfate, sulfite, soda, NSSC, etc.

    Chemical  Recovery--The  recovery  of  chemicals  in  sulfate
cooking liquor  after  it is  used  to  cook  wood in  the  digester
(spent liquor).   It  is expressed  as  a  percentage  determined  by
dividing the  total  alkali  to  the digesters,  minus the  sodium
sulfate added  to liquor,  by  the total  alkali  in  the  cooking
liquor going  to  the digester  after correcting  for  any  change in
liquor inventory.

    Chip Pile--Chips that  are  stored  outside in a  mound type of
structure usually located near the pulp mill  so that chips can be
conveniently conveyed from it to  the digester storage.

    Chipper--A piece of equipment in  the woodyard/pulp  mill area
used to  "chip"  whole  logs.   It consists  of an  enclosed, rapidly
revolving disk  fitted  with surface-mounted knives  against which
the logs  are  dropped  in  an endwise  direction  in  such  a manner
that they are reduced to chips, diagonally to the grain.

    Chlorination—(1)  The mixing  and  reacting  of  chlorine water
or gas with pulp in the bleaching operation.  (2) The application
of chlorine to  mill  water  supply and  sewage  for disinfection or
oxidation of undesirable compounds.

    Chlorination  Stage--The  step  in  a  multi-stage  bleaching
process  ("C" stage)  where chlorine water or gas is mixed, allowed
to react, and then  washed  as  an  initial  operation  in a complete
pulp bleaching system.

    Chlorinator--A device for adding a chlorine-containing gas or
liquid to mill  wastewater.   Sometimes  the  term is also  used to
refer to the chlorine mixer in the bleach plant.

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                              -148-
    Chlor ine--A  greenish-yellow,   poisonous,  gaseous  chemical
element (Cl2)  used  in bleaching  pulp  and  water purification in a
pulp and paper mill.

    Chlorine Consumption—Actual amount of  chlorine consumed  to
bleach pulp, expressed as pounds of chlorine used per air dry ton
of pulp bleached, or a percentage on the same basis.  Tf may also
be expressed on a bone dry basis.

    Chlorine Dioxide Solution--A very unstable  water  solution of
chlorine dioxide gas  (C1C>2) produced  in the chemical preparation
area of a pulp mill.   It is used in the pulp  bleaching process.

    Chlorine Dioxide Stage--The step  or steps  in  a  multi-stage
bleaching process ( "D"-stages)  where chlorine dioxide solution is
mixed with pulp,  allowed to react,  and  then  washed  as  one of the
operations making up a complete pulp bleaching system.

    Chlorine Evaporator--A specially constructed, thermostatically
controlled vessel using  hot water  or  steam  to  vaporize liquid
chlorine transferred from  tank cars to  a pulp mill  bleach plant.
This vaporized product  is  used  in the chlorination  stage  of a
bleaching process, as  well as  to make  up hypochlorite  bleaching
liquor.  Also called chlorine vaporizer.

    Chlorine Mixer--A mixing device used  in  the  bleach plant to
mix chlorine water or gas with  unbleached  pulp.
    Chlorine Requirement—The amount of elemental  chlorine
required to achieve a specified final brightness level of pulp in
the bleaching process.   it  is  supplied in the  form  of elemental
chlorine and/or bleaching agents  such  as  hypochlor ites ,  chlorine
dioxide, etc.

    Chlorolignin--The product  of   reaction  between  lignin  in
unbleached pulp and chlorine in  the chlorination stage of a multi-
stage pulp bleaching system.

    Clay—A naturally  occurring,   earthy,  fine-grain  material
compsed of  a  group of crystalline  clay minerals  with  a natural
basic structure of  aluminosil icates  whose hydrous  chemical  form
is 2\\2Q' A12°3 * 2si°3*   Ifc  i-s commonly  used  in  the  paper  industry
to make  up  paper   filling   and   coating  materials.   Clays  are
sometimes altered by  further refining, heat treatment,  etc., to
enhance or extend their end uses, eg., calcined clay  and delaminated
clay.

    Coated Paper—A term  applied  to  any type  of  paper  whose
surface has been treated  in such a way as to  apply  a coating in
order to enhance its finish characteristics.

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                              -149-


    Coating—(1) The  process of  treating  a  sheet  of paper  or
paperboard so that  a  coating material  layer  of a clear  film  is
applied to its  surface.   (2) Refers  to the  coating  material  or
film substance  before coating.    (3)  The  coating  layer  that  is
formed on the paper and paperboard sheet.

    Consistency—(1) A measure  of the  fibrous material  in  pulp
solutions, e.g., pulp  and  water, or  stock (pulps  and additives)
and water.   It  is  expressed as  a percentage  of this  material  in
the solution, in  terms of  bone  dry  (BD) , oven dry  (OD) ,  or  air
dry (AD) weight.  (2)  That property of adhesives or other coating
material related to  viscosity,  plasticity,  etc.,  that makes  it
resistant to deformation or flow.

    Continuous Digester--A wood-cooking vessel  in which chips are
reduced to their  fiber  components  in  suitable chemicals  under
controlled temperature and  pressure  in a  continuous operation.

    Continuous Pulping Processes--Any pulping   process  in  which
the fibrous  raw  material and cooking  chemicals move  through the
successive processing phases in a continuous  fashion.

    Converting Mill—A name sometimes applied to a paper or paper-
board mill which does  not   produce  the  pulp  it  uses on  site.

    Countercurrent Washing--(1)  method of washing pulp by running
the wash  water  countercurrent  to  the  flow of pulp  through  the
process.  Examples include  countercurrent intra-stage washing  in
a multi-stage bleaching  process (to  minimize  effluent)  and  the
countercurrent flow of wash  water  to  pulp  flow  on  vacuum-type
brownstock washers  (to  minimize  water  use  and  maximize  black
liquor recovery).  (2)  The washing of pulp within a Kamyr continuous
digester  (before blowing) in which the  wash water  flows counter-
current to the pulp flow in the process.

    Delignificat ion--The separation of  the lignin  component  from
the cellulose  and  carbohydrate  materials  of  wood  and  woody
materials by chemical treatment, such as the cooking of chips and
the bleaching of pulp.

    Dewater--(1) The tendency of solids  in a slurry to aggregate
and cause the draining of  water from  standing  or  flowing sludge
or pulp slurry  in  a  pipeline,  sometimes to  the point where the
remaining solids become  thick enough to  make removal difficult,
or to  obstruct  free  flow through the line  or a restriction  such
as a valve.  (2)  The process by  which  some of  the water is removed
from the pulp stock, increasing the consistency.

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                              -150-
    Digester--(1)  A  pressure  vessel   used  to  chemically  treat
chips and  other  cellulosic  fibrous   materials  such  as  straw,
bagasse, rags, etc.,  under  elevated temperature and  pressure  in
order to  separate fibers  from  each   other.   It produces  pulp.
(2) In a waste treatment  plant,  it is a closed  tank that decreases
the volume  of  solids and  stabilizes  raw sludge  by  bacterial
action.

    Dye--(1) A natural or synthetic, organic or inorganic substance
used to make  up materials  to  Impart a color to  pulp  slurries  or
the paper  or  paperboard  shee b  in  papermaking,  or  to  make  up
coating material  to   color  their  surfaces.  The   name  is  used
interchangeably with the common paper mill  term, dyestuff.  (2) The
act of  coloring  (or  changing the color of) any  material (stock,
paper, etc.)  by bringing  it  into  contact  with  another  material
(dye)  of a  different color  in  such a manner that  the resulting
color will be more or less permanent.

    Extraction Stage—That stage in a  multi-stage pulp bleaching
operation("E"-stage), usually  following  the  chlorination  stage,
in which sodium hydroxide (NaOH) is  used to  remove water insoluble
chlorinated lignin and other colored components  not  removed in an
intermediate washing  operation.  Also  referred  to as  the caustic
stage or alkaline extraction stage.

    Fine Papers--High-quality writing,  printing,  and  cover-type
papers having  excellent   pen   and   ink  writing  surface  charac-
teristics .

    First  Stage--A  pulp  mill  reference  to  the   chlorination
stage (C-stage)  of  a multistage pulp  bleaching  operation,  which
traditionally has  been  the  first  step.   Recent  technological
developments have introduced other chemicals for use in the first
step.

    Free Chlorine--Elemental chlorine  in  the pulp bleaching pro-
cess which is in solution and not compounded with lignin elements
in chlorinated pulp slurries.

    Green Liquor—A liquid  that  is  formed during  the  sulfate
chemical recovery process  by dissolving  smelt  from the  recovery
furnace in a dissolving tank.   The clear liquid takes on a greenish
tinge.

    Green Liquor Clarification--The removal of   suspended  solids
(dregs) from  green liquor,  prior to causticizing  in a pulp mill,
by settling it in any one of several types  of sedimentation units
after flocculation.

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                              -151-
    Groundwood--Pulp and  paper  made  up  of  mechanical  fibers
produced by the grinding of pulpwood.

    Groundwood Pulp--A fibrous  slurry  produced  by  mechanically
abrading the fibers  from barked  logs through  forced  contact with
the surface of a revolving grindstone.  It is used extensively in
the manufacture of newsprint and publication papers.

    Hardwood--Pulpwood from broad-leaved dicotyledonous deciduous
trees.

    Hardwood Pulp--Pulp produced  from the  wood   of  broad-leaved
dicotyledonous deciduous trees.

    High Density Storage--The storage of pulp  slurries  in  a high
consistency condition, usually  after the bleaching  proccess  and
just prior to the stock preparation.

    High Temperature Bleaching--0perating the   bleaching  stages
(hypochlorite or chlorine dioxide)  of a multistage pulp bleaching
system at temperatures higher than considered conventional.

    High Temperature Chlorination--0perating the  first  bleaching
stage (chlorination)   of  a  multistage pulp bleaching  process  at
higher temperatures  (usually  110°F  to  120°F)  than  considered
conventional (less than 80°F).

    Hog Fuel--Raw bark, wood waste,  and other extraneous materials
which are pulverized  and used as a fuel for power boilers  in a mill.

    Hydrated  Lime   (CaOH2)—Partially  slaked  lime  produced by
adding water to lime (CaO).

    Hypochlori te--Reducing-type of bleaching chemical, usually in
the form  of calcium hypochlorite  or sodium  hypochlorite,  used
extensively in the bleaching of chemical pulps.

    Hypochlorite Stage--The step or  steps ("H"-stages) in a multi-
stage bleaching process in which hypochlorite bleaching chemicals
(usually calcium  or  sodium  hypochlorite)  are mixed,  allowed  to
react, and washed.

    K Number--A value, also  called  permanganate  number,  which  is
the result  of  a  laboratory test for indirectly  indicating  the
lignin content,  relative  hardness,  and  bleachability  of  pulps
usually having lignin contents below 6 percent.  It is determined
by the number of milliliters of tenth normal permanganate solution
(0.1 KMnC>4)  which  is absorbed by 1  gram of  oven  dry pulp under
specified conditions.

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                              -152-
    Kappa Number--A value obtained by a laboratory test procedure
for indirectly indicating the  lignin  content,  relative hardness,
or bleachability  of higher  l.ignin content  pulps,  usually  with
yields of 70 percent of  more.   It  is  determined  by the number of
milliliters of  tenth normal  permanganate  solution  (0.1  KMnC>4)
which is  absorbed  by 1  gram  of  oven  dry  pulp  under specified
conditions, and  is  then  corrected  to 50 percent  consumption of
permanganate .

    Kraft Process — The sulfate  chemical  pulping   process.   Also
any equipment used  as well  as  any intermediate or final products
derived from the process.   It means "strength"  in German, and is
a common pulp mill name  for the sulfate process.

    Kraft Cooking Liquor — A chemical mixture consisting primarily
of sodium hydroxide  (NaOH)  and sodium sulfide  (Na2S) .  It is used
to cook wood  chips and  convert  them  into wood  pulp.   Sometimes
called sulfate cooking liquor.

    Kraft Digester—A pulpwood  cooking  vessel  in  which  sulfate
cooking liquor, consisting  of  sodium  hydroxide (NaOH)  and sodium
sulfide (Na2S) active chemicals,  is  used as the  cooking medium.

    Kraft Paper--High-streng th paper made from  sulfate pulp.  It
is usually  made  with a  naturally  brown  color  using  unbleached
pulp, but it can also be made  of  bleached pulp and dyed to other
colors.  Also known as sulfate paper.

    Kraft Pulp--Wood pulp produced by  the  sulfate chemical process
using cooking liquor.  It is made up primarily of sodium hydroxide
(NaOH) and sodium sulfide (Na2$) /  using  basically softwood species
of pulpwood.  Also known as sulfate pulp.

    Kraft Pulping Liquor--A cooking chemical solution  made up of
sodium-based chemicals such as  NaOH,  Na2$,  Na2C03,  and
    Kraft Recovery Cycle--The series  of   unit  processes  in  a
sulfate pulp mill  in  which  the  spent cooking liquor is separated
from the pulp by washing, concentrated by evaporation, supplemented
to make  up  for  lost  chemicals,  and  burned   to   recover  other
chemicals.  These recovered  chemicals are converted  to new cooking
liquor by  reacting  them  with   fresh  and  recovered  lime   in  a
causticizing operation.

    Lignin--A brown-colored  organic  substance  which acts  as an
interfiber bond  in  woody  materials.  It is  chemically separated
during the  cooking  process  to  release the  cellulose  fibers to
form pulp, and is  removed  along with other  organic materials in
the spent cooking  liquor during  subsequent  washing  and bleaching
stages .

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                              -153-
    Lignin Content--The amount of lignin present in the composition
of the  raw  fibrous  materials  used  in  pulping  and  in  the  pulp
after cooking and washing.

    Lime (CaO)—A pulp mill chemical  obtained by burning limestone
(CaCoJ)and used to prepare cooking and bleaching liquors.  It is
also used in  causticizing  sulfate and soda  cooking  liquors, and
to make up milk of lime [Ca(OH)2l  for  the sulfite cooking process.
See also Limestone.

    Lime  Kiln—A  refractory  lined,  open-end,  inclined  steel
cylinder located  in  the lime  recovery area  of a pulp  mill  and
mounted on rollers.  It is rotated about its longitudinal axis as
lime mud  (CaCC>3)  is  fed  in  the  higher end,  and burned  to  form
lime (CaO)  as it travels to the lower discharge end.

    Lime Milk—The calcium  hydroxide  [Ca(OH)2]  formed  by  the
reaction of lime (CaO)  with water  (H20).

    Lime Mud--The sludge  which  is  primarily  calcium  carbonate
(CaCO^) that  settles  out  and is  separated  from the  white liquor
during the clarification operation in the causticizing process in
a pulp mill  recovery  cycle  prior to pumping  over  to  the  lime
recovery area.  Also called white mud.

    Limestone (CaCO-^)--A naturally  occurring  mineral  which  is
heated to  form  lime.   It  is  used  by pulp  mills  in  preparing
cooking and bleaching  liquors,  causticizing of  sulfate  and  soda
cooking liquors, and other uses.  See also Lime.

    Mechanical Pulp--Pulp produced by reducing  pulpwood  logs and
chipsintotheir fiber components by  the use of mechanical energy,
via grinding stones, refiners, etc.

    Medium Consistency—A generalized  reference  used to describe
pulp slurries having  consistencies within  the  approximate range
of 6  to 15  percent,  although  it  may  vary somewhat  depending
on where in  the pulp and papermaking process the  reference  is made.

    Multistage Bleaching—Any pulp-bleaching process  consisting of
two or more   stages  of operation in  continuous series,  rather
than in one single step.

    Oven Dry  (OP)—Moisture-free conditions of pulp and paper and
other materials  used  in  the  pulp  and  paper  industry.   It  is
usually determined by drying a  known sample to  a constant weight
in a completely dry atmosphere at a temperature of 100°C to 105°C
(212°F to 221°F).  Also called bone dry (BD).

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                              -154-
    Paper--A homogeneous sheet of  felted  cellulose  fibers,  bound
together by  interweaving  and  by the  use  of bonding  agents,  and
made in a variety of types.  It is used for a multitude of purposes
such as writing, printing, wrapping, clothing,  industrial, domes-
tic, sanitary, etc.

    Paper Additive—Chemical or  other material  added  to  paper,
paperboard, or  their  stock slurries  to impart  specific physical
and visual properties to  the  sheet,  such as wet  strength,  water
repellency, and fire resistence.  See also Additives.

    Paper Machine—Thee primary machine in  a paper  mill on  which
slurries containing fibers and other constituents are formed into
a sheet by the  drainage of water,  pressing, drying, winding into
rolls, and sometimes coating.

    Paper MJ11--A factory  or  plant location where  various  pulps
in slurry  form  are mechanically  treated,  mixed with  the proper
dyes, additives, and  chemicals,  and  converted  into  a  sheet  of
paper by  the  processes  of drainage,  formation, and drying  on a
paper machine.  Some paper mills also finish the paper  in various
ways.

    Permanganate Number—A value,  also  known  as  K number,  that
indicates the relative hardness or bleachability of chemical pulp
usually having  lignin contents below  6 percent.  It is determined
by the  number  of  milliliters  of  one-tenth  normal  potassium
permanganate solution (KMnC>4)  that  is absorbed  by  1 gram of oven
dry pulp  under   specified  and  carefully  controlled  conditions.

    Peroxide--A short name for sodium  peroxide  (Na2C>2) or hydrogen
perox ide  (H22)   which  are used  to  made  up  bleach   liquor   for
bleaching mechanical-type pulps.

    Peroxide  Bleaching  Stage--A  sodium  or  hydrogen  peroxide
bleaching step  or  steps  ("P"-stages)  sometimes used in the later
part of the multi-stage chemical-bleaching sequence as  one of  the
operations making up the complete pulp-bleaching system.

    Process Water—Any water  in a  pulp  and paper  mill  that  is
used to dilute, wash, or carry raw materials, pulp, and any other
materials used  in the process of making pulp and paper.

    Pulp--A  fibrous material produced  by mechanically or chemically
reducing woody  plants  into   their  components  parts   from  which
pulp, paper, and paperboard sheets are formed after  proper  slushing
and treatment,  or  used for dissolving  purposes (dissolving pulp
or chemical cellulose)  to  make rayon,  plastics,  and  other synthetic
products.  Sometimes called wood pulp.

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                              -155-
    Pulp Bleaching--The process  of  purifying and  whitening  pulp
in a pulp  mill  by chemically  treating  it to alter  the coloring
matter and to impart a higher brightness to the pulp.

    Pulp Cooking--The process of  reacting  fiber-containing mate-
rials with suitable chemicals, usually under high temperature and
pressure, in order to reduce them into their component parts with
the fiber portion  separated  in  the form of  pulp.   More commonly
known as pulping.

    Pulp MJ11--A plant in which  pulp is mechanically or chemically
produced from  fibrous  materials  such as   woody  plants, together
with other associated processes such as pulp washing and bleaching.
Chemical preparation and cooking chemical  recovery operations are
also conducted there.

    Pulp Washer--A piece  of  pulp  mill  equipment  designed  to
separate soluble,  undesirable  components  in  a  pulp  slurry  from
the acceptable  fibers,  usually  by some type  of  screening method
combined with  diffusion  and  displacement  with  wash  liquids,
utilizing vacuum or the natural force of gravity.

    Pulping Processes—Processes for converting fibrous raw mate-
rial into pulp.  They are usually classified by either the nature
or degree  of  the  chemical  and/or mechanical treatments  used  in
the pulping action.

    Recovery Boiler—A combination  unit  in  a pulp mill  used  to
recover the spentchemicals from  cooking  liquor and  to  produce
steam.

    Recovery Furnace--The unit  in a  sulfate  pulp mill  in which
concentrated spent  cooking  liquor  (black  Liquor)  is burnt  to  a
smelt to  recover  inorganic  sodium  salts  and to  generate steam.

    Recovery Plant--The area, building, or buildings where all of
the process  units  considered   to  be  included   in  the  chemical
recovery cycle of a pulp mill are located.

    Rosin--A material made up of a suspension and  used  for internal
sizing of paper and paperboard.   It is obtained as a residue from
the distillation of  gum  from  resinous southern  pines.  Sometimes
called colophony.

    Rosin Size--Rosin made up as a suspension and  used  for internal
sizing of  paper  and paperboard  to  enhance its  ability  to repel
moisture and water.

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                              -156-
    Salt Cake--A form of natural sodium sulfate  (Na2S04) added to
the thick  black  liquor just  prior  to incineration  in  a sulfate
recovery furnace where  it  is converted to  sodium sulfide  (Na2S)
to provide  one  of  the active chemicals  in  the subsequent makeup
of raw  cooking  liquor   in  the  sulfate  pulping process.   Also
referred to as glauber's salt.

    Seal  Tank--A  receiving  tank  located  beneath  vacuum-type
washers and filters.   The  watei:  drops into  it through a pipeline
and forms a seal to create a vacuum in the sheet-forming cylinder
portion of  the   unit.    Sometimes  referred  to  as   a   seal  pit.

    Sediment—Any material  thaL  settles  out  of pulp  slurries,
liquid solution,  treated water,  wastewater,  and other  fluids.

    Semibleached Kraft (SBK)—Pulp made  by  the   sulfate  process
which has  not  been  bleached  to  the  extent that normally  fully
bleached pulp has.   It is used to make up end products considered
of lower quality.
    Semibleached Pulp--Pulp which has been  only lightly bleached
to what  is  ordinarily  considered  a very  low  brightness  range.

    3howers--Water jets or  sprays  used  throughout  pulp and paper
mills to wash wire mesh  screens,  wires,  wet felts, and pulp pads
on paper machines,  cyl indrical-type washers, pulp  screens,  pulp
drainers, etc.

    Slaking/Causticizing--A two-stage  chemical  process  in  the
causticizing plant of an  alkaline  pulp mill in  which  the  sodium
carbonate (Na2CC>3)  in  the  green  liquor  is  converted  to  sodium
hydroxide (NaOH)  to  produce  white  liquor.  The first  stage  is
slaking, which  consists  of the addition  of lime  (CaO)  to green
liquor where  is  reacts   with  water  to  form   calcium  hydroxide
[Ca(OH)2l.   The second  stage is causticizing, in  which the calcium
hydroxide reacts  with  the   sodium  carbonate  to  form  sodium
hydroxide.   Both stages overlap.

    Slime--An undesirable  slippery,  glutinous  film  formed  by
microorganisms and the agglomeration of nonbiological matter.  It
is found throughout  the  pulp  and  paper  stock   flow and  storage
system.

    Siimicide--Toxic chemical  substance added   to  the pulp  and
paper process to inhibit the growth of undesirable microorganisms
that cause slime.

    Sodium Hydroxide (NaOH)--A strong  alkali-type   chemical  used
in making up cooking  liquor  in alkaline pulp mills.   It  is commonly
referred to  in  the  mill  as  caustic,  caustic  soda,  or  lye.

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                              -157-
    Sodium Hypochlorite (NaOCl)--A chemical  used as  one  of  the
bleaching agents in multi-stage pulp mill bleach plants.

    Softwood--Wood obtained from  evergreen,  cone-bearing species
of trees,such  as  the pines,  spruces, hemlocks,  etc.,  which are
characterized by having needles.

    Softwood Pulp—Pulp produced from the wood of evergreen coni-
ferous species  of  trees,  such as pines,  spruces, hemlocks, etc.

    Spent Liquor (SL)--Used cooking  liquor  in  a chemical  pulp
mill which is separated  from  the pulp after the cooking process.
It contains the  lignins, resins, carbohydrates, and other extracted
substances from the material  being  cooked.   Usually, this liquor
is processed through  a recovery  cycle  to produce  fresh cooking
liquor and steam for process use and/or power generation.

    Sulfate Process--An alkaline  pulp manufacturing process  in
which the active components of the liquor  used  in cooking chips in
a pressurized vessel   are  primarily  sodium  sulfide  (Na2S)  and
sodium hydroxide  (NaOH)  with  sodium sulfate   (N32S04)   and  lime
(CaO)  being used to replenish  these  chemicals  in recovery opera-
tions.  Sometimes referred to as the kraft process.

    Sulfate Pulp--Fibrous material used  in pulp,  paper, and paper-
board manufacture,  produced  by  chemically  reducing wood  chips
into their component parts  by  cooking  in  a vessel under pressure
using an alkaline cooking liquor.  This liquor consists primarily
of sodium  sulfide  (Na2S)   and  sodium  hydroxide   (NaOH).   Also
referred to as kraft pulp.

    Unbleached Pulp--Pulp that has not been  treated  in a bleaching
process and can be used  as is  in  inferior  grades  of  paper  and
paperboard.

    Washer—Pulp mill  equipment  designed  to  separate  soluble,
undesirable components  in  a   pulp   slurry   from  the  acceptable
fibers.  It usually consists  of some type  of  screening  method
combined with  diffusion  and   displacement  with  wash  liquid,
utilizing vacuum, or the natural force of gravity.

    Water Supply--The primary  source  of  natural  water  used in a
pulp and paper  mill,  such as  streams, rivers,  lakes,  and  wells.

    White Liquor—Cooking liquor  formed   by  refortifying  green
liquor in  the  causticizing  operation of an  alkaline-type  pulp
mill so that  it contains  the  active chemicals  that  will  reduce
chips into  their  fiber  components  by  dissolving  the  lignin
cementing material during the digester operation, thereby producing
pulp.

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                              -158-


    White Liquor Clarification---The removal of  calcium carbonate
(CaCC>3)  and other impurities  fron the causticizing liquor, usually
by gravity sedimentation  in  units  called  clarifiers.   This takes
place in  the  liquor  recaustici zing  process  of  a  pulp mill  in
order to obtain a clear liquor for cooking wood.

    White Water—Mill waters  which have a white, cloudy appearance
due to a very  fine dispersion  of  fibers picked  up when separated
from pulp suspension on paper machines, washers, thickeners, save-
alls, and  other  pulp-filtering equipment.   It  may also  contain
fine suspensions of sizing, dyestuffs, and filling materials, and
it is reused  in  the  papermaking process  or it  is  refiltered to
reclaim the suspended fibers.

    Wood—That part  of  the  stem of a plant,  located  between the
bark and the pith, which  is one of the primary  sources for fiber
used in the manufacture of pulp and paper.
All definitions for  Section  B and some definitions  in Section C
were obtained  from Pulp and Paper Dictionary, Lavigne,  John R.,
Miller Freeman Publications, 1936.

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                              -159-


C.  Utilities and Wastewater Treatment

    Activated Sludge--The settled  solids  after  treatment of pulp
and paper  mill  effluent  by aeration  with microorganisms.   The
solids are  collected at  the bottom  of  a  clarifier  tank  after
mixing with oxygen  in an aeration  tank.   Part of  the  sludge  is
recycled back  to  the  aeration  tank   to  maintain  high  solids
concentrations and efficient treatment.

    Activated Sludge Process--The treatment  of  pulp  and  paper
miLl effluent with  air  to  oxygenate  the biological  mass.   See
Activated Sludge.

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

    Biological Effluent Treatment--Process in which living micro-
organisms are mixed   with  incoming  wastewater  to  a  paper  mill
wastewater treatment  plant,  and use the  biologically degradable
organics in  waste  as  food-stuffs  or an  energy  source,  thus
effectively removing them from applied wastewater.

    Biological Oxidation--Breaking down (oxidizing)  organic carbon
by bacteria  that  utilize   free dissolved  oxygen   (aerobic)  or
"chemically bound" oxygen (anaerobic).

    Boiler--Broad or  general  term  for a  steam-generating  unit.
It is referred to as  an  industrial boiler when primarily used to
generate steam for  process   requirements  such as  in  a  pulp and
paper mill, or  as a  recovery  boiler  when  used  in  the  chemical
recovery cycle of a pulp mill.

    Boiler Slowdown—Per iod ic or continuous drains  from the drum
and/or waterwall   headers  to  remove  spent  precipitated feedwater
treatment chemicals from the unit.

    Clarification-- (1) The  removal  of turbidity   and  suspended
solids by  settling   in  mill wastewater  treatment.   (2)   In  the
causticizing plant in a pulp mill,  it  refers  to  the settling out
of suspended materials from  green and white liquors.

    Clarifiers--Storage tanks  in  which   suspended  solids  are
allowed to settle and be removed  from  green  and  white liquors in
the causticizing   areas  of a pulp mill.   Tank used  in wastewater
treatment for separation of  settleable solids.

    Effluent--Pulp or paper mill wastewater discharges to receiving
waters including   streams,   lakes,   and other  bodies  of  water.

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                              -160-
    Fly Ash--Entrained, partially  burned  dust,  soot, and  other
materials and chemicals that are carried over with the flue gases
emitted from  the  smoke  stacks  of  power  and  recovery  furnaces.

    gpm--Gallon per minute.

    Influent—Mill wastes,  water,  and  other  liquids, which  can
be raw  or  partially  treated,  flowing  into  a  treatment  plant,
reservoir,  basin, or holding pond.

    Leachate--Liquid containing dissolved chemicals  picked  up by
flowing the liquid through  a  material,  such  as water through the
contents of a landfill.

    MGD--MJ11ion gallons per day.

    MLSS--Mixed-liquor suspended solids.

    MLVSS--Mixed-liquor volatile; suspended solids.

    Outfall—The mouth of conduit drains  and  other  conduits from
which a mill effluent discharges; into receiving waters.

    Primary Sludge—The settlings removed from the first stage of
a wastewater treatment plant which  consists of  a sludge settling
tank.  The   sludge  is  normally  dried  over   vacuum   filters  and
disposed of in landfills or  dried and burned in the power furnace.

    Primary Treatment--The removal  of suspended  matter  from mill
wastewater  by sedimentation.   It  is usually  the  first stage in a
multistage  wastewater treatment process,  where substantially all
floating or settleable solids are mechanically removed by screening
and sedimentation.

    Secondary Wastewater Treatment--Biological treatment of some
pulp and paper  mill effluents  after  sedimentation  in  a  primary
wastewater  treatment plant.

    Sedimentation—The settling  of  suspended  solids  from pulp
slurries, liquid solutions, treated  water, wastewater,  and other
fluids.  It is  usually  accomplished by  reducing  the  velocity of
the liquid  below the point  where it can  transport  the  suspended
material.

    Sedimentation Basin—A large container in which wastewater is
retained so that any suspended  solids will settle by gravity and
then can be removed.

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                              -161-
    Sludge--Solid material filtered out of  mill  wastewater  which
is either disposed  of  in  landfill operations or  burned  in  power
bo ilers.

    Vacuum Filter--Any type of slurry  filter  in  which suction is
employed to deposit and form a pad of  solids  on  the  surface of a
separating material (screen)  with  the  liquid  flowing through it.

    Wastewater--Water carrying waste materials  from  a mill.   It
is a mixture of water, chemicals, and dissolved or suspended solids.

    Water Softener--Apparatus designed   to  remove the  dissolved
calcium and magnesium  minerals  that produce  hardness  from  water
to prevent scaling in power and  recovery boilers.

    Water Treatment--The processing  of mill  source  waters  from
rivers, lakes, and streams to remove impurities by sedimentation,
filtration, and the addition of chemicals  including  alum,  sodium
carbonate and chlorine.

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                      ATTACHMENT A







USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN  SCREENING STUDY




                     JUNE 20,  1986

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                                                                    6/20/86

           USEPA/PAPSR INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY


Background and Project Introduction

     Results from the National Dioxin Study indicate that 2378-TCDD has been
.Detected in fish and river sediments collected downstream from sane pulp and
paper mills located in various parts of the country.  The Petenwell Flowage in
Wisconsin, the Rainy River in Minnesota,  and the Androscoggin River in Maine
"have been identified as areas containing levels of dioxin to date.  Current
wastewater treatment plant sludges from some Maine,  Minnesota, and Wisconsin
mills contain parts per trillion (ppt) levels of 2378-TCDD and other PCDDs and
PCDFs.  Available EPA data indicate that, within the paper industry, bleached
kraft mills have the highest levels of 2378-TCDD in wastewater sludge.  This
would indicate that current process operations may be responsible.  However,
there are currently no data to document potential process sources of dioxins
nor to explain the wide range of sludge concentrations at bleach kraft mills.
The paper industry has initiated a sampling program for paper nri.ll wastewater
treatment plant sludges.  At this writing, paper industry data are not available.

     The U.S. Environmental Protection Agency (USEPA), the American Paper
Institute (API) and the >fational Council of the Paper Industry for Air and Stream
Improvement (NCASI), have decided to conduct a cooperative screening study of
five bleached kraft mills to determine possible process sources of PCDDs and
PCDFs and quantify raw waste, sludge, and final effluent loadings of PCDDs and
PCDFs.  The cooperative screening study is being conducted to determine the
formation and fate of PCDDs and PCDFs in bleached kraft pulp and paper making
operations and respective wastewater treatment facilities.  The cooperating
parties believe a screening study of this nature can most efficiently be con-
ducted by combining the knowledge and resources of federal and state governments
and industry.

     On March 5, 1986, the USEPA sent a formal request for information and
cooperation to the Boise-Cascade Corporation with respect to its International
Falls, Minnesota, mill.  Since this cooperative screening study is expected to
generate information fully satisfying that asked for in USEPA1 a March 5, 1986,
request, USEPA hereby agrees to withdraw that request pending satisfactory
execution of the cooperative screening study.

Screening Study Objectives

  1.  Determine, if present, the source or sources of 2378-TCDD and other PCDDs
      and PCDFs at five bleached kraft pulp and paper mills.

  2.  Quantify the untreated wastewater discharge loadings, final effluent
      discharge  loadings,  sludge  concentrations,  and  wastewater  treatment
      system efficiency for 2378-TCDD and other PCDDs and PCDFs.  Determine raw
      wastewater and final effluent levels of selected other organic compounds.

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                                      A-2                            6/20/86

General Project Organization and Responsibilities

  1.  Joint USEPA and Industry Responsibilities

      Responsible for:  (1) study design? (2) field coordination of sanpling
      collection program;  (3) providiiig personnel and equipment for sanpling;
      (4) providing quality assurance review of analytical data from all
      sarrples; (5) development of final report; (6) public, local government,
      and media relations.

  2.  USEPA

      Responsible for: (1) approval of sanpling locations; (2) contract
      analytical support;  (3) coordination of field sanpling with participating
      State Agencies; (4)  selection and prioritization of sarrples for analysis;
      (5) providing confidential treaiunent of process related information in
      accordance with Agency regulaticxis; (6) preparation of final report, and
      (7) public, local government, and media relations as necessary.  For
      USEPA the study will be directed through the Office of Water Regulations
      and Standards, Industrial Technology Division and Monitoring and Data
      Support Division.

  3.  Industry

      API and NCASI will each direct jxnrtions of the industry efforts, with the
      assistance of the five mills participating in the study.

      Responsible for:

      (1) providing study sites and a proposed sanpling plan for each site;
          (Participating Mills and NG^SI)

      (2) contracting for analytical support; (NCASI)

      (3) providing access to facilities, processes and production information
          to USEPA; (Participating Mills)

      (4) public, local government, and media relations as necessary.
          (API and Participating Mills)

      (5) Should a step in the kraft pulp and papermaking process be isolated
          as a major source of dioxin, the industry agrees to undertake a
          further investigation in attempt to determine its source and formation.

General Field Sanpling Plan

A complete set of samples at each mill will be obtained during a single sanpling
event.   Individual samples will be collected over a 24-hour period or other
suitable composite sanpling period.  Where appropriate, process additives may
be  grab sampled.  The approximate level of detail of sanpling to be conducted
at  each mill is presented in Table 1 along with analytical requirements.  The

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                                      A-3                            6/20/86

outline presented in Table 1 will be used as a guide for developing specific
sanpling plans for each mill.  .Ml sanples will be collected with appropriate
documentation, coding, and custody procedures.  Samples will be kept chilled
•luring collection and shipment to the analytical laboratory.  Process operating
conditions and production records iuring the survey will be recorded and made
available to study participants at the conclusion of each mill-specific sanpling
event.

General Analytical Plan

     Table 1 also presents a general analytical plan, and Table 2 presents
additional detail on sanple prioritization.  Sanples and analyses are prioritized
to conserve analytical resources.  Priority 1 analyses will be conducted and
reviewed prior to initiating Priority 2 analyses.  USEPA, NCASI, and industry
participants will consult to select Priority 2 sanples and analyses.  Analytical
costs for each mill will be shared on the basis of 25 percent funding by USEPA
and 75 percent funding by industry for all Priority 1 sanples and up to a
maxinun of 15 Priority 2 sanples.  Industry's share of the total analytical
cost for the screening study shall not exceed $150,000.

Quality Assurance Review

     The coded analytical data will be forwarded from the contract laboratory
simultaneously to the EPA and the NCASI quality assurance managers.  The quality
assurance managers will complete timely reviews of the data, consult with each
other and transmit the data to the EPA and NCASI project managers.  Should the
quality assurance managers disagree as to whether certain sanples require
reanalyses or followup analyses, the matter will be referred to the USEPA and
NCASI project managers for resolution.  Analytical costs associated with further
analyses beyond that normally conducted by the analytical laboratory to resolve
analytical problems will be shared by USEPA and industry on the same basis noted
above.  An outline of the Quality Assurance Project Plan for this screening study
is presented as Attachment 1.

Confidentiality

     Section 308(b) of the Clean Water Act, 33 USC § 1318(b), provides that
confidential treatment may be afforded to trade secrets which are contained
in information collected by, or submitted to, USEPA except that confidential
treatment is precluded for "effluent data." Information collected pursuant to
this dioxin screening study can be afforded such confidential treatment in
accordance with 40 CFR Part 2.  The participating companies may make claims of
confidentiality on information submitted to USEPA as specified in 40 CFR §
2.203(b).  USEPA will treat such submitted information in accordance with its
regulations found at 40 CFR Part 2.

     USEPA shall choose the appropriate manner in which to release the report
for this dioxin screening study after considering the confidentiality provisions
in the Clean Mater Act and Agency regulations and after consultation with the
participating mills, NCASI, and API.

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                                       A4                           6/20/86

Other Matters

     Any other matters regarding study design, study implementation, analytical
issues, etc., will be referred to the USEPA and industry project managers in a
timely fashion as they arise for resolution with other parties.

Final Report

     The cooperating parties agree that the final report of this screening
study will be limited to a technical document responsive to study objectives.
USEPA will have primary responsibility for preparation of the final report.
NCASI and API will provide input to the development of the final report and have
the opportunity to provide comments on review drafts.  In the event industry
participants do not agree with EPA's evaluation and conclusions regarding the
data resulting from this screening study, NCASI and API may provide separate
views regarding the data for inclusion in the final report.

     The undersigned signatories consent to, and approve this USEPA/Paper
Industry Cooperative Dioxin Screening Study:
Michael C. Farrar
Vice President
Environment and Health
American Paper Institute

Isaiah Gellman
Executive Vice President
National Council
  of the Paper Industry for
Air and Stream Improvement
Alexander C. McBride, Chief
Water Quality Analysis Branch
Monitoring and Data Support Division

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                                                                    6/20/86

                                    TABLE 1

               GENERAL SAMPLING PLAN AND ANALTYICAL REQUIREMENTS

                                                             ANALYTICAL PACKAGE


A.  Background Samples
      Treated River Water                                        2,3,4,5,6
      Treated River Water Sludge                                 1
      Wood Chips                                                 1

B.  Pulping Process
      Combinel Process Wastewaters                               2,5

C.  Chemical Recovery Plant
      Recovery Plant Contdned Wastewaters                        2
      Recovery Plant Waste Solids (Lime Mud)                     1

D.  Bleach Plant
      Pulp (Bleached and Unbleached)                             1 or 2
      Individual Sewered Streams from Bleachines                 1 or 2
      Contained Bleach Plant Process Wastewaters                  2,5
      Bleaching Agents Or Solutions                              1

E.  Paper Machines
      Combined Paper Machine Wastewaters                         2,5
      Process Additives (Alum, Clay, Dyes, Other Chemicals)      1
      Slimicides                                                 1 or 2

F.  Utilities, Wastewater Treatment
      Powerhouse Wastewater                                      2,5
      Powerhouse Ash to Treatment                                2
      Wastewater Treatment Primary Sludge                        2
      Wastewater Treatment Secondary Sludge                      2
      Wastewater Treatment Composite Sludge                      2
      Combined Untreated Process Wastewater                      2,3,4,5,6
      Final Treated Process Wastewater Effluent                  2,3,4,5,6
      Other Wastewater Streams to Treatment                      1,5
      (e.g. landfill Leachates)

Analytical Packages

    1.  Isomer specific analyses for TCDDs and TCDFs
    2.  Package 1 plus 2378-substituted and selected bioaccumulative PCDDs and
        PCDFs
    3.  Suspected precursor compounds: Chlorinated phenols, vanillins, and
        guaiacols
    4.  Non-polar compounds: HRGC scan for non-polar compounds
    5.  TSS: Total suspended solids
    6.  BODg: Five-Day biochemical oxygen demand

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                                      A6                            6/20/86

                                    TABLE 2


                             ANALYTICAL PRIORITIES
                                                              Estimated
PRIORITY 1 - Samples to be analyzed at all plants         Number of Sanples

   a.  Process Relatel
         Pulp (in - out)                                          2-6
         Bleach Plant Wastewaters                                 4-12
         Powerhouse Ash to Treatment                              1
         Selected Additives                                       2

   b.  Effluent Related
         Combined Bleach Plant Wastewaters                        1
         Combined Untreated Process Wastewaters                    1
         Final Treated Process Wastewater Effluent                1
         Composite Wastewater Sludge                              1
Priority 2 - Sanples to be selected from Table 1                  15
             for analysis based upon Priority 1 results

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                                         A 7
             UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                               WASHINGTON.  D.C.  20460
                                  JJi 16
                                                                   OFFICE OF
                                                                    WATER
Michael C. Farrar
Vice President
American Paper Institute
1250 Connecticut Avenue, N.W.
Washington, D.C.  20036

Dear Mr. Barrar:

     This letter is to inform you of a minor modification to the  analytical
scope of our cooperative dioxin screening study.   Specifically, EPA and NCASI
participants in the study have agreed to eliminate the analyses for certain
selected bioaccumulative PCDFs and for the non-polar compounds, both of which
were listed in the agreement.  The reasons for eliminating these  analyses
were 1) they were not directly related to the objectives  of  the study, 2)
they would require additional analytical methods  development and  resulting
costs, and 3) they could delay completion of the  analytical  efforts which are
directly related to the study objectives.  Attached is an amended version of
Table 1 from the agreement showing the changes.

     The study appears to be progressing well.  Jim McKeown  and Ray Whittemore
of NCASI attended a meeting of our regional coordinators  for the  study on
July 8, 1986, in Boston.  At this meeting we were able to review  what we had
learned from the Boise Cascade sampling effort and to develop a tentative
schedule for the remainder of the study.  We hope to be able to complete the
field work this calendar year and the analytical  work within two  or three
months after that.

                                                 Sincerely,
                                                Alec McBride, Chief
                                                Water Quality Analysis
                                                  Branch  (WH-553)
Attachment

cc:  Russ Blosser,  NCASI
     Gary               ~
     Tom O'Farrell

-------
                                        A 8

                                    TA'JLE  i

                GENERAL SAMPLING PLAN AND AMALIYICAL REQUIREMENTS

                                                             ANALYTICAL PACKAGE


A.  Background  Sanples
      Treate.1 River Water                                        2,3,^5,6
      Treated River Water Sludge                                 1
      Wood Chips                                                 1

B.  Pulping Process
      Combinei  Process Wastewaters                               2,5

C.  Chemical Recovery Plant
      Recovery  Plant Combined Wastewaters                        2
      Recovery  Plant Waste Solids (lime' Mud)                     1

D.  Bleach Plant
      Pulp {Bleached and Unbleached)                             1 or 2
      Individual Sewered Streams from Eleachines                 1 or 2
      Combined  Bleach Plant Process Wastewaters                  2,5
      Bleaching Agents Or Solutions                              1

E.  Paper Machines
      Combined  Paper Machine Wastewaters                         2,5
      Process Additives (Alum, Clay, Dyes,  Other Chemicals)      1
      Slimicides                                                 1 or 2

F.  Utilities,  Wastewater Treatment
      Powerhouse Wastewater                                      2,5
      Powerhouse Ash to Treatment                                2
      Wastewater Treatment Primary Sludge                        2
      Wastewater Treatment Secondary Sludge                      2
      Wastewater Treatment Composite Sludge                      2
      Combined  Untreated Process Wastewater                      2,3,V^5,6
      Final Treated Process Wastewater Effluent                  2,3,Jt5,6
      Other Wastewater Streams to Treatment                      1,5
      (e.g. Landfill Leachates)
Analytical Packages

    1.  Isomer specific analyses for TCDDs and TCDFs
    2.  Package 1 plus 2378-substituted and BBlaptoai TalBaeeuiimluUim PCDDs and
        PCDFs
    3.  Suspected precursor conpounds: Chlorinated phenols, vanillins, and
        guaiacols

    5.  TSS: Total suspended solids
    6.  8005: Five-Day biochemical oxygen demand

-------
                                        A9
             UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                              WASHINGTON. D.C. 20460
PR>P

                                  JUL  I  6 i986

                                                                   OFFICE OF
                                                                    WATER

Isaiah Gellman
Executive Vice President
National Council of the Paper Industry
  for Air and Stream Inprovement, Inc.
260 Madison Avenue
New York, N.Y.  10016

Dear Mr. Gellman:

     This letter is to inform you of a minor modification to the analytical
scope of our cooperative dioxin screening study.   Specifically,  EPA and NCASI
participants in the study have agreed to eliminate the analyses  for certain
selected bioaccumulative PCDFs and for the non-polar compounds,  both of which
were listed in the agreement.   The reasons for eliminating these analyses
were 1) they were not directly related to the objectives  of the  study, 2)
they would require additional analytical methods  development and resulting
costs, and 3) they could delay completion of the  analytical efforts which  are
directly related to the study objectives.   Attached is an amended version  of
Table 1 from the agreement showing the changes.

     The study appears to be progressing well. Jim McKeown and  Ray Whittemore
of NCASI attended a meeting of our regional coordinators  for the study on
July 8, 1986, in Boston.  At this meeting we were able to review what we had
learned from the Boise Cascade sampling effort and to develop a  tentative
schedule for the remainder of the study.   We hope to be able to  complete the
field work this calendar year and the analytical  work within two or three
months after that.

                                                 Sincerely,
                                                Alec McBride, Chief
                                                Water Quality Analysis
                                                   Branch  (WH-553)
Attachment

cc:  Russ Blosser, NCASI
     Gary Amendolai/
     Tom O'Farrell

-------
                                    TABLE  1

                Gf-NERAL SAMPLING  PIJ^I AND ANALTYICAL REQUIREMENTS

                                                             ANALYriCAL PACKAGE


A.  Background  Samples
      Treated River Water                                        2,3,^5,6
      Treated River Water Sludge                                 1
      Wood Chips                                                 1

B.  Pulping Process
      Combinel  Process Wastewaters                               2,5

C.  Chemical Recovery Plant
      Recovery  Plant Combined Wastewaters                        2
      Recovery  Plant Waste Solids (Lime Mud)                     1

D.  Bleach Plant
      Pulp (Bleached and Unbleached)                             1 or 2
      Individual Sewered Streams from Bleachines                 1 or 2
      Combined  Bleach Plant Process Wastewaters                  2,5
      Bleaching Agents Or Solutions                              1

E.  Paper Machines
      Combined  Paper Machine Wastewaters                         2,5
      Process Additives (Alum, Clay, Dyes, Other Chemicals)      1
      Slimicides                                                 1 or 2

F.  Utilities,  Wastewater Treatment
      Powerhouse Wastewater                                      2,5
      Powerhouse Ash to Treatment                                2
      Wastewater Treatment Primary Sludge                        2
      Wastewater Treatunent Secondary Sludge                      2
      Wastewater Treatment Composite Sludge                      2
      Combined  Untreated Process Wastewater                      2,3,\^5,6
      Final Treated Process Wastewater Effluent                  2,3,^5,6
      Other Wastewater Streams to Treatment                      1,5
      (e.g. landfill Leachates)
Analytical Packages

    1.  Isomer specific analyses for TCDDs and TCDFs
    2.  Package 1 plus 2378-substituted nni aal»rt>a TiiaiitaiummluUiii'u PCDDs and
        PCDFs
    3.  Suspected precursor compounds: Chlorinated phenols, vanillins, and
        guaiacols

    5.  TSS: Total suspended solids
    6.  BODj: Five-Day biochemical oxygen demand

-------
                                         A9

             UNITED STATES ENVIRONMENTAL' PROTECTION AGENCY
j'^*°                        WASHINGTON. D.C.  20460


                                   JUL  I 6 £86

                                                                   OFFICE OF
                                                                    WATER


 Isaiah Gellman
 Executive Vice President
 National Council of the Paper Industry
   for Air and  Stream Improvement,  Inc.
 260 Madison Avenue
 New York, N.Y.  10016

 Dear  Mr. Gellman:

      This letter is to inform you  of a minor modification to the analytical
 scope of our cooperative dioxin screening study.  Specifically, EPA and NCASI
 participants in the study have agreed to eliminate the analyses for certain
 selected bioaccumulative PCDFs and for the non-polar compounds, both of which
 were  listed in the agreement.  The reasons for eliminating these analyses
 were  1) they were not directly related to the objectives of the study,  2)
 they  would require additional analytical methods development and resulting
 costs, and 3)  they could delay completion of the analytical efforts which are
 directly related to the study objectives.  Attached is an amended version of
 Table 1 from the agreement showing the changes.

      The study appears to be progressing well.  Jim McKeown and Ray Whittemore
 of NCASI attended a meeting of our regional coordinators for the study on
 July  8, 1986,  in Boston.  At this meeting we were able to review what we had
 learned from the Boise Cascade sampling effort and to develop a tentative
 schedule for the remainder of the  study.  We hope to be able to conplete the
 field work this calendar year and the analytical work within two or three
 months after that.

                                                 Sincerely,
                                                 Alec McBride,  Chief
                                                 Water Quality Analysis
                                                   Branch (WH-553)
Attachment

cc:  Russ Blosser, NCASI
     Gary Amendolai/
     Tom O'Farrell

-------
                                     TABLE 1

                GPNEKAL SAPLING P!^VI ,VJD ANrXLTYICAL REQULRSHENTS

                                                              ANALYTICAL PACKAGE


A.  Background Samples
      Treated River Water                                        2,3,^5,6
      Treated River Water Sludge                                 1
      Wood Chips                                                  1

B.  Pulping Process
      Combined Process Wastewaters                                2,5

C.  Chemical  Recovery  Plant
      Recovery Plant Combined Wastewaters                        2
      Recovery Plant Waste Solids (Lime Mud)                      1

D.  Bleach Plant
      Pulp (Bleached and  Unbleached)                              1 or 2
      Individual Sewered  Streams from Bleachines                  I or 2
      Combined Bleach  Plant  Process Wastewaters                   2,5
      Bleaching Agents Or Solutions                               1

E.  Paper Machines
      Combined Paper Machine Wastewaters                          2,5
      Process Additives (Alum, Clay, Dyes,  Other Chemicals)       1
      Slimicides                                                  1 or 2

F.  Utilities,  Wastewater Treatment
      Powerhouse Wastewater                                       2,5
      Powerhouse Ash to Treatment                                 2
      Wastewater Treatment Primary Sludge                        2
      Wastewater Treatment Secondary Sludge                      2
      Wastewater Treatment Composite Sludge                      2
      Combined Untreated  Process Wast.ewater                      2,3,\^5,6
      Final Treated Process  Wastewater  Effluent                   2,3,^5,6
      Other Wastewater Streams to Treatment                      1,5
      (e.g. Landfill Leachates)
Analytical Packages

    1.  Isoner specific analyses  for TCDDs  and TQDFs
    2.  Package 1 plus 2378-substituted  ami eali»fr«i teJ8a8«umulalii»B PCDDs and
        PCDFs
    3.  Suspected precursor compounds?: Chlorinated phenols,  vanillins,  and
        guaiacols
            r^**""""""   — - - y~        _  — — ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
    5.  TSS: Total  suspended solids
    6.  BODj: Five-Day biochemical o;i
-------
                         ATTACHMENT  B







   USEPA/PAPER INDUSTRY COOPERATIVE  DIOXIN SCREENING STUDY




SAMPLING PROCEDURES, SAMPLE  PRESERVATION,  AND SAMPLE HANDLING

-------
                               ATTACHMENT B
            USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
         SAMPLING PROCEDURES, SAMPLE PRESERVATION,  AND SAMPLE HANDLING

A.  Haters, Wastewaters, Pulps, High Moisture (Liquid) Sludges

    1.  Definitions

        Grab Sample - A  discrete sample  collected manually  over  a  period  of
            time not to exceed 15 minutes.

        Composite Sample - A  sample  formed  by combining grab samples taken  at
            periodic time  intervals   over  a  specified  sampling  period.   In
            order to  form  a  representative  composite,  the  volumes  of  the
            individual  grabs may be proportioned according to the time intervals
            or according to the total  flows occurring during the time intervals.

        Sampling Container - The precleaned  stainless steel  or  glass  container
            used to  obtain  grab samples  from  the  flow  of material  at  the
            sampling site.

        Sampling Device -  The apparatus  to  which  the  sampling  container  is
            attached to  collect  grab samples.   One  gallon for  liquids  and
            slurries and one quart for solids.

        Composite Sample Bottle -  The  precleaned   glass  bottle which  becomes
            the final repository  of  the  composite  sample  for  shipment to  the
            analytical  laboratory.

        Aliquot Bottles - Precleaned  glass  containers into  which  grab  samples
            are apportioned  for  the  purpose  of   providing  the   appropriate
            volumes of the  grab sample  for  preparing composite samples  where
            more than  one composite  sample  bottle is  required at a  sampling
            site.

    2.  Precleaning  of  Sampling Containers,  Aliquot  Bottles, Composite  Sample
        Bottles, and Sampling Devices

        Prior to the survey, the sampling  containers,  aliquot bottles, composite
        sample bottles,  and  that  portion  of the  sampling  device  that   will
        contact the sample shall be cleaned  as follows:

                        Water and Detergent  Wash
                        Water Rinse (deionized)
                        Methylene Chloride Rinse or Hexane Rinse
                        Oven Dry or Air Dry

        For transport to the  field, sampling devices shall be wrapped in aluminum
        foil, shiny  side in.   Precleaning  of aluminum  foil  is not  required.
        Any cleaning  in  the   field  shall  be in  accordance with  the  above.

                                    Bl

-------
                                 B2
3.  Passivation  of  Sampling  Containers,  Aliquot Bottles,  and  Composite
    Sample Bottles

    Prior to  initiation   of   sampling,  each  sampling  container,  aliquot
    bottle, and composite sample bottle  must be  prerinsed  with the material
    to be  sampled  to passivate  any adsorptive  sites  on the  containers  or
    bottles.  This shall  be done  at  the outset  of the  survey and prior  to
    use of any new sampling containers or aliquot bottles that are introduced
    due to breakage  or modification  of  the sampling  plan.   Passivation  of
    sampling containers  or  sample  bottles  is  not   necessary  for  solids
    samples.

4.  Pretreatment and Preservation of  Selected Samples

    During reconnaissance prior to the  survey,  sites containing  or  having
    the potential to contain total residual chlorine  and  pH  values  outside
    the neutral  range  shall   be   identified.   An  additional  portion  of
    each sample  suspected  of having  a  chlorine  residual  or  requiring  pH
    adjustment shall  be transported to  a  field  laboratory for analysis  of
    chlorine residual and/or pH.   For each  grab sample at such  sites, the
    total residual chlorine shall  be determined amperometrically  or  by wet
    chemical  methods and  recorded.  The  residual  chlorine  shall then  be
    neutralized as soon as practical  with  crystalline, reagent grade  sodium
    or potassium thiosulfate (35  irig/ppm  Cl2/liter)  prior  to  adjustment  of
    pH with 6 M sulfuric  acid.

    For composite  samples designated  for  analysis of  selected  chlorinated
    phenolic compounds the pH  of each grab sample  shall  be adjusted to less
    than 2 standard  units,  using 6 M  sulfuric  acid,  prior to  addition  to
    the composite  sample bottle.   The pH  of the composite sample  shall  be
    checked at the conclusion  of the  survey to insure  that a  pH less  than 2
    has been achieved.  All  sample;; shall  be chilled from time of collection
    through delivery to the analytical  laboratory.

5.  Sampling Procedures

    Prior to obtaining each grab sample, the sampling container and sampling
    device shall be rinsed twice with  the material  to be sampled.  Sufficient
    volume of grab sample shall  be obtained at one time to fill  the aliquot
    bottles for all composite sample bottles at  a sampling  site.  For  liquid
    samples, the  grab  sample must  be  thoroughly  mixed  (manually  shaken)
    while preparing the aliquots.  Each  aliquot  bottle shall  be filled from
    the sampling container in  quarter-volume increments on a  rotating basis
    to insure that each  composite sample bottle  receives  a  representative
    portion of  the grab  sample.   For  pulp samples,  each sample  shall  be
    collected manually with a  rubber  or  latex glove and dewatered by  manual
    squeezing upon collection prior to introduction to the sample container.
    Where necessary,   for  safety reasons  a  pulp  sampling  device  such  as a
    stainless steel  spoon  or  wooden  paddle dedicated  to  that site  may  be
    used to collect the individual grab  samples.

-------
                                        B3
        If it is not feasible to obtain sufficient volume of liquid  sample with
        one grab  sample,  multiple  grab  samples may  be  obtained.   In  these
        cases, the aliquot bottles shall  be filled  with  equal  portions  of each
        grab sample  obtained.   When  not  in  use, the  sampling container  and
        aliquot bottles shall be kept in the ice chest  designated for  that site
        or otherwise secured and protected from contamination.

    6.  Sample Identification and Coding

        Each composite sample  bottle shall  be  identified  with a gummed  label
        bearing a  sample  identification  number  unique to  the sampling  site.
        The composite sample bottles  shall be placed in ice  chests which  shall
        be clearly  identified  by sample  number  and sample  site  name  for  the
        duration of the sampling survey.  Samples from  a  given  sampling  station
        shall be  retained  in  an ice  chest or  ice chests dedicated  to  that
        sampling station  only.   Each composite  sample  bottle   for analysis  of
        selected chlorinated phenolic  compounds  shall  be distinguished with  a
        bright yellow tag  for identification during  the sampling event.   Sample
        identification by   site  shall   not  be  provided   to   the  analytical
        laboratory.

    7.  Sample Handling and Shipping

        Upon completion  of  the  survey,   a  second tag  bearing   the   sample
        identification number  and the  analytical   package  required  shall   be
        attached to each  composite sample  bottle.  The  composite sample  bottles
        shall be sorted by  site  into  Priority  1  and Priority 2 analysis groups
        and packaged in ice chests accordingly.   The ice chests  shall  be clearly
        marked as Priority I or Priority 2.  The ice chests  shall be  packed  to
        prevent sample breakage  and  iced  to maintain  low  sample temperatures.

B.  Composite Wastewater  Sludge (Semi-Solid)

    1.  Definitions

        Grab Sample - A discrete sample  collected  manually over  a  period  of
            time not to exceed 15 minutes.

        Composite Sample  -  A sample  formed  by  mixing grab  samples  taken  at
            periodic time  intervals.

        Sampling Device -  Precleaned stainless  steel spoon, attached to  a  pole,
            if necessary.

        Grab Sample Preparation Pan  - Precleaned  aluminum  pan  used  for  field
            homogenization of  sludge  grab  samples prior   to  introduction  of
            aliquots into  the composite sample  bottles.

        Composite Sample  Bottle -  The  precleaned  glass  bottle which  becomes
            the final repository  of  the composite  sample  for   shipment to  the
            analytical  laboratory.

-------
                                  B4
2.  Precleaning of Composite Sample bottles and  Sampling Devices

    Prior to  the  survey, the  composite  sample  bottles, the  grab  sample
    preparation pans, and the sampling devices  shall  be cleaned as  follows:

                    Water and Detergent Wash
                    Water Rinse (deionized)
                    Methylene Chloride Rinse or  Hexane Rinse
                    Oven Dry or Air Dry

    For transport  to the  field, sampling devices  shall  be wrapped in aluminum
    foil, shiny side in.  Precleaning  of aluminum  foil  is not  required.
    Any cleaning  in the  field  shall   be  in  accordance with  the  above.

3.  Passivation of Composite Sample Bottles and  Sampling Devices

    Passivation of composite sample bottles and sampling devices  for sludges
    is not essential.   Prior to initiation  of  sampling, composite  sample
    bottles, grab   sample preparation  pans, and  sampling  devices  may  be
    prerinsed with  final treated   wastewater  effluent  to  passivate  any
    adsorptive sites on the  containers or  devices.   This may be done at the
    outset of the  survey and prior  to use  of any new containers or  sampling
    devices that  are introduced due to  breakage  or  modification of  the
    sampling plan.

4.  Preservation of Samples

    Composite samples  shall  be  iced  from  collection to  delivery to  the
    analytical laboratories.

5.  Sampling Procedures

    The stainless  steel  spoon  shall  be used  to  obtain a  sludge grab sample
    of sufficient  volume to  make up aliquots for all  composite  samples at
    a given site.   The  sludge shall  be  placed in the grab sample preparation
    pan and mixed  with the stainless steel  spoon until a uniform  appearance
    is evident.  The mass shall  be quartered and requartered.   A  rotating
    system shall be used to  add the proper volume aliquot to each composite
    sample bottle.

6.  Sample Identification and Coding

    Each composite  sample bottle shall be identified with a gummed  label
    bearing a  sample identification  number  unique to  the  sampling  site.
    The composite sample bottles shall  be  placed in ice  chests which  shall
    be clearly  identified by sample  number  and sample  site  name  for  the
    duration of the  sampling survey.  Sample identification by  site  shall
    not be provided to the analytical laboratory.

-------
                                  B5
7.  Sample Handling and Shipping

    Upon completion  of  the  survey,  a  second  tag  bearing  the  sample
    identification number  and the  analytical   package  required  shall  be
    attached to each composite sample bottle.  The composite sample bottles
    shall be sorted by  site  into  Priority  1  and  Priority  2  analysis groups
    and packaged in ice chests accordingly.  The ice chests shall be clearly
    marked as Priority 1 or Priority 2.  The ice  chests  shall  be packed to
    prevent sample  breakage  and  iced to maintain low  sample  temperatures.

Process Additives

1.  Definitions

    Grab Sample - A discrete  sample  collected manually  over a  period  of
        time not to exceed 15 minutes.

    Grab Sampling Container -  The  precleaned   glass  or  stainless  steel
        container used to  obtain  the grab sample.   In  many cases  a  glass
        sampling container may be the final grab sample bottle.

    Sampling Device -  The  apparatus  to which  the  sampling  container  is
        attached to  collect  grab  samples.   One  gallon  for liquids  and
        slurries and one quart for solids.

    Final Grab Sample Bottle -  The  precleaned  glass bottle  which  becomes
        the final  repository  of   the   grab  sample for  shipment  to  the
        analytical laboratory.

2.  Precleaning of Grab Sampling Containers,  Final Grab Sample Bottles, and
    Sampling Devices

    Prior to the  survey,  the  grab  sampling  containers, final  grab sample
    bottles, and that portion  of  the  sampling  device that  will  contact the
    sample shall be cleaned as follows:

                    Water and Detergent Wash
                    Water Rinse (deionized)
                    Methylene Chloride Rinse  or Hexane Rinse
                    Oven Dry or Air Dry

    For transport to the field, sampling devices shall be wrapped in aluminum
    foil, shiny  side  in.   Precleaning  of aluminum foil  is  not  required.
    Any cleaning  in  the   field  shall  be  in  accordance  with the  above.

-------
                                  B5


3.  Passivation of  Grab  Sampling Containers and Final  Grab  Sample Bottles

    Passivation of  grab  sampling containers and final  grab  sample bottles
    for liquid  samples  shall  consist  of  a rinse  with  the material to  be
    sampled. Grab sampling  containers  and  final   grab  sample  bottles  for
    solid samples shall  not be passivated.

4.  Pretreatment and Preservation of Samples

    Samples shall  not  be pretreated  or  chemically preserved,  except  that
    any samples with  residual  chlorine  shall  be  .treated with sodium  or
    potassium thiosulfate as  soon  as  practical  to  neutralize  the chlorine.
    Samples shall  be  kept  chilled  from  collection  to   delivery  to  the
    analytical laboratory.

5.  Sampling Procedures

    Representative grab  samples shall  be obtained  as appropriate.

6.  Sample Identification and  Coding

    Each final grab sample  bottle  shall  be identified with a  gummed  label
    bearing a  sample  identification  number  unique to  the sampling  site.
    The final grab sample bottles shall be placed  in ice chests which  shall
    be clearly  identified  by  sample  number  and sample  site  name  for  the
    duration of the sampling  survey.   Sample identification  by site  shall
    not be provided  to the analytical  laboratory.

7.  Sample Handling  and  Shipping

    Upon completion   of  the  survey,   a  second  tag   bearing  the  sample
    identification number  and the  analytical   package  required  shall  be
    attached to each  final  grab  sample  bottle.   The  final   grab  sample
    bottles shall  be sorted by  site into Priority  1  and  Priority  2 groups
    for analysis  and packaged in  ice  chests  accordingly.  The ice chests
    shall be  clearly marked as  Priority 1  or  Priority  2.  The ice chests
    shall be  packed to  prevent  sample breakage and  iced to  maintain  low
    sample temperatures.

-------
                    ATTACHMENT C







    ANALYTICAL PROTOCOL FOR THE DETERMINATION  OF




      2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN  AND




         2,3,7,8-TETRACHLORODIBENZOFURAN IN




PAPER MILL PROCESS SAMPLES AND PAPER MILL  EFFLUENTS

-------
                                                      June 12, 1987
                                                   REV June 22, 1987


           WRIGHT  STATE UNIVERSITY, DAYTON, OHIO 45435

            ANALYTICAL PROTOCOL FOR THE DETERMINATION
           OF  2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN AND
  2,3,7,8-TETRACHLORODIBENZOFURAN IN PAPER MILL PROCESS SAMPLES
       (WOODCHIPS  AND PAPER  PULP) AND PAPER MILL EFFLUENTS
      (SLUDGE, ASH, MUD, TREATED AND UNTREATED WASTEWATER):
                       DIOXIN I ANALYSES
      I.   SUMMARY OF  SAMPLE RECEIPT AND HANDLING PROCEDURES

     Samples are  shipped  to Wright  State  University  (WSU),

Dayton,  Ohio,  via  Priority  Carrier  (such as Federal  Express  or

UPS Overnight)  or  are  delivered  by  U.S.  EPA personnel  and upon

arrival  at the  WSU  Central Receiving Area,  the  Laboratory Sample

Custodian or his designate  is notified.   The  Sample Custodian

proceeds  to Central  Receiving,  signs the  carrier's shipping

documents, and  any Chain-of-Custody documentation  received with

the samples, takes  custody  of the shipment, and  transports  the

shipment  to the  Laboratory.   The samples  are then carefully

unpacked within a hood  located in  a secure room, the condition of

each sample is  noted  and the individual  sample  numbers  assigned

by the person (s)  who collected the samples in  the  field  and  the

accompanying descriptions of the samples are  recorded in  a

Laboratory  Sample  Log-In   Book.    Also,  at this time,   an

Intralaboratory Control Number is  assigned  to each sample by  the

Laboratory  Sample  Custodian, and this  identifying  number  is

entered  in the Laboratory  Sample Log Book and is also recorded on

a  label  affixed to the sample vessel.   Subsequently, a  Receipt

Memorandum is prepared  by the Laboratory  Sample Custodian,  which

provides  a  detailed listing and description of  the  samples

received,  and  this is. forwarded  to  the  Laboratory Director.
                         Cl

-------
Accompanying  this  Sample  Receipt  Memorandum  are  Chain-of-Custody

documents  and  any other  pertinent  shipping  documents  which

accompanied the  samples.   The  original  Sample Receipt Memorandum

and associated  documentation become a permanent  component of the

appropriate contract  folder  which  is maintained  in  this

Laboratory.   Copies of  the Sample  Receipt  Memorandum and

associated documentation are ultimately appended to  reports

issued by  this  Laboratory which summarize  analytical  results

obtained for  the samples.  If requested by U.S. EPA,  signed chain-

of-custody documentation  establishing  receipt of the samples by

Wright State  is  provided to the requesting organization.

     Samples  are stored in locked refrigerators if  appropriate,

and samples not requiring refrigeration  are  stored in  locked

cabinets which  are located in secure,  locked rooms.  The Sample

Custodian  controls access  to  the samples,  and only authorized

personnel are permitted access to  the samples,  for  the purpose of

obtaining aliquots of the samples for  analysis.  All Laboratory

Personnel  who  handle  the samples  are  required  to  sign the

Intralaboratory Sample Tracking Form which  eiccompanies the

samples  and extracts prepared  therefrom,   throughout the

Laboratory, during all phases of preparation  and analysis.


    II. PROCEDURES UTILIZED FOR STORING AND PREPARING SAMPLES
          FOR ANALYSIS, INCLUDING DRYING SOLID SAMPLES
                  AND FILTERING AQUEOUS SAMPLES

A.  Storage of  Samples

     1.  Refrigerate  all  of  the  samples (at  5°C) upon receipt in

the Laboratory  and proceed with  the  procedures  outlined below as

soon as practical.
                         C2

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B.   Sample  Preparation



     1.   Sludge Samples



     a.   Open  the sample container and  using a spatula, break the



sludge into small particles  (about  2  cm diameter or  less)  and



stir the  sample vigorously to make it as  homogeneous as possible.



Remove an  aliquot of  this sample  (approximately  5  g)  for  an



"oven-dried  solids as-received"  determination,  using  the



procedures  described  below  (Section  II.B.l.d.). Remove  the



remaining sample  from  the container  and  distribute  it uniformly



on a stainless steel screen which is supported  at  a  distance  of



about 1  cm above  a sheet  of  aluminum foil, both  the foil  and the



screen  being contained within  a  desiccator containing  an



appropriate water  sorbent.   To minimize the possiblity  of



contamination or cross-contamination  of the sample, only  one



sample at  a time is dried in a  given desiccator.   Allow  the




sample to remain  in  the desiccator until it is  essentially dry,



as  indicated  by  the sample  color, consistency,  and ease  of



mixing.   For each  group of five  sludge  samples  which  are



desiccated,  prepare  a laboratory blank  as follows.  Place  a 15 cm



Whatman  #42 filter  on  a  stainless steel screen supported  at  a



distance  of 1 cm above a  sheet of  aluminum  foil  contained  in  a



desiccator and allow the  filter  to remain in the desiccator for



the  same period  as  that  which  was used  for that  sample  of  the



five which required  the longest  drying  time.  Subsequently remove



the  filter  from  the  desiccator  and  continue  with  the



homogenization,  drying,   and other sample preparative  steps



described below.
                         C3

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     b.   When the sample has been dried sufficiently, remove  it



from the desiccator  and  transfer it to a laboratory blender  which



is housed within  a  glove box  or  similar  enclosure.   Following



homogenization in  the blender, remove an aliquot {approximately 5



g) of the blended solids, accurately weigh this  sample  aliquot,



and  subject  it  to an  oven-dried solids determination,  as



described in Section II.B.l.d. of this protocol.



     c.    Place the  remaining desiccated,  blended sample into  a




clean sample  bottle fitted  with a  Teflon-lined  screw cap,  and



store the bottle  in a  refrigerator (5°C).   An aliquot  of  this



desiccated,  blended  sample is subsequently  analyzed for  2,3,7,8-



TCDD and  2,3,7,8-TCDF  by applying  the extraction and  analysis



procedures  which  are  described in  Sections  IV. and V.,



respectively,  of  this protocol.



     d.    Determination  of oven-dried-solids on a  sample  aliquot



is accomplished  by placing  the weighed  aliquot into  a  tared



aluminum  boat which is then placed in an  oven  maintained  at



105°C.  After heating  for  a period of  twenty-four  hours, the



aluminum  boat  containing  the sample is removed  from the  oven,



allowed to cool for  30 minutes in a desiccator,  and then  weighed.



The  boat and  sample  are  then returned   to   the  oven  for  an



additional  four-hour  period,  after which,  the boat is again




removed from  the  oven,   allowed  to  cool  and weighed again.    The



latter procedure   is repeated until  the  weight  of the sample  as



indicated by two  successive weighings is observed to be constant.



From the  observed weight loss upon drying,  the  percentage  of



oven-dried-solids  in the original sample can be determined.   This



result,  as determined for an  aliquot of the sample  as  received,






                         C4

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is reported as the "initial oven-dried solids  as  received."   The



oven-dried  weight loss, as  determined  for an aliquot of  the



previously  desiccated sample (a separate aliquot  of which  is



subsequently analyzed for  TCDD/TCDF)  is  used only  to determine




the actual weight of  the sample  aliquot which  is  analyzed on the



oven-dried solids basis.



     2.   Wood Chip Samples




     a.   Samples of wood chips in which the chips are relatively



large (typically 1-1.5 inches in  length) are initially reduced to



smaller particle size (2 cm diameter or less)  using  a laboratory




mill.  This  mill is  cleaned  thoroughly  before  each sample  is



introduced.   The pulverized wood sample resulting from  this



operation  is subsampled and  dried using  exactly the  same



procedures described  for sludge  samples in the foregoing Section




II.B.I.



     3.   Ash Samples



     a.    Ash Samples are prepared using  the  same procedures  as



described above for sludge (Section II.B.l.),  with  the exception



that these  samples cannot  be supported on a  screen  to  dry,  and



are therefore placed  into  a  shallow,  flat dish in  order  to dry



them in the  desiccator.  The  ash is  spread  as a  thin layer  over



the bottom of the dish and is gently  stirred periodically during



the drying period.



     4.   Paper Pulp Samples




     a. Remove  the pulp sample  from  the container, and  then



express as much water from the sample as  possible by compressing



it  with  a spatula after wrapping  the sample  in aluminum  foil.
                          C5

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Using the spatula, separate the sample mass into pieces which are



about 2  cm  or  less  in diameter,  and  distribute  these pieces



uniformly on a  stainless steel screen supported about  1  cm  above



a sheet  of  aluminum  foil,  both the  screen  and the  foil  being



placed in  a desiccator.   Allow the sample  to remain in  the



desiccator until it  is essentially dry,  as gauged by color  and



consistency.  For each group  of five pulp samples,  prepare  a



laboratory  blank  using the  procedures  described in  II.B.I.



Proceed with the subsampling  and  other drying procedures,  as



described for sludge samples,  beginning with Section II.B.l.b.



     5.  Slurry-Type  Samples  (Secondary  Sludge,  etc.)



     a.    Shake  the  sample bottle  vigorously  so as to  obtain  a



uniform  suspension  of  the  sample and when the  sample  is



homogeneous throughout, as judged by visual inspection, remove an



aliquot  of the  sample  and subject  it to a Total Suspended  Solids



Determination, as described  in  Standard  Methods  For  the



Examination of   Water and Wastewater,  17th  Edition,  APHA,AWWA,



WPCF, 1986, Method 209C.   Allow the  remainder  of  the  sample to



stand under  refrigeration and when the solids appear to  have



totally  settled to  the bottom  of  the  container,  filter  the



supernatant using a  previously desiccated  and  tared Gelman  Type



A/E  filter  contained  in a glass filtering  funnel.  Remove  the



solids from the sample container using  a  clean  spatula  and



utilize three 100 mL aliquots  of HPLC water  to accomplish  three



successive  rinses  of the sample  container,  and  to effect  a



quantitative transfer  of the  solids  from the sample container to



the  filter.  Following separation of the  water  from  the  solid



remove the solid along with the  filter paper  from the  funnel and





                         C6

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distribute  the  solids and the filter paper  on a stainless steel



screen supported  about  1 cm  above a sheet of aluminum foil, both



the screen  and the foil being placed  in a desiccator.  Allow the



sample to  dry  until it is  friable.    For each  group of  five



samples, prepare a laboratory  blank  using the  procedures



described in II.B.I.   Proceed  with the  subsampling and other



drying procedures described  for  sludge  samples,  beginning with



Section II.B.l.b.  Note that  the tare  weights of all  filters used



in the separation of the liquid and solid phases of these  samples



must be  subtracted  from the combined solids-filter weight to



determine the  actual weights of  the  solids  samples prepared,



since the filter  and solids  cannot be  readily separated.



     6.  Water  and Wastewater Samples



     a.  Clean and  prepare  four new  2 L bottles  fitted  with




Teflon-lined caps.   Mark  the  1  gallon bottle  containing  the



aqueous  sample, as received, to  show the  original  level  of the



liquid in  the  bottle.   Shake the bottle  vigorously until  all



solids in the bottle  (which  may have settled  to the bottom of the



bottle if  the  sample was  undisturbed  for some  time prior to



analysis)   are  suspended,  as  visually  estimated.    Pour



approximately  equal portions of  the  resuspended  aqueous  sample



from the 1 gallon bottle into each of the four 2 L bottles using



a  funnel.  To  accomplish this transfer,  pour small portions from




the  1  gallon bottle into each of the 2  L bottles in succession,




repeating this cycle as many times as necessary  to  dispense all



of  the contents  of the 1  gallon container.    Following  each



pouring  step,  recap the 1  gallon bottle and shake it vigorously
                         C7

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to ensure that  any particulate in the liquid remains suspended.



     b.   After all of  the  contents  of  the 1 gallon bottle  have



been transferred to  the  four 2  L bottles, rinse  the 1  gallon



bottle  successively with  two  50  mL  portions  of  HPLC grade  water,



accumulating these rinses in a 250 mL graduated beaker.  Transfer



one-fourth of each  of these accumulated water rinses  to each  of



the four 2 L bottles.   Rinse  the 250  mL beaker  successively  with



two 40 mL portions of  HPLC water, transferring one-fourth  of



these rinses to each of the four 2 L bottles.  Recap all four 2 L



bottles  and retain for  subsequent extraction and analysis.



     c.    Rinse the  original  1  gallon  empty  sample  bottle



successively with  two 50 mL  portions  of  methylene  chloride,



accumulating these  in the 250 mL beaker used earlier.   Transfer



these methylene chloride  rinses  to a clean 250 mL  bottle  fitted



with a Teflon-lined cap.   Rinse the 250 mL beaker successively



with two  50 mL portions of  methylene  chloride,  and  pool  these



rinses  with  the other  accumulated  methylene chloride  rinses  in



the 250 mL bottle.   Reserve the:  pooled  methylene  chloride  rinses



for later splitting and combination with  the methylene chloride



rinses  collected as described in section III.B.  below.



     d.    Select one  of the  2 L bottles  containing  the  split



water/wastewater sample,  and add to this bottle a solution  of the



13Ci2-labelled TCDD  and  TCDF internal standards,  prepared  by



combining the 20 pL  of  Standard  4310-1  with  1.0 mL  of  acetone  in



a  glass  test tube.   Rinse  the  test tube  with  0.5 mL acetone,



followed by a  second  0.5 mL portion of acetone,  and transfer



these  rinses   to  the  aqueous sample.



     e.   Place a  Teflon-coated,  magnetic  stirring  bar  in  the





                         C8

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sample container, and  stir  the aqueous sample using  a  magnetic



stirplate  for  15 minutes  to  disperse the  spiking  solution.



Position the stem of  a  glass  filtering  funnel to discharge into a



pre-cleaned 5 L round bottom  flask and  place a filter (Whatman 42



filter,  fluted  fold)  into the funnel.



     f.   Decant  and/or pour the  internal  standard-spiked  water



sample  from the 2 L bottle into  the filter  and  collect  the




filtrate in the 5 L  flask.



     g.   Rinse the empty 2  L sample container  sequentially with



three 100  mL aliquots  of HPLC  grade  water,  pouring  each  rinse



through  the filter, and  collecting  the  filtrate in  the  5  L



vessel.  Check  to ensure that  all residual   particulates  and



sediments are removed  from the  original sample container by  the



aqueous rinsing procedure.   Retain  this filtrate  for  subsequent



extraction  using the  procedures  described in Section III.



     h.   Transfer the combined  filter  and  particulate  to a  clean



Petri dish  and place them into  a desiccator.   Allow these solids



to  dry  completely  (as indicated by constant weight  upon



successive  weighings).   Retain  these solids  for  subsequent



extraction  as described in Section IV.B.



     i.   Rinse the  original 2 L sample  container  sequentially



with  three 50 mL aliquots  of   methylene  chloride.   Pour  the



rinsates through the  empty funnel  and  collect in  a clean 1000 mL




glass bottle fitted  with  a  Teflon-lined lid.   Retain  this  for



subsequent  combination  with the  methylene chloride extract of  the



aqueous filtrate,  obtained as described in Section III.
                         C9

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     7.   Exceptional  Samples

     Some  of the  samples  received may  be  too wet to  dry

efficiently in a  desiccator,  but  may  still not contain sufficient

liquid to permit separation  of the  phases  by filtering or other

such  means.   Such samples will  be distributed  on  sheets of

aluminum foil and allowed to air-dry at ambient temperature  on a

bench top.   For  such  samples, the surface area will be  recorded,

so that  a  correction can  be made,  if  this is  necessary,  for

contamination or  cross-contamination of the samples.   The extent

of contamination of such samples  will  be  estimated by placing a

filter paper blank  in the same area where these samples are  air-

dried and  this blank  will  subsequently be analyzed for 2,3,7,8-

TCDD and 2,3,7,8-TCDF.  If  the blank is found to be positive for

these compounds,  the  corresponding  levels  of these compounds in

the samples  will be  corrected for  the levels  detected  in the

blank.


  III.  PROCEDURES  FOR EXTRACTING 2,3,7,8-TCDD AND  2,3,7,8-TCDF
                      FROM  AQUEOUS FILTRATE

     The  internal-standard-spiked,   aqueous  filtrate   resulting

from  application of  the  procedures  described in Section II.B.6.

is extracted utilizing the  following procedures.

     A.  Add 400 mL of methylene  chloride  to  the  aqueous filtrate

contained  in  the 5 L flask  (from the step described  in Section

II.B.S.g.).   Place a magnetic stirring bar  into  the  5 L flask,

place the flask on  a  stir-plate,  and stir  the liquid in  the  flask

for 16 hours.

      B.  Discontinue  stirring  of the contents  of the  5 L flask,

allow the aqueous and organic phases to separate,  then remove the


                         CIO

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organic layer using a pipette,  and place  it in  the  1000 mL bottle

containing the accumulated methylene chloride  rinsates collected

as described in Section II.B.6.1.   At  this  point, also add to the

contents of this same 1000 mL bottle,  one-fourth  of  the methylene

chloride  rinsates  collected as  described  in  Section II.B.6.C.

Retain  the  rest  of  the  latter  rinsate for subsequent splitting

among  the  extracts of the other  three splits of  the original

aqueous sample, if these are subsequently analyzed.

     C.   Sequentially,  repeat the extraction  of the  aqueous

filtrate two additional times using a  100 mL portion of methylene

chloride  each  time,  and combine  each  extract  with the  original

extract in  the  1000  mL bottle.   Reserve this pooled extract for

later combination with the Soxhlet extract of the particulate and

filter, as described in Section IV.


       IV.  PROCEDURES FOR SOXHLET-EXTRACTING 2,3,7,8-TCDD
             AND 2,3,7,8-TCDF FROM DRIED BULK SOLIDS
                 AND FILTERED WASTEWATER SOLIDS

A.  Dried Sludges, Ash Samples, Wood Chips and  Paper Pulp

     Solid  samples  of  these types,  prepared  as  described in

Section II, are extracted using the following procedures.

     1.  Prepare a glass Soxhlet  extraction thimble (90 mm by 35

mm) for use by rinsing it sequentially with methanol,  acetone and

methylene  chloride.   Add silica  to form a 3-6  mm layer on the

surface of the glass frit at the bottom of the  thimble, and place

a 10 mm layer of glass wool over the layer of silica.

     2.   Prepare  a  Soxhlet  extraction  apparatus, consisting of  a

Soxhlet extraction  tube,  a  250 mL Erlenmeyer flask and  a water-

cooled condenser,  for use by rinsing it sequentially  with


                          Cll

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methanol,  acetone,  and  methylene chloride,  and  allowing it  to



air-dry.   Place  175  mL  of a solution consisting of  50%  benzene



and 50% acetone (by  volume), along with about 10 pre-cleaned  2 mm



glass  beads,  into  the  Erlenmeyer  flask.   Place  the Soxhlet



thimble (prepared as described  in Step IV.A.I.)  into the  Soxhlet



extraction tube,  assemble the Soxhlet-extraction  apparatus,  heat



the contents of  the  Erlenmeyer  flask  to  reflux  temperature,  and



continue  the  Soxhlet extraction procedure  for a  period of  3



hours.



     3.  Remove the  heat  source  from the Soxhlet apparatus, allow



the  apparatus  to cool,  and then  decant  the benzene/acetone



solution  into  a  clean,  250 mL  flint  glass  bottle  and seal  the



bottle with a Teflon-lined screw cap.   This solution is retained



in case additional analyses  are  required to check the cleanliness




of the Soxhlet  apparatus,  as a QC measure.



     4.   Place  a fresh  175 mL  aliquot of  50:50  (volume/volume)



benzene/acetone into  the Erlenmeyer  flask  of   the Soxhlet



extraction apparatus and  re-connect the  Soxhlet  extraction  tube



to the Erlenmeyer flask.  Remove  the  layer of  glass  wool from the



glass  thimble.   Transfer  an  accurately weighed  aliquot



(approximately 7-10  grams,  depending upon the sample type)  of the



previously  desiccated solid sample,  prepared as  described in



Section II,  from the sample  bottle containing the dried sample to



the Soxhlet extraction thimble.



     5.   Using a microsyringe,  add  the  appropriate internal



standard  solution (Standard  Solution 4610-1, described in Section



IV.D.I.)  to  the  solid sample  in the Soxhlet  extraction thimble.
                         C12

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Place the previously removed glass wool (Step IV.A.4.)  on top of



the sample  in the glass  thimble. Place  the condenser  on the



Soxhlet extraction  tube  and heat the  solvent reservoir  so that



the extraction solvent refluxes.   Soxhlet extract the sample for



a period of 16 hours, then discontinue heating the apparatus and



allow it to cool  to ambient  temperature.




     6.  Remove  the  Soxhlet extractor  from the  Erlenmeyer flask



reservoir and replace the extractor with a 3-ball Snyder column.




Resume heating the reservoir and concentrate the benzene/acetone



extract to  a  volume of  about  15 mL.   Rinse the  Snyder column



twice with small  quantities  of hexane,  then continue heating and



concentrating the  solution  in  the reservoir with  the  column  in



place until a  final volume  of  10  mL  is attained.



     7.   Using  a  10  mL disposable pipette,  transfer  the




concentrated solution obtained in Step IV.A.6.  to  a pre-rinsed,



125 mL  flint  glass  bottle fitted  with  a  Teflon-lined screw cap.



Rinse  the  Erlenmeyer flask  four  times using 10 mL  aliquots  of



hexane, transferring each rinse solution to the 125 mL bottle,  to



effect  a  quantitative  transfer  of  the  concentrate  from  the



Erlenmeyer flask  to the  bottle.



     8.   Proceed with the  remainder  of  the clean-up  and



analytical procedures described in Section V.



B. Soxhlet Extraction of Water  and Filtered Wastewater Solids



     1.   Remove  the desiccated  filter  and associated  solids



resulting from filtration of a  water/wastewater sample containing



particulates ,  as described  in Section II,  from its sample



container, and immediately  place the  filter  and solids  into  a



Soxhlet  extraction  thimble which  has  been  pre-cleaned,  as






                         C13

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described above in Step IV.A.I.




     2.   Pre-clean a Soxhlet  extraction  apparatus  as described  in



Steps IV.A.2 through IV.A.4.




     3.   Concentrate  the  methylene chloride extract  resulting



from extraction  of  the aqueous  filtrate which has  been pooled



with other methylene chloride rinsates  (obtained as described  in



Section   III.B.)  by  transferring about  150  mL  of  the methylene




chloride extract to  a 250  mL  Erlenmeyer  flask,  attaching  a 3-ball



Snyder column to  the  flask and  heating  the  flask to concentrate



the methylene chloride.  Continue to transfer 150 mL aliquots  of



the methylene  chloride extract  to the  Erlenmeyer  flask  as  each



portion   is  reduced  in volume by concentration, until  the volume



of the  extract  is reduced to about  25  mL.   Then add  150  mL  of



50:50 volume: volume  benzene-acetone to the  Erlenmeyer  flask




containing the residue from  the methylene chloride concentration



and reconnect the flask to tne Soxhlet extractor.    Note that  it



is not  necessary to  spike  this sample  with internal standards



since the wastewater  sample  was previously  spiked with  internal



standards prior to filtering.



     4.    Heat  the Soxhlet apparatus and  extract  the  filter  and



solids  for  a period  of  16  hours, then  discontinue  heating  and



allow the apparatus to cool.   Remove and  concentrate the extract



as described  in Section IV.A.6.  Transfer  the concentrate   to  a



new sample bottle, as described in Section IV.A.7.



     5.    Proceed  with  the remainder  of  the clean-up and



analytical procedures described in Section V.
                          C14

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   V.   PROCEDURES  FOR  ISOLATING  AND  QUANTITATING 2,3,7,8-TCDD
          AND 2,3,7,8-TCDF  PRESENT IN ORGANIC EXTRACTS
           OF PAPER  MILL  PROCESS AND EFFLUENT SAMPLES

A.   Preliminary  Separation  of  2,3,7,8-TCDD  and  2,3,7,8-TCDF
     From Other Chemical Residues in the  Extracts  Obtained As
     Described in  Sections  III,  and  IV.

     Organic extracts  obtained utilizing the procedures described

in Sections III.  and  IV.  are  subjected  to the  f rac tionation

procedures which follow.

     1.   Add  30 mL  of aqueous  potassium  hydroxide  (20%  w/v)  to

the bottle  containing  the  sample  extract,  seal the  bottle and

agitate it for a period of  10 minutes.   Aspirate and discard the

aqueous phase, retaining  the  organic phase.

     2.   If  the aqueous  layer from  the  previous step appears to

be colored  following the base extraction  procedure,  then repeat

this operation (Step V.A.I.).

     3.  Add 30 mL of  double-distilled water to  the organic phase

from Step V.A.I.,  seal the  bottle,  and  agitate the  mixture for a

period of 1 minute.  Again,  aspirate  and discard the  aqueous

phase,  retaining the organic  phase.

     4.  Add 30 mL of  concentrated sulfuric acid to the residual

hexane extract from the previous  step,  seal  the  bottle,  and

agitate  it for a period of 10 seconds.   If  emulsions  form,

centrifuge  the  bottle  to achieve separation of the  organic and

acidic aqueous  phases.   Remove and discard the aqueous acidic

layer,  retaining the organic  layer.

     5.   Repeat  the   concentrated sulfuric  acid  wash  (the

foregoing step) this  time  adding  30 mL of sulfuric  acid to the

sample extract,  and  agitating  the acidified sample  for 10

minutes.   Again, aspirate and discard the aqueous  layer.   Repeat


                         C15

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this step until the  acid  layer  is visibly colorless.

     6.   Repeat Step V.A.3.

     7.   Add  5 g of  anhydrous sodium  sulfate  to  the organic

extract  and allow the mixture ^o stand for at least 15 minutes.

     8.   Quantitatively transfer  the  organic  extract,  using

hexane to  rinse the  sample  bottle,  to a  clean test  tube,  and

reduce the volume to approximately  5 mL by passing  a  stream of

pre-purified nitrogen  over  the extract,  while  maintaining  the

test tube at 55°C in a water  bath.

     9.    Proceed  with the  liquid  column  chromatographic

procedures described in Section V.B.

B.  Liquid  Column Chromatographic Procedures  for Isolating
    2,3,7,8-TCDD and 2,3,7,8-TCDF From Extracts Previously Washed
    with Acids and Bases

     1.   Fabricate a glass  chromatography-columri (20  mm OD x 230

mm  long)  tapered to 6 mm OD  on  one end.   Pack the  column,  in

succession, with a plug of  glass  wool (silanized),  1.0 g silica,

2.0 g silica containing 28%  (w/w)  I  M NaOH, 1.0  g  silica,  4.0 g

silica containing 30% (w/w) sulfuric  acid, and 2.0 g silica.

     2.   Quantitatively transfer  the concentrated extract

obtained in Step V.A.8., along with two rinsings  of  the  sample

container,  using 1 mL portions  of hexane each time,  to the column

and elute  the  column with  90 mL  of  hexane.   Collect  the  entire

eluate and concentrate to  a  volume  of 1-2  mL  in a  centrifuge

tube.

     3.    If  any layer of  the  silica gel  column implemented in

Step V.B.2. becomes visibly colored as the  column is eluted,

repeat Steps V.B.I,  and V.B.2.
                         C16

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     4.   Prepare a liquid chromatography column (11 mm OD  x  120



mm)  by packing the  constricted  end with a plug of silanized glass



wool  and  then adding  three grams of  Woelm  basic  alumina



(previously activated overnight at  600°C  in a muffle  furnace  and



placed in a desiccator for 30 minutes just prior to use).



     5.   Aspirate  the  concentrated extract obtained  in Step



V.B.2. and transfer it  onto the  alumina  column  prepared  in Step



V.B.4.   Rinse the test tube  which  contained the  concentrate



successively with  two 1 mL  portions  of  hexane,  each time



transferring the rinse solution to the alumina column.



     6.    Elute the  alumina  column  as follows:  (a)   Elute  the



alumina  column with  10 mL of  3%  (v/v)  methylene  chloride-in-



hexane,  taking care not  to let the  column  become  completely  dry



during the elution,  and discard the  entire eluate.  (b)   Elute  the



column with 15  mL  of  20% (v/v) methylene chloride-in-hexane  and




discard the entire eluate.  (c)   Elute  the  column with 15  mL  of



50%  (v/v)  methylene  chloride-in-hexane,   retain this  entire



eluate,  and reduce  the volume to  about 1.0 mL by passing a stream



of pre-purified nitrogen over the  solution while  heating  the



solution in a 55°C  water bath.



     7.    Prepare  a second alumina  column  as described  in  Step



V.B.4.,  transfer the concentrated eluate  obtained  in  Step V.B.6.



to the column,  and elute the column as described  in  Step V.B.6.



Collect the column  eluate and concentrate it to a volume  of about



1 mL.



     8.   Prepare a liquid chromatography  column  by cutting off  a



9-inch  disposable  Pasteur  pipette 1.25 cm  above  the  tip



constriction  leaving  a  straight  glass  tube with  an  indentation






                         C17

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approximately 2.5 cm  inch  from the top.  Insert  a filter  paper



disk  in the tube  and position  the disk 2.5  cm below  the



indentation.   Add a sufficient quantity of  PX-21  Carbon/Celite



545 (prepared as described in Section V.C.  of  this  Protocol)  to



the tube to  form a  2  cm length of the Carbon/Celite.   Insert  a



glass wool plug on  top of  the Carbon/Celite.   Pre-elute  the



column sequentially  with 2  mL of.  a 50% benzene/50% ethyl acetate



solution (v/v),  2 mL  of  50%  methylene chloride/50%  cyclohexane,



and 2  mL of  hexane,  and  discard  these  eluates.   Transfer  the




residual sample extract  (in  1  mL of hexane) resulting  from  the



alumina column cleanup  (Step  V.B.7.)  onto  the  top of  the



Carbon/Celite column,  along with  1  mL of a hexane rinse  of  the



original  sample vessel.   Elute  the  column with 2 mL of  50%



methylene  chloride/50% cyclohexane solution  and 2 mL of  50%




benzene/50% ethyl acetate  and discard  these  eluates.  Invert  the



column  and  elute it  in the  reverse  direction  with  4  mL  of



toluene, retaining this  eluate.  Concentrate the collected column



effluent to a volume of  about  1 mL using a stream of pre-purified



nitrogen.



     9.  Prepare a  third alumina  column as described in Step



V.B.4., transfer the concentrated eluate  from the  second alumina




column sequence to this  column, elute  the column,  and collect  the



eluate  as  already  described i:a  Step V.B.6,  in  a  test tube.




Concentrate  the collected eluate  to a  volume of  about 1 mL,  then



quantitatively transfer the concentrate  to  a 3  mL  micro-reaction



vessel  (Reacti-vial) ,  using two  1  mL  portions  of  methylene



chloride to  rinse the test  tube,  and  also  transferring these to
                         CIS

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the micro-reaction  vessel.   Concentrate  the solution in  the



latter vessel  just  to dryness ,  using  a  stream of  dry Nz ,  as



described previously.   Rinse the walls of the  micro-reaction



vessel using 0.5 mL  of methylene chloride,  and again concentrate



just to   dryness.  Seal   the vessel  and store it   in a freezer



(-15°C).   Just  prior  to  GC-MS analysis, remove  the  vessel from



the freezer,  allow  it to  warm to  ambient  temperature,  and



reconstitute  the residue  in the  vessel  by  adding  10  pL  of




Standard 4643-1 to the  vial.






C.  Reagents and Chemicals




     Reagents and chemicals  used in  implementing the procedures



described herein  and the  sources of  these are described in the



following.




     1.  Potassium hydroxide, anhydrous, granular sodium sulfate



and sulfuric acid (all  Reagent Grade):  J.T.  Baker Chemical Co.,



Glen Ellyn,  IL,  or  Fisher Scientific Co.,  Cincinnati,  OH.   The



granular sodium  sulfate  is purified  prior to  use by  placing  a



beaker containing the  sodium sulfate in  a 400° C oven  for four



hours, then  removing  the  beaker and allowing it  to cool  in  a



desiccator.   Store  the  purified  sodium  sulfate  in a bottle



equipped with a Teflon-lined screw cap.



     2.  Acetone, hexane, methylene  chloride,  benzene,  ethyl



acetate,  methanol, toluene,  cyclohexane,  isooctane:   "Distilled



in Glass" Burdick and  Jackson, Muskegon, MI.



     3.  Dodecane and Tridecane (Reagent Grade):   Sigma Chemical



Co., St.  Louis,  MO.




     4.  Basic Alumina (Activity Grade 1):   ICN  Pharmaceuticals,
                         C19

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Cleveland, OH.   Immediately  prior  to use,  the alumina  is

activated by heating for at least 16 hours at 600° C in  a  muffle

furnace and then  allowing  to  cool  in  a  desiccator  for  30 minutes

prior to use.

     5.   Silica  (Bio-Sil  A  100/200  mesh):   Bio-Rad,  Rockville

Centre,  NY.   the  Bio-Sil A  is conditioned prior to  use  by

initially placing a 200  g  portion of  the silica  in a 30 mm  x  30

cm long glass  tube  (the  silica gel is held i/i place by  glass  wool

plugs)  which  is  placed  in a  tube  furnace.   The  glass tube  is

connected to a pre-purified nitrogen cylinder through a series  of

four traps  (stainless  steel  tubes,   1.0  cm  OD  x  10 cm  long)*.

Trap Number 1 contains  a  mixture composed  of  Chromosorb  W/AW

(60/80  mesh coated with 5% Apiezon L) ,  graphite  (100  mesh,  1-M-

USP),  and  activated carbon  (50  to  200  mesh),  in  a  7:1.5:1.5

ratio.   Chromosorb  W/AW  and Apiezon L were obtained from Supelco,

Inc.,  Bellefonte,   Pennsylvania;  graphite  was obtained  from

Ultracarbon Corporation, Bay City, Michigan;  activated  carbon was

obtained from Fisher  Scientific Co.,  Cincinnati,  Ohio.   Trap

Number 2 contains Molecular Sieve 13X (60/80  mesh,  obtained  from

Supelco, Inc., Bellefonte,  Pennsylvania).  Trap Number  3 contains

silica gel impregnated with 309s  (w/w)  sulfuric  acid  (prepared  as

described in V.C.6. below).   Trap Number 4 contains  Carbosieve S

80/100  mesh,  (obtained from Supelco,  Inc.,  Bellefonte,

Pennsylvania) .   The first step in conditioning  the  Bio-Sil A

entails  heating  the glass  tube  containing the  200 g  aliquot  of

silica for 30 minutes  at 180°C while  purging  with nitrogen (flow

*.   See T. J. Nestrick and  L.  L. Lamparski,  Anal.  Chem 53,  122
(1981)  for additional details and rationale regarding use  of
these traps.


                         C20

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rate 50-100 mL/minute),  subsequently  the  tube  is  removed from the



furnace and allowed  to  cool  to  room  temperature.  Methanol  (175



mL)  is then passed through the  tube,,  followed  by  175 mL methylene




chloride.   The tube containing  the silica is then returned  to the



furnace,  the  nitrogen  purge is again  established (50  to 100



mL/minute flow),  the tube is heated at 50°C for  10 minutes, then



the temperature is gradually increased to 180°C over a period of




25 minutes  and maintained at 180°C for  90  minutes.   Heating is



then discontinued but the nitrogen purge  is maintained until the



tube  cools to  room temperature.    Finally,   the  silica  is



transferred to a clean,  dry,  glass  bottle  and capped  with a



Teflon-lined screw cap for storage in  a  desiccator.



     6.   Silica  Gel  Impregnated  with Sulfuric  Acid  (30% w/w) :



Concentrated sulfuric acid (4.4  g)  is  combined with 10.0 g  silica



gel (conditioned  as described above)  in  a screw capped bottle and



agitated  to mix  thoroughly.  Aggregates are dispersed  with a



stirring  rod  until a uniform  mixture is obtained.   The   HzS0«-



silica gel  is  stored in  a  screw-capped  bottle (equipped  with a




Teflon-lined cap).



     7.   Silica Gel  Impregnated with  Sodium Hydroxide: IN  Sodium



hydroxide (30 g)  is combined with  100  g  Bio-Sil A (conditioned as



described above)   in a  screw capped  bottle  and  agitated  to mix



thoroughly.  Aggregates  are dispersed  with a stirring rod until a



uniform mixture is obtained.  The NaOH-silica gel is stored in a



screw-capped bottle (Teflon-lined  cap).



     8.   Carbon/Celite:    A 10.7 g  aliquot of  PX-21  carbon



(Anderson Development Co., Adrian,  Michigan) is combined with 125
                         C 21

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g of Celite 545  (Fisher Scientific Co.)  in a 250 mL glass  bottle,



fitted with  a  Teflon-lined cap,  and  the mixture is  shaken to



obtain a  uniform mixture.  The Carbon/Celite mixture is  stored  in



the screw-capped bottle.



     9.  Nitrogen  {Pre-purified)  and  Hydrogen (Ultra High



Purity):  Airco, Inc., Montvale, NJ.




D.  Calibration and  Spiking Standards



     Stock  standard solutions  of  the  appropriate  TCDD and  TCDF



isomers,  and mixtures thereof,  are prepared  in  a glovebox,  using



weighed  quantities of  the  siuthentic isomers.   These stock



solutions  are contained  in appropriate  amber bottles and are



stored tightly stoppered in  a. refrigerator.  Aliquots  of the



stock  standards are removed  for  direct  use or for  subsequent



serial dilutions  to prepare working standards.   These  standards



must  be  checked  regularly  (by  comparing  instrument  response



factors for  them over a  period  of time)  to  ensure that  solvent



evaporation or other losses have  not occurred  which  would  alter



the standard concentration.  The standard  solutions which may  be



required to perform the quantitative analyses of 2,3,7,8-TCDD and



2,3,7,8-TCDF are listed below.



     1.  Internal Standard  Solution   4610-1.    An  aliquot  of



this  solution is added to samples which  are to be analyzed  for




2,3,7,8-TCDD  and  2,3,7,8-TCDF.  Prepare a stock  solution



containing the following isotopically-labelled  TCDD  and TCDF



compounds  in isooctane  at the  indicated  concentrations:   0.05



ng/pL  *3Ci2-2,3,7,8-TCDD,  0.02  ng/pL  37C14-2,3,7,8-TCDD,  0.05



ng/pL  13Ci2 -2,3,7, 8-TCDF, anci 0.02 ng/pL 3 7 Cl« -2 , 3 , 7 ,  8-TCDF .



Typically  a  twenty  microliter aliquot  of  this  standard solution






                          C22

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is added to each  sample aliquot  prior to preparation  and the



13Ci 2-labelled materials serve as  internal standards  for use in



quantitation.   Recovery of these standards is also used  to  gauge



the overall efficacy of the  analytical  procedure.



     2.  Standard  Solution  4643-1.    Prepare a stock  solution




containing 0.05 ng  of  1 3 Ci 2 -1, 2 , 3 , 4-TCDD and 0.10  ng of 3 7 C14 -



1,2,7,3-TCDF/ML  tridecane.  A  10  microliter   aliquot  of  this




standard is added to the  final  extract obtained for each sample



just prior to GC-MS analysis.   When the DB-5 capillary column is



employed, the *3Ci2-1,2,3,4-TCDD is used as an external  standard



in  the quantitation   of  the 1 a Ci 2 -2 , 3 , 7 , 8-TCDD  and  the *• 3 Ci 2 -



2,3,7,8-TCDF internal standards  present in the final extract, and



the percent  recovery  of  each of  these 13Ci2-labelled  internal



standards  is calculated  on the basis  of  this quantitative



analysis.   The  37C14-1,2,7,8-TCDF  external standard is  employed




in quantitating the concentration  of 13Ci2-2,3,7,8-TCDF  when the



hybrid  DB-5/DB-225  capillary   column  is  implemented  in



quantitating 2,3,7,8-TCDF.  These  latter results are subsequently



implemented  in  calculating the  percent recovery of  the 13 Ci2 -



2,3,7,8-TCDF  internal  standard achieved during the  analysis



performed using the hybrid column.



     3.   Standard  Solutions  4616-1, 4616-2,  4617-1,  and 4617-2.



Prepare  four  separate calibration standards  as  follows:   (a)




Standard 4616-1,  0.2 ng/pL  2,3,7,8-TCDD,  0.2 ng/pL  2,3,7,8-TCDF,



0.05  ng/pL  13C12-2,3,7,8-TCDD,  0.05  ng/uL   J3Ci2-2,3,7,8-TCDF,



0.02  ng/uL  37Cl«-2,3,7,8-TCDD,  0.02  ng/pL   3 *Cl<-2,3,7,8-TCDF,



0.05  ng/pL  13Ci2-1,2,3,4-TCDD and  0.10 ng/pL  37Cl«-1,2,7,8-TCDF;
                          C23

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(b)  Standard 4616-2, 0.05  ngr/pL 2 , 3 , 7 , 8 -TCDD ,  0.05  ng/pL



2,3,7,8-TCDF plus  the same concentration of isotopically-labelled



standards  included in  4616-1;  {c)  Standard  4617-1,  0.01  ng/pL



2,3,7 , 8-TCDD,  0.01 ng/pL 2 , 3 , 7 , 8--TCDF plus  the  same concentration




of isotopically-labelled standards  included in  4616-1;  (d)



Standard 4617-2, 0.0025 ng/pL, 2,3,7,8-TCDD, 0.0025  ng/pL 2,3,7,8-



TCDF plus   the  same concentration  of isotopically-labelled



standards included in  4616-1;  (e)  Standard  4636-1,  2.0  ng/pL



2,3,7,8-TCDD,  2.0  ng 2,3,7,8-TCDF plus the  same concentrations of



isotopically-labelled standards included in 4616-1.  Aliquots of



these standards  are  injected  to  obtain  data which  is implemented



in constructing  the calibration  curve  used  in  quantitating



2,3,7,8-TCDD and 2,3,7,8-TCDF.



     4.   Standard   Mixture   109071-1.     Prepare   an isooctane



solution containing 0.05 ng/pL  concentrations of each of  the



following TCDD  isomers:    1,3,6,8-TCDD;   1,2,3,7-TCDD; 1,2,3,9-



TCDD; 2,3,7,8-TCDD;  1,2,3,4-TCDE  and 1,2,8,9-TCDD.  Two  of  the



isomers  in  this  mixture  are  used   to  define  the  gas



chromatographic  retention time window for  TCDDs  (1,3,6,8-TCDD is



the  first  eluting TCDD  isomer  and  1,2,8,9-TCDD is the last



eluting TCDD isomer on  the  DB-5  GC  column) .   The  remaining



isomers serve to  demonstrate that  the 2,3,7,8-TCDD  isomer is



resolved from the other  nearest eluting  TCDD  isomers, and that



the  column  therefore yields  quantitative  data for the 2,3,7,8-




TCDD isomer  alone.



     5.   Standard  Mixture   4612-2.     Prepare   a  solution



containing  0.250  ng/pL  2,3,7,8-TCDF in  tridecane.  This standard



is implemented when  it  is desired to add only native 2,3,7,8-TCDF






                         C24

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to a sample.

     6.   Standard  Mixture  76179-1.    Prepare   a  solution

containing approximately 0.250  ng/ML  of each  of  the  37 TCDF

isomers (exclusive of 2,3,7,8-TCDF) in isooctane.  This  standard

is used when it is desired to add all of  the TCDF isomers  except

2,3,7,8-TCDF  to a sample.   This  standard is also implemented  to

determine the relative retention  times  of the TCDF isomers  and,

when this  standard  is co-injected  with  an  aliquot  of  standard

4612-2, the efficacy  of  a  particular gas chromatographic  column

for  separating 2,3,7,8-TCDF from  each  of the  37  other TCDF

isomers can be ascertained.

     7.   Standard   Mixtures  4614-1   and  4614-2.   For Mixture

4614-1, prepare a solution  containing  0.025 ng 2,3,7,8-TCDD and

0.025 ng  2,3,7,8-TCDF  per  microliter  of tridecane.   For mixture

4614-2, prepare a solution  containing  0.005 ng 2,3,7,8-TCDD and

0.005 ng  2,3,7,8-TCDF.   These  standards  are employed when it  is

desired to simultaneously add both native 2,3,7,8-TCDD  and  native

2,3,7,8-TCDF to a sample.

E. Gas Chromatographic-Mass Spectrometric (GC-MS) Procedures for
    Quantitating  2,3,7,8-TCDD  and  2,3,7,8-TCDF  Present  in
    Sample Extracts

     Sample extracts prepared by the procedures described  in the

foregoing are analyzed by GC-MS  utilizing the  instrumentation and

operating parameters listed below. Typically, 1 to 5 pL  portions

of  the  extract  are  injected into  the  GC.   Sample  extracts are

initially analyzed using the DB-5  capillary  GC  column  at  a  mass

spectral resolution  of 1:600 to obtain data on the concentration

of 2,3,7,8-TCDD and  to ascertain if 2,3,7,8-TCDF or other isomers
                         C25

-------
which coelute with 2,3,7,8-TCDF are present.   If  the  latter are

detected in this analysis,  then another  aliquot of the sample is

analyzed in a separate  run, using a newly developed hybrid column

which consists  of a 10 meter  length of  a 0.25  mm  I.D.  fused

silica open  tubular  DB-5   capillary  column coupled with  a 30

meter section of a   0.25 mm  I.D. DB-225  column.  Again,  the mass

spectrometer is operated at  low resolution  (1:600).   The hybrid

column uniquely  separates  2,3,7,8-TCDF  from  the  other  37  TCDF

isomers  and therefore yields  definitive data on the concentration

of 2,3,7,8-TCDF  in  the extract which  is  analyzed.  However,  in

some instances compounds are  present  in  the sample extract which

give rise  to  ion  masses which, at low  (1:600)  mass  resolution,

interfere  with the  quantitation  of  2,3,7,8-TCDF.    In  these

instances the analysis  of  the sample  extract can be repeated, at

the option of  USEPA/NCASI, using the  DB-5/DB-225  hybrid column,

but  this  time at a  mass  spectral resolution  of  1:6,500.   The

instrumentation and operating parameters  utilized  in  these

analyses are as follows.


     1.    Gas Chromatograph;    Perkin-Elmer Sigma III  or Varian

3740

          a.   Injector:   Configured  for  capillary column,

splitless/split injection  (split  flow on  60  seconds  following

injection):  injector temperature,  280°C.

          b.  Carrier gas:

               i) For   DB-5  column:   Hydrogen, 30  Ib.  head
                   pressure  (MS-25 jet separator); 18  Ib.  head
                   pressure  (MS-30  direct coupled)
                          C26

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              ii)   For DB-5/DB-225  column:  Hydrogen,  30  Ib.  head
                   pressure  (MS-25  jet separator);  18  Ib.  head
                   pressure (MS-30  direct coupled)

          c.   Capillary Column  1:   For quantitation of  2,3,7,8-

TCDD (isomer  specific)  and 2,3,7,8-TCDF (non-isomer specific), 60

M x 0.25 mm ID fused silica coated  with a 0.25 micron film of DB-

5, temperature programmed,  see  Table  1 for temperature  program.

Capillary  Column  2:   For quantitation of  2,3,7,8-TCDF  (isomer

specific),  10 M x  0.25 mm ID fused silica  column  coated with  a

0.25 micron film of DB-5 coupled with  a 30  M x 0.25 mm  I.D. fused

silica  column coated  with a 0.25  micron  film of  DB-225.  This

column  is  temperature  programmed as indicated  in   Table  2.

          d.   Interface Temperature:   250°C

     2.  Mass Spectrometer:  Kratos MS-30 or Kratos MS-25

          a.   lonization Mode:   Electron impact  (70 eV)

          b.   Static  Resolution:   1:600 (10%  valley)  or  1:6,500

depending upon instrumentation.

          c.   Source Temperature:   250°C

          d.   Accelerating  Voltage:   2KV  or 4KV, depending upon

instrument.

          e.   Ions  Monitored:   Computer controlled Selected Ion

Monitoring, See Tables  1  and 2  for list of ion masses  monitored

and time  intervals  during which ions  characteristic of  2,3,7,8-

TCDD and  2,3,7,8-TCDF  are monitored.    Note that  in  the  case of

quantitation  of  the   2,3,7,8-TCDF,  the  hexachlorinated

diphenylether molecular ion, which could give  rise to an

interference at m/z  304  and 306,  is also monitored as  indicated

in Table 2.
                          C27

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     3.   Calibration  Procedures:



          a.   Calibrating the MS Mass Scale:  Perfluorokerosene,



decafluorotriphenyl  phosphine,  or any other accepted mass marker



compound must be  introduced  into the MS,  in  order  to calibrate



the  mass  scale  through at  lea.st m/z  350.     The procedures



specified by  the  manufacturer  l:or the  particular  MS instrument



used are to be employed  for  this purpose.   The  mass calibration



should be rechecked  at  least  at  8 hr.  operating intervals.




          b.   Table  1 shows the  GC temperature program typically



used  to  resolve  2,3,7,8-TCDD  from each of  the  21 other  TCDD



isomers  and  indicates  the  ion-masses  monitored  and the  time



analytical sequence  implemented  for isomer  specific quantitation



of 2,3,7,8-TCDD and  non-isomer  specific quantitation of 2,3,7,8-



TCDF. This temperature  program  and ion monitoring time cycle must



be established by each  analyst  for the particular instrumentation



used by injecting aliquots of Standard Mixture 109071-1,  as well



as the calibration mixtures (4616-1,  4616-2, 4617-1, and 4617-2)



into  the GC-MS.   It  may be  necessary to adjust  the temperature



program and  ion monitoring  cycles  slightly based  on  the



observations from analysis  of these mixtures.



          c.   Checking GC Column Resolution for 2,3,7,8-TCDD and



2,3,7,8-TCDF:  Utilize Standard  Mixture 109071-1 to check the DB-5




column resolution for 2,3,7,8-TCDD, and utilize  a combination of



Standards  4612-2 and  76179-1  to  verify that 2,3,7,8-TCDF  is




separated from all of the other TCDF isomers on the hybrid DB-5/



DB-225 column.  A 25% valley  or  less must be obtained between the



mass chromatographic peak observed for 2,3,7,8-TCDD and adjacent



peaks arising from other TCDD  isomers and  similar separation of






                         C28

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2,3,7,8-TCDF  from other neighboring TCDFs is required.  Analyze



the  column  performance  standards using the  instrumental



parameters specified above  and  in Table  1  and 2.   The column



performance  evaluation must be  accomplished  each time  a new



column is installed  in the gas chromatograph,  and at the



beginning and conclusion  of  each 8 hour operating period.  If the



column resolution is  found  to be insufficient to resolve  2,3,7,8-




TCDD and 2,3,7,8-TCDF from their neighboring  TCDD and  TCDF



isomers,  respectively,  (as  measured on  the two  different columns



used  for resolving   these  two isomers),  then  a new  DB-5 and/or



DB-5/DB-225 hybrid GC column must be installed.



          d.   Calibration  of  the  GC-MS-DS system to  accomplish



quantitative  analysis of  2,3,7,8-TCDD and 2,3,7,8-TCDF  contained



in the sample extract is  accomplished by analyzing a series  of at



least  three working  calibration standards.  Each of  these



standards is prepared  to contain  the same concentration of each



of  the  *3 Ci 2 -2,3,7,8-TCDD  and  *•3Ci 2-2,3,7,8-TCDF  internal



standards used here  but  a  different  concentration of  the native



2,3,7,8-TCDD  and 2,3,7,8-TCDF.   Typically, mixtures  will  be



prepared so  that  the  ratio  of  the  native 2,3,7,8-TCDD and



2,3,7,8-TCDF  to  the isotopically-labelled TCDD/TCDF  ranges



between  0.05 and  4.0 in  the four  working  calibration mixtures.



Prior to injecting aliquots  of actual sample extracts,  an aliquot



of a standard containing typically 0.2  ng of *3Ci2-1,2,3,4-TCDD



and  0.4  ng of  3 7 Cl< -1, 2,7 , 8-TCDF  (Standard 4643-1)  is  used  to



dilute the extract  in the  sample vials  and  is therefore co-



injected along with the sample extract,  in order to obtain data
                         C29

-------
permitting calculation of the percent  recovery  of the  13 Ci2 -



2,3,7,8-TCDD  and *3Ci2-2,3,7,8-TCDF internal standards.  When the



analysis of  the extract  is  performed  using the  DB-5  capillary



column, the  *• 3 Ci 2 -1, 2 , 3 , 4-TCDD standard is implemented  as  the



external standard  in  quantitating  both  1 3Ci 2-2,3,7,8-TCDD  and



13Ci2-2,3,7,8-TCDF.   However,  when the  hybrid DB-5/DB-225 column



is employed in analyzing the 2,3,7,8-TCDF,  the 37C14-1,2,7,8-TCDF



is implemented  in quanitiating  the  1 3Ci2-labelled TCDF internal




standard.   Equations  for  calculating relative  response  factors



from the calibration data derived  from  the calibration standard



analyses,  and for calculating the  recovery of the l aCi 2-2,3,7,8-



TCDD and  1 3 Ci 2 -2 , 3 , 7 , 8-TCDF ,  as  well  as the  concentration  of



native  2,3,7,8-TCDD  and 2,3,7,8-TCDF  in  the  sample  (from  the



extract analysis),  are  summarized  below.



     Daily checks  of  the  imstrument  performance  will  be



accomplished using Standard 4617-1.   This standard will  be



injected at  the  beginning of  each  work-day (or the beginning of



each 8-hour  shift)  and  RRF  values for  2,3,7,8-TCDD and 2,3,7,8-



TCDF will  be  calculated.  If  either  of  these RRF values deviate



from the values  contained in  the  calibration curve by  more than



+20%, then a second injection will be made and  RRF values  for the



two compounds will be  again calculated.   If either of  these RRF




values  also fail to agree  with the calibration  curve by more than



±20%,  then the  entire  series  of  calibration  standards  will  be



analyzed,  new  RRF values  will  be   calculated, and  a  new



calibration  curve will  be constructed  and applied in subsequent



analyses.
                          C30

-------
4.  Equations  Used for Calculating  Analytical  Results
   from the GC-MS Data

a.   Equation  1:   Calculation of  Relative Response Factor for
                   native  2,3,7,8-TCDD  (RRF2)  using   13Ci2-
                   2 , 3,7,8-TCDD  as an  internal  standard.
    RRF2  =

    where:
(AsCis /Ai sCs )

As
= SIM  response for 2,3,7,8-TCDD ion at
  m/z 320 + 322
              At s   = SIM response  for  * 3 Ci 2 -2 , 3 , 7 , 8-TCDD  internal
                     standard ion  at m/z 332 + 334
Ci
                   = Concentration of  the  internal  standard
                   = Concentration of  the  2,3,7,8-TCDD  (pg./pL.)
b.  Equation 2: Calculation of Relative Response Factor for
                   13Ci2-2,3,7,8-TCDD  (RRFb)
            RRFb

      where:  At


              Ae


              Ci
    = (Al s Ce s /Ae s Cl s )

    =  SIM response for 1 3Ci 2-2,3,7,8-TCDD
       internal standard ion at m/z 332 + 334

    =  SIM  response for J3Ci2-1,2,3,4-TCDD
       external standard at m/z 332 +  334

     =   Concentration  of the  1 3 Ci 2 -2 , 3 , 7,8-TCDD
       internal standard (pg./pL.)

     =   Concentration of the  13 Ci  2-1 , 2 , 3,4-TCDD
       standard (pg./jjL.)
                          C31

-------
c.   Equation 3:    Calculation of concentration of  native 2,3,7,8-
                  TCDD using *3Ci2-2,3,7,8-TCDD as internal
                  standard

Concentration,  pg./g.  = (As)  (Is)/(Ais)(RRFz)(W)

    where:    As   = SIM response for 2,3,7,8-TCDD  ion at
                    m/z 320 + 322

              Ais  = SIM  response  for  the  A3Ci2-2,3,7,8-TCDD
                    internal standard ion at m/z 332  + 334

              Is   = Amount  of  internal standard added  to  each
                    sample (pg.)

              W   = Weight of sample in grams

           RRFz    = Relative response factor from  Equation  1

d.   Equation  4:    Calculation  of % recovery  of  * 3 Ci 2-2 , 3 , 7 , 8-
                   TCDD internal standard

     % Recovery = 100(At• ) (E» ) / (At» ) (Ii ) (RRFb)

              Ais   = SIM response for *• 3 Ci 2 -2, 3, 7 , 8-TCDD
                     internal standard ion at m/z  332 + 334

              Aes   = SIM response for *3Ci2-1,2,3,4-TCDD
                     external standard ion at m/z  332 + 334

              Es    = Amount of l3Ci2-1,2,3,4-TCDD  external
                     standard co-injected with sample extract

              Ij    = Theor'etical amount  of  l 3 Ci  2 -2 , 3 , 7 ,  8-TCDD
                     internal standard in injection

           RRFb     = Relative response factor from Equation 2
                          C32

-------
e.   Equation  5;   Calculation of  Relative  Response Factor for
                   native 2,3,7,8-TCDF  (RRFc ) using * 3 Ci 2 -
                   2,3,7,8-TCDF as an internal standard.
RRFc =

where:
        (As Ci s /Ai 9Cs )

        As
                   = SIM  response for 2,3,7,8-TCDF ion at
                     m/z 304 + 306
              At s   = SIM response for l 3 Ci 2 -2 , 3 , 7 , 8-TCDF internal
                     standard ion at m/z  316 + 318

              Ci s   = Concentration of the internal standard
                     (pg./pL. )

              Cs   = Concentration of the 2,3,7,8-TCDF  (pg./gL.)
f.  Equation 6:  Calculation of Relative Response Factor for
                 1 3 Ci 2 - 2,3,7,8-TCDF  (RRFd)  (When  analysis  is
                 performed using DB-5 Column)
      RRFd

where:  Ai s
                  =   (AlsCes /AesCls )

                  =  SIM response for l 3 Ci 2 -2 , 3 , 7 , 8-TCDF
                     internal standard ion at m/z 316 + 318

                  =  SIM  response for * 3 Ci 2 -1 , 2 , 3 , 4-TCDD
                     external standard at m/z 332 + 334
              Ci s  = Concentration of  the * 3 Ci 2 -2 , 3 , 7 , 8-TCDF
                     internal standard  (pg./pL.)

              Ce s  = Concentration  of  the l 3 Ci 2 -1 , 2 , 3 , 4-TCDD
                     external standard  (pg./pL.)
   Equation  7:     Calculation   of  Relative Response  Factor for
                   1 3C12 -2,3 ,7, 8-TCDF  (RRFe )   (When  analysis is
                   performed using DB-5/DB-225 Hybrid Column)

    RRFe  =   (Al s Ce s /Ae s Cl s )

    where Ai s  =   SIM response for * 3 Ci z -2 , 3 , 7 , 8-TCDF
                   internal standard ion at m/z 316 + 318

          Aes  =   SIM response for 3 7 Cl< -1 , 2, 7 , 8-TCDF
                   external standard at m/z 312

          Ci s  =   Concentration of the 1 3 Ci 2 -2 , 3 , 7 , 8-TCDF
                   internal standard  (pg/pL)

          Ces  =   Concentration of the 3 7 C14 -1 , 2 , 7 , 8-TCDF
                   external standard  (pg/pL)
                          C33

-------
h.  Equation 8:




Concentration, pg

    where:     As



              Al 3
              W

           RRFc

i.   Equation  9:



     % Recovery =

              Ais
           RRFd

j.  Equation 10;




     % Recovery

          AlB
          Es
          RRFe
 Calculation  of  concentration  of  native  2,3,7,8-
 TCDF  using L3Ci2-2,3,7,8-TCDF as internal
 standard

./g. = (As)  (Is )/(Ai3 ) (RRFc ) (W)

 =  SIM response  for  2,3,7,8-TCDF  ion  at
   m/z 304 +  306

 =  SIM  response  for  the  l 3 Ci 2  -2 , 3 , 7 , 8-TCDF
   internal standard ion at m/z 316 +  318

 =  Amount of internal  standard added  to each
   sample  (pg.)

 =  Weight  of  sample  in grams

 =  Relative response factor from  Equation  5

  Calculation  of %  recovery  of  l3Ci2-2,3,7,8-
  TCDF  internal standard (When analysis  is
  performed using DB-5 Column)

 100 (Ais ) (Es )/(Aes ) (Ii ) (RRFd )

  = SIM response for *3Ci2-2,3,7,8-TCDF
    internal  standard ion at m/z  316  + 318

  = SIM response for *3Ci2-1,2,3„4-TCDD
    external  standard ion at m/z  332  + 334

  = Amount of *•3Ci2-1,2,3,4-TCDD  external
    standard  co-injected with  sample  extract

  = Theoretical amount  of *3 Ci  2 -2 , 3 , 7,8-TCDF
    internal  standard in injection

  = Relative  response factor from Equation  6

 Calculation  of  % recovery of  *3Ci 2-2,3,7,8-TCDF
 internal  standard  (when analysis is performed
 using hybrid DB-5/DB-225 column

 =  100 (Ais) (Es)/(Aes) (It)  (RRFe)

=  SIM  response  for  J3Ci2-TCDF internal
    standard  ion at m/z 316 +  318

 =  SIM response for 37C14-1,2,7,8-TCDF  external
    standard  ion at m/z 312

 =  Amount of 37Cl4-1,2,7,8-TCDF  external
    standard  in injection

 =  Relative  response factor from Equation  7
                          C34

-------
     5.   Criteria Applied  for  Qualitative  Identification  of



            2,3,7,8-TCDD and 2,3,7,8-TCDF



          a.   Mass  Spectral responses  must  be observed  at  both



the molecular and fragment ion masses  corresponding to the  ions



indicative of TCDD and  TCDF  (see  Tables  1  and  2)  and  intensities



of these ions must maximize  essentially simultaneously  (within  +



1 second).   In  addition,  the  chromatographic retention times



observed  for 2,3,7,8-TCDD  and  2,3,7,8-TCDF  must be  correct



relative to the  appropriate stable-isotopically labelled internal



standard.




          b.   The ratio of the  intensity of  the response  for  the



molecular ion,  [M] * ,  to the response for the  [M+2]+  ion  must be



within ±15%  of  the  theoretically expected  ratio  for  both the



native TCDD  and  native TCDF  signals  (for example,  0.77  in  the



case of TCDD and TCDF;  therefore, the  acceptable range for  this



ratio is 0.65 to 0.89).




          c.   The  intensities of the  ion  signals for  either



2,3,7,8-TCDD  or  2,3,7,8-TCDF  are considered  to be  detectable if



each exceeds the  baseline noise  by  a  factor of at least  2.5:1.



          d.     For reliable  detection  and quantitation of



2,3,7,8-TCDF, it is also necessary to  monitor the  molecular  ion



of  hexachlorinated  diphenyl  ether which,  if present,  could give



rise to fragment  ions  yielding  ion masses  identical  to those



monitored as indicators of the  TCDF.   Accordingly, in  Tables  1



and 2, the appropriate ion-mass for hexachlorinated  diphenyl




ether  is  specified  and  this  ion-mass  must be  monitored



simultaneously with the 2,3,7,8-TCDF ion-masses.   Only  when the
                         C35

-------
response for the diphenyl ether ion-mass is not detected  at  the



same time as  the  2,3,7,8-TCDF  ion  mass  can the signal  obtained



for 2,3,7,8-TCDF be  considered unique.



F.   Quality  Assurance/Quality Control Procedures




     1.   The Quality Assurance and Quality Control  procedures



itemized below will be  implemented throughout the course  of  the



Dioxin I analyses:




          a.   Each sample  analyzed  is  spiked  with  stable



isotopically-labelled  internal standards, prior to  extraction  and



analysis.  Recoveries  obtained for each of these standards  should



typically be in the range  from  40-120%.   Since these  compounds



are used as  true internal standards however,  lower  recoveries do



not necessarily invalidate the analytical results  for native



2,3,7,8-TCDD and 2,3,7,8-TCDF, but may result in higher  detection



limits than  are desired.




          b.    Processing  and analysis of  at least one  method



blank sample is generally accomplished for each set  of samples.



          c.   It  is  desirable  to analyze at  least  one   sample



spiked  with representative native TCDD/TCDF for each set  of



samples.  The results  of this einalysis  provides  an  indication of



the efficacy of the entire  analytical procedure.  The results of



this  analysis  will be  considered  acceptable if the  detected



concentration of the native  2,3,7,8-TCDD and  2,3,7,8-TCDF  added



to  the  sample is within +.50%  of  the  known  concentration.



     d.   At  least  one  of the  samples  analyzed  out of  each  set is



usually analyzed in duplicate  and  the results of the  duplicate



analysis are included  in the report of data.



     2.   A  report  describing  the  results of  the  analyses






                         C36

-------
discussed above will,  at  a minimum,  include  copies  of original



mass  chromatograms  obtained  during  analyses  of  the  sample



extracts and associated calibration  standards,  a  description of



the  analytical methodology  employed,  and  tabulations  of



calculated results.   Calculations  and manipulation  of  data are



most efficaciously  accomplished using computerized data reduction



techniques.   The tabulations  of calculated  results  provided in



the  report  will  include  a  set  of  tables   showing  the



concentrations  of  2,3,7,8-TCDD  and  an additional  set  of tables



showing the concentrations of  2,3,7,8-TCDF which were measured in



each sample. Also  shown  in the tables are  the  quantity of each



sample  analyzed; the detection  limits  for  those  samples which



were found to contain no  2,3,7,8-TCDD or 2,3,7,8-TCDF;  the GC-MS



instrument implemented in the analysis;  the date and time of the



analysis; the ratio of the intensities of m/z  320 vs. m/z  322 and



m/z 332 vs.  m/z 334  for  TCDD  and the ratio of the intensities of



m/z 304 vs.  m/z 306 and m/z 316 vs.  m/z 318 for TCDF; the  percent



recovery of  the  internal  standard  (l3Ci2-2,3,7,8-TCDD  or 1 3Ci 2 -



2,3,7,8-TCDF);  and  the ion  intensities for  the  following m/z's:



320, 322, 257,  332  and 334  for  TCDD,  and  304,  306,  241,  316 and



318 for  TCDF.  Examples of  typical  tables  of the  type  described



above  are  provided in Attachment  A. Other  tabulations  of data



shown  in Attachment  A which will  be provided in  the  report



include  a table showing  a summary of  the calibration  data




obtained for 2,3,7,8-TCDD and  2,3,7,8-TCDF,  which show the date



of  the calibration;   the  GC-MS  instrument  implemented;  the  WSU



identification  number of  the calibration solution;  the calculated
                         C37

-------
response factors and the mean response factors obtained for



native 2,3,7,8-TCDD, native 2,3,7,8-TCDF, l3CL2-2,3,7,8-TCDD and



13C 12-2,3,7,8-TCDF; and the \ valley observed for the GC separation



of the 2,3,7,8-TCDD from adjacent-eluting TCDD isomers and of the



2,3,7,8-TCDF from adjacent-eluting TCDF isomers.   A typical



calibration summary presentation  is provided in Attachment A.



Additional tables which present calibration data and results



obtained for each individual sample in a more detailed manner



than that  given in the summary  tables mentioned earlier are also



shown in Attachment A.
                              C2,8

-------
                                                                      I    I    I    I
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r->
  *• x:
c"-»
    C3
pt*  »~O
o


o  tr>
va co
c=»
 I   t~3
v» «c
bd      •*-!
                                                                                                                o>  ••-«
                                                                                                                «n  AJ
                                                                                                                <0  wt
                                       CO  Ul  *->
                                               C39

-------
                     *-»  o>      ac
                     rt»  O      *—*
                     a  .«-H  »»-i   • •
                    -.-I  *_>   C3  ,

                     b  i~.   o  sc*
                     »»i  O  ••-*  —•
                     o. a>  -»->

                    -e  E-«  o«5   o
        O  03
             C=3
        as  i-^-
        C^  "•»
        =3  >-•
        O*  BC
<^a
        va  -a:
CO     Q
wU      I   O>
CO     V>  SE
.-<     as  •—t
E-*      I   «o
        <-J  =D
        «>
             CO
        as  to
                         • •-*        d       k«
                                                                                                4>       *-»
                                                                                            ca  6-«       at
                                                                                                 a>      AJ
                                                                   C40

-------
                       ATTACHMENT A
REPRESENTATIVE TABLES OF DATA OBTAINED IN DIOXIN I ANALYSES
                         C41

-------
                                               ririsnt  State univsrsitv. Davrop.  C"iio    •»;»55

                                Ses'jits  or  3C/T5 flrialyse; of Extracts  for  2. 3. 7. 6-TerraunioroDiDeri:o-:3-3:oxi.'i
                                 Corceritratioris Founa  (oicocrs'ss 2er nrsn  of ssmoie or aarts-ser-triiiion;
                                                D65 Column ilsoreer £cec:f:c for 2,3.7.3 TCiw)


                       Ccr.c.  "euro
             *ei:nt          :':'~         I.istr.            Ion Irr.  -atios    *  c.            Ion Intensities  a. 2.
              o  a.    re;;.     rC'C  3.     ID   Date  Tiue 313/3; 2  332/33-*  Sec.        323       322       2f7

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DF32-313      5.53J       l/.a            p£2frt 331237 l'3:-»2  3. 5J     3.75    7i.5    4. 5H-?5  5. 6*E^o5  3. 35E-I-35  3.23E+K  4. r-fE+K

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  a.   For natsr ==r;o:°s tr>= wirni of tne saaioie aiicuo: was caicuiatBo  bv muuiaiving tne  vo!'ri« of wa*sr anaiv:eo bv l.K~f&.
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         Src:ccoi for refer=nc2 co Total SuscerDeo Sohcs Detersinationi,  an  ahc'jot  of -rts ariea soiia  w=s tnen removea  ~-T^~
         wei:ne'3 Dr:or  1:0 araiysis.

  D.   .^DC = fliniswa Cetectaois Ccncsntration

  c.   % Sec. = Percent  recovEry for 13C12-2. 3.7. 3-TCDD internal  star-tare

  o.   The rio:£:iori  used here  ro ^esicnate ion intensifies  is e.xcoreritiai notation.  Trie ntwcer oreceairiO E snouic ce rauuir'-iea
         oy a factor of 13 raiseo to tne cower of trie nuraoer  foiicwinn £.   inerefore tne cssinnation 7.6i£-35 idc:cates 7c3. >r^.

  e.   (\ necative sicn  orscecino tne oeaK intensity value cited  iraicates tnat no response was ooserveo  at tnat ;n/; v.nicn  eyr~C3  tne
         noise  isvei DV a factor of 2.5 or greater.  The r.u'noer  foiiomng tne /"iS^ative sinri is tne ooserveo TOISS level at :*a: w:.
                                                         C42

-------
                                                            TABLE  2



                                               origin 5tar,e univ5rs:v/.  Davton. Cmo    "f-^S

                                 xesuirs of rC/iTS ^.isivses of Extra-is for 2. 3. 7. 3-7etraCnio'"oiMren:cr|.ir3n
                                 Concentrations ro'jnc loicoaraMS  :er sraro of siraote or  oarts-cer— iniiionj
                                                                D55 Co i 'jcn


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i-PB ?L.c>;n     l'3.i''3      ND       3,465   r£5f.n 331537 13:35           i'.ai   63.5     -9.9E+33  -i.tE^  -4. l£+t'-»   5.5i£i-3b  6.i;£-v5S

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                                                          C43

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                                                        C44

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                                               C45

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                                                             TABLE  5
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-------
                                                              TABLE 12
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                                                          C47

-------
                                                             TABLE  29
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           78
                                                             TABLE  30
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                                                           C48

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                    TABLE 39
    WRIGHT STATE UNIVERSITY, DAYTON, OHIO 45435

ADDITIONAL DATA RESULTING FROM ANALYSES OF SAMPLES
          FOR EPA/NCASI PAPER MILL STUDY
EPA
I.D.
DF024603
DE020920
DF024513
RGI-S6357
Sample
Type
Sludge
Sludge
Sludge
Slurry
% Moist
As Rece
5.8
61.7
83.3
—
                                              Total
                                         Suspended Solid
                                               5188  mg/L
                   C49

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                   ATTACHMENT D






        NCASI METHODS FOR THE ANALYSIS OF




CHLORINATED PHENOLICS IN PULP INDUSTRY WASTEWATERS

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ncasl
technical bulletin
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT. INC, 260 MADISON AVENUE. NEW YORK. N.Y. 10016
    NCASI METHODS FOR THE ANALYSIS OF CHLORINATED PHENOLICS



           IN PULP INDUSTRY WASTEWATERS
            TECHNICAL BULETIN NO, 498








                JULY 1986



                 Dl

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                                  D2
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT, INC.
260 MADISON AVE. NEW YORK, N.Y. 10016 (212) 532-900(1
                                                              Russell O. Blosser
                                                              Technical Director
                                                               (212) 532 9001
                                        July 25, 1986
    TECHNICAL BULLETIN NO.  498
         NCASI METHODS  FOR THE ANALYSIS OF CHLORINATED PHENOLICS
         	IN PULP INDUSTRY WASTEWATERS	
         Analytical  measurement method development  and  evaluation
    represents a significant portion of the National Council  program.
    The attached  technical  bulletin is  another on  this subject  and
    deals with methods for analysis  of chlorinated phenolics in pulp
    industry wastewaters.

         The  first technical  bulletin  on this  subject was issued as
    Stream  Improvement Technical Bulletin  No.  347.   This technical
    bulletin reflects  the  improvements in the method made since then.
    It  discusses  the  modifications  made to the  original  procedures
    and why these were required.

         The  bulletin  includes  (a)  the revised  gas  chromatographic
    procedure  for  analysis  of chlorophenols in water and  (b)  an im-
    proved  gas  chromatographic/mass  spectrometer  procedure  which
    permits identification of six additional compounds of interest.

         The  laboratory investigation  of these procedures  and prepa-
    ration  of  the  technical  bulletin was carried  out by Lawrence E.
    LaFleur, Organic  Analytical  Program Manager.   He  was assisted by
    Mr. Kenneth Ramage.  Both  are  located  at the West Coast  Regional
    Center.

         Your comments and questions on the contents of  this  bulletin
    are solicited  and should  be directed  to  this office  or  to  Mr.
    LaFleur,  NCASI   West  Coast  Regional   Center,   P.O.  Box  458,
    Corvallis, OR 97339, telephone  503-754-2015.
                                         ours very truly,
                                        Russell 0. Blosser
                                        Technical Director
    ROB:mh
                        CN«on« Count* at (• Pip«r kvtuMry to, A, **} SMm ImprcMiranl toe 1

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                              D3

                        TABLE OF CONTENTS

                                                            Page

  I  INTRODUCTION                                             1

 II  DISCUSSION OF NCASI METHOD  CP-85.01                      1

     A.    Scope and Application                                1

     B.    Reagents                                            1

     C.    Sample Preservation                                 2

     D.    Procedure Modifications Due to Matrix Effects       2

     E.    Calibration                                         2

     F.    Quality Control                                     2

III  DISCUSSION OF NCASI METHOD  CP-86.01                      3

     A.    Scope and Application                                3

     B.    Acetylation Procedure                                4

     C.    GC/MS Analysis Procedure                            4

 IV  SUMMARY AND FUTURE STUDIES                                5

  V  LITERATURE REFERENCES                                    5

APPENDICES:

     APPENDIX A:  NCASI Method CP-85.01                     A-l
                  CHLORINATED PHENOLICS IN WATER BY
                  IN SITU ACETYLATION/GC-ECD DETERMINATION

     APPENDIX B:  NCASI Method CP-86.01                     B-l
                  CHLORINATED PHENOLICS IN WATER BY
                  IN SITU ACETYLATION/GC/MS DETERMINATION

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                                D4
      NCASI METHODS  FOR THE ANALYSIS OF CHLORINATED PHENOLICS
                   IN PULP INDUSTRY WASTEWATERS
                        I   INTRODUCTION

     As part of NCASI's ongoing methods development and evalua-
tion program, the procedures used for the analysis of chlorinated
phenolic compounds characteristic of bleached pulp mill effluents
have been continually improved and refined since the original
method evaluations were reported in Technical Bulletin No. 347
(1).  The purpose of this report is to provide analysts with a
revised method which reflects the improvements which have been
incorporated into the earlier procedure, thereby bringing them up
to date with current practices.  The following section highlights
some of the changes.  Appendix A presents NCASI Method CP-85.01
in standard methodology format.

     It also became apparent that a GC/MS confirmation method
would be desirable, particularly when NCASI Method CP-85.01 was
applied to new matrices.  Section III of this report discusses
the modifications to the in situ acetylation which were required
to adapt the method for GC/MS analysis.  The procedure, NCASI
Method CP-86.01, is presented in standard methodology format in
Appendix B.

            II   DISCUSSION OF NCASI METHOD CP-85.01

A.   Scope and Application

     NCASI Method CP-85.01 reflects an expansion in scope and
application both in terms of the number of analytes and the
types of matrices to which it has been applied.  The increased
number and diversity of analytes was in part due to the availa-
bility of standards (initially by in-house synthesis, more
recently through commercial suppliers) but mostly to provide
data necessary to evaluate and monitor the environmental signifi-
cance of the wider array of sample matrices being analyzed.
Information needs pertaining to environmental samples which have
undergone anaerobic degradation prompted inclusion of certain
chlorinated phenols which aren't normally found in bleach pulp
mill effluents.  The additional chlorinated guaiacols and
catechols and the chlorinated benzaldehydes resulted from a
desire to better characterize bleach pulp mill effluents.  The
specific method modifications or adaptations required to accommo-
date the expanded scope are discussed below.

B.   Reagents

     The chlorinated benzaldehyde compounds (i.e. chlorovanill-
ins, chlorohydroxybenzaldehyde and chlorosyringaldehyde) were
found to form hemi-acetals when stored for prolonged periods in
alcohol solvents such as methanol.  Thus, Method CP-85.01 calls
for preparation of stock solutions of these analytes in acetone

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                               D 5
and that working solutions be made up fresh just prior to use
and be subsequently discarded.  This short exposure to tnethanol
has not presented any problems.

C.   Sample Preservation

     Sample and extract preservation studies showed that with
acidification to a pH of two with I^SO*, samples stored refriger-
ated for up to 30 days showed no significant changes in analyte
concentrations.  The data documented storage up to that length of
time but did not indicate 30 days was an upper limit.  Storage
beyond this time would have to be supported with additional
information.  Similarly, refrigerated extracts were found to be
stable over a 30 day period.

D.   Procedure Modifications Due To Matrix Effects

     One problem encountered with some of the different matrices
resulted from the inherent buffering capacity of the sample.
The normal carbonate buffer added to the sample failed to raise
the pH adequately enough to insure ionization of some of the
weakly acidic analytes resulting in low recoveries.  To resolve
this problem, the pH of the sample is adjusted to 11.6 with 5
percent NaOH following the addition of the carbonate buffer.
This provides both the desired final pH and buffering capacity.

     Other matrix problems can be minimized by using a smaller
aliquot of the sample and adjusting to the final volume with
reagent water.  This is required when the concentrations of
analytes exceed the linear range of the GC-ECD but also is an
option to minimize matrix effects.  It should be recognized that
this directly influences detection limits.

     The sample preservation requirements had to be modified to
include addition of sodium thiosulfate to remove residual
chlorine, particularly in bleach plant process stream samples.

E.   Calibration

     The single point calibration procedure described in Techni-
cal Bulletin No. 347 was abandoned in favor of a six point
calibration curve.  Although the calibration procedure is
definitely more time consuming, it substantially improved the
accuracy.  A daily calibration check was added to the quality
control plan to test the validity of the calibration curve.

F.   Quality Control

     A table summarizing NCASI quality control (QC) data has been
included to provide guidelines of what method performance might
be anticipated.  Many of the replicate analyses in the QC data
set were at or near the detection limit, so the reported relative
percent differences reflect method performance over the entire

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                                D6
working range of the procedure.  Generally, relative percent
differences of less than 15 to 20 percent can be expected with 35
percent being a suggested upper control limit.

     The replicate determination requires that the analyte be at
measurable levels in order to provide the data to estimate the
precision, so, for many compounds which are not commonly encount-
ered (i.e. 3,5-dichlorophenol, 3,4-dichlorophenol, 2,3,6-tri-
chlorophenol, etc.) there is little data available.  Recovery
determinations do not suffer from this limitation and the
summary data provided in the method gives a much better estimate
due to the larger number of data points.  In general, recoveries
of 90 to 100 percent can be expescted for chlorophenols, chloro-
guaiacols and chlorinated benzaldehyde type compounds with the
relative standard deviations of the recoveries of these compounds
ranging from 15 to 25 percent.  Chlorocatechol recoveries are
more in the range of 70 to 80 percent with relative standard
deviations of 22 to 37 percent.

     Both the replicate data and the recovery summaries show
that the chlorocatechols remain the most difficult group of
compounds to quantify.  The chlorovanillins also seem to cause
problems, but this may be due to lesser experience since they
were the last group of analytes incorporated into NCASI Method
CP-85.01.  The lower sensitivity of the monochloro- and dichloro-
compounds of all classes of compounds makes their detection and
quantification more difficult thus giving rise to generally
lower precision and recovery.

            Ill   DISCUSSION OF NCASI METHOD CP-86.01

A.   Scope and Application

     NCASI Method CP-86.01 was developed to provide a means of
qualitatively confirming compound identifications while semi-
quantifying the concentrations.  The method as presented has not
been used as extensively as NCASI Method CP-85.01 and therefore
the performance characteristics are not as well documented.  For
this reason, the scope of the method has been limited to semi-
quantitative.  This does not imply that the concentration data
obtained by NCASI Method CP-86.01 is inaccurate, just that the
precision and accuracy of the method has not been well docu-
mented.

     The lower sensitivity of the electron capture detector for
compounds with a single chlorine atom prevents their analysis by
NCASI Method CP-85.01.  The higher selectivity of a GC/MS
analysis and adjustments made to make up for the inherently
lower sensitivity of the mass spectrometer operated in the full
scan mode allows the scope of NCASI Method CP-86.01 to be
extended to include mono-chloro compounds.  The ability to
quantify compounds which are not chromatographically separated
through the use of extracted ion current techniques further
allows the scope of the method to be expanded.  Thus, six addi-

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                               D 7
tional compounds can be detected and semi-quantifled by NCASI
Method CP-86.01.

B.   Acetylation Procedure

     The lower sensitivity of a GC/MS compared to an BCD required
that the sample volume be increased in order to achieve similar
detection limits.  Thus, three 100 mL portions were acetylated
in situ, extracted with three portions of hexane and the hexane
extracts were combined and concentrated prior to analysis.  It
was felt that this approach more closely approximated the
acetylation procedure used in NCASI Method CP-85.01 and would be
less likely to cause problems due to unforeseen difficulties.  It
also provided a simple means for the analyst to increase or
decrease the sample size to accommodate individual sensitivity
requirements without raising questions about the applicability of
the in situ acetylation and/or extraction on larger sample
volumes.

     The quantitation technique used in NCASI Method CP-85.01
does not require quantitative recovery of the analytes since the
internal standard is spiked into the sample prior to acetylation
and extraction.  This effectively corrects for recovery.
However, in the case of the GC/MS procedure, it was considered
beneficial to improve the absolute recovery of the analytes to
further help improve sensitivity.  This was accomplished by
combining three sequential hexane extracts from each acetylated
sample aliquot prior to concentration.

     Since the quantitation technique still relies on the
calibration procedure mimicking the sample analysis procedure,
appropriate modifications in the procedures for the preparation
of the GC/MS calibration standards were incorporated into the
method.

C.   GC/MS Analysis Procedure

     A 30m DB-5 fused silica column was used for the analysis,
not because of improved chromatography, but as a compromise to
minimize overhead time required to change columns.  All other
in-house GC/MS analyses routinely performed in our laboratory
utilize a DB-5 column and since relatively few chlorophenolic
conformational analyses are required and the DB-5 column provided
adequate separations, there seemed to be no reason not to use
it.  Therefore, for at least those analytes listed in NCASI
Method CP-85.01 which are chromatographically separated, either
a DB-5 or a DB-1 column could be used for GC/MS analysis.  A less
sophisticated gas chromatograph temperature program had to be
used due to the software limitations of the HP-5993 GC/MS data
system.  Analysts should use their own judgement in making any
changes in the recommended temperature program.  Any changes
deemed appropriate should be relatively straightforward and, with
appropriate documentation through quality assurance, should not
alter the applicability of the method.

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                               D 8
                 IV   SUMMARY AND FUTURE STUDIES

     NCASI Methods CP-85.01 and CP-86.01 as presented in Append-
ices A and B represent the culmination of NCASI laboratory
method evaluations and refinements.  Although vigorous or formal-
ized ruggedness testing has not been conducted, analysts skilled
in trace environmental analyses should be able to conduct the
procedure and, with appropriate quality assurance documentation,
generate reliable data.

     The Methods have essentially been subjected to single
laboratory validation studies.  It is hoped that through distri-
bution of these procedures that other laboratories will become
familiar with the methods.  The inevitable positive feedback can
be incorporated into improved protocols.  This will set the stage
for critical interlaboratory validation studies.  Upon completion
of those studies, the performance characteristics of the Methods
should be fully determined.

     The results of such an intercalibration study were recently
described by Starck, et.al.(2).  The procedure used was quite
similar to NCASI Method CP-85.0L.  The authors reported that
recoveries of greater than 80 percent were generally achievable
for analyte concentrations above 20 ppb.  Below this concentra-
tion, the recoveries ranged from 60 to 70 percent.  As is consis-
tent with NCASI Method CP-85.01 performance characteristics, the
chlorocatechols were found to exhibit the highest variabilities
in the recoveries reported.  However, this study relied heavily
on spiked water (presumably reagent water) data.  The relative
standard deviation of the chlorocatechol results for the waste
water sample was 40 to 54 percent and the recoveries of these
analytes were 0 to 10 percent.  Thus, there remain significant
matrix effects which have not been resolved by their methodology.

     Future interlaboratory studies should cover a wider range
of analytes (the study mentioned above only discussed six
compounds), address the preparation and accuracy of calibration
standards and cover as wide a range of matrices and concentra-
tions as possible.  The resulting data will then complement the
study described above and complete the documentation of the
methods performance characteristics.

                    V   LITERATURE REFERENCES

(1)  "Experience With the Analysis of Pulp Mill Effluents for
     Chlorinated Phenols Using an Acetic Anhydride Derivatization
     Procedure," NCASI Technical Bulletin No. 347 (June 1981).

(2)  Starck, B., Bethge, P.O., Gergov, M., Talka, E., "Determina-
     tion of Chlorinated Phenols in Pulp Mill Effluents - An
     Intercalibration Study," Paperi ja Puu - Papper och Tra, 12,
     745-749 (1985).

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                 D9
               APPENDIX A

                  NCASI

             METHOD CP-85.01

    CHLORINATED PHENOLICS IN WATER BY
IN SITU ACETYLATION/GC-ECD DETERMINATION

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                                D10
                              NCASI

                         METHOD CP-85.01

                CHLORINATED PHENOLICS IN WATER BY
            IN SITU ACETYLATION/GC-ECD DETERMINATION
1.0  Scope and Application

     1.1  Method CP-85.01 is used to determine the concentration
of chlorinated phenols, chlorinated guaiacols, chlorinated
catechols and chlorinated benzaldehydes (i.e. vanillins, and
syringaldehyde) in water samples.  Specifically, Method CP-85.01
can be used to determine:
Chlorinated Phenols

3,5-dichlorophenol
3,4-dichlorophenol
2,6-dichlorophenol
2,4-dichlorophenol
2,3,6-trichlorophenol
2,4,6-trichlorophenol
2,4,5-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol

Chlorinated Guaiacols

4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
Chlorinated Catechols

3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol

Chlorinated Benzaldehydes

6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde

Miscellaneous Compounds

trichlorosyringol
     1.2  This method has been used to analyze untreated and
biologically treated pulp mill effluents, landfill leachates and
receiving waters and bleach plant effluents.

     1.3  The method has been found unsuitable for groundwater
samples which contain high levels of non-chlorinated phenols
(i.e. creosote contamination) or samples where pentachlorophenol
and/or 2,3,4,5-tetrachlorophenol are present and are suspected
to have undergone anaerobic degradation.

     1.4  When Method CP-85.01 is used to analyze unfamiliar
samples, quality assurance duplicates and recovery samples
should be run and compound identifications should be supported
by qualitative GC/MS.

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                                 Dll
2.0  Summary of Method

     2.1  Method CP-85.01 provides in situ derivatization,
extraction and gas chroraatographic conditions for the detection
of ppb levels of chlorinated phenolics.  Samples are neutralized,
spiked with the Internal Standard, then buffered with K^CO^ in
order to form the phenolate ions which are then converted in
situ (i.e. in the aqueous matrix) to their acetate derivatives
by the addition of acetic anhydride.  The chlorophenolic acetates
thus formed are extracted with hexane.  A 1 uL to 2 uL portion
of the hexane extract is injected into a gas chromatograph using
a Grob type splitless injection technique and is chromatographed
on a fused silica capillary column using electron capture
detection.  The standards used to determine the calibration
curve are prepared by spiking the Internal Standard and the
appropriate levels of analytes into blank water and then analyz-
ing in the same manner as the sample.

     2.2  The Internal Standard used in the method 3,4,5-tri-
chlorophenol has been identified as a persistent anaerobic
degradation product of 2,3,4,5-tetrachlorophenol and/or penta-
chlorophenol.  Other workers analyzing samples containing these
compounds which have been subjected to anaerobic conditions have
substituted 2,6-dibromophenol as the Internal Standard.

     2.3  The sensitivity of Method CP-85.01 usually depends on
the level of interferences rather than on instrumental limita-
tions.  The lower detection (LDL) and lower quantitation limits
(LQL) listed in Table 1 represent sensitivities that generally
can be achieved in biologically treated effluent with some
degree of reliability and confidence.  Actual detection limits
would have to be determined on each sample.

     2.4  Additional compounds can be determined by CP-85.01 but
have not been validated on the above mentioned sample matrices.
Chromatographic data for these compounds is given in Table 2.

3.0  Interferences

     3.1  When Method CP-85.01 was applied to groundwater samples
collected in the vicinity of a source of creosote, (i.e. wood
preservation plant) the high levels of non-chlorinated phenols
caused poor recoveries and the method was unsatisfactory.

     3.2  The Internal Standard, 3,4,5-trichlorophenol, has been
shown by some researchers to be a persistent anaerobic degrada-
tion product of 2,3,4,5-tetrachlorophenol and pentachlorophenol.

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                                 D12
      TABLE 1        CHROMATOGRAPHIC CONDITIONS, DETECTION
                      LIMITS AND QUANTITATION LIMITS FOR
                METHOD CP-85.01 IN TREATED PULP MILL EFFLUENTS


Compound
Relative
Retention
Timea'b

L:DLC
(ug/L)

LQLd
(ug/D
2,6-dichlorophenol
2,4-dichlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,4,6-trichlorophenol
2,4,5-trichlorophenol
2,3,6-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol
4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
trichlorosyringol
                               0.526
                               0.564
                               0.592
                               0.661
                               0.738
                               0.864
                               0.818
                                 164
                                 646
1,
I,
                               0.956
                               1,
                               1,
                               1,
  086
  380
  469
                               1.723
                                ,109
                                ,262
                               1.337
                               1.494
                               1.673
                               1.991
                               1.207
                               1.567
                               1.636
                               1.777
ND
3.0
ND
ND
1.2
1.2
ND
0.8
0.6
3.5
3.5
0.6
0.6
0.6
ND
ND
3.0
ND
1.5
1.0
ND
ND
ND
ND
ND
5.0
ND
ND
2.4
ND
ND
1.5
1.0
7.0
7.0
1.5
1.0
1.0
ND
ND
5.0
ND
4.0
2.5
ND
ND
ND
ND
ND
a
c
d
Not Determined
Retention times of acetate derivatives relative to
3,4,5-trichlorophenol acetate
15 m x 0.25 mm I.D. fused siilica DB-1, 0.25 micron film
thickness.  Helium carrier (p. = 31  cm/sec at 125°C)
90 percent argon/10 percent, methane detector make-up gas (30
mL/min).
Oven programed from 45°C after a one mimite hold at 15°C/
min to 100°C and then at 2°C/min to 165° then 20°C/min to
230°C.  Under these conditions the retention time of
3,4,5-trichlorophenol aceta.te is 17.080 minutes.
LDL Lower Detection Limit
LQL Lower Quantitation Limit
Method CP-85.01 would have to be modified appropriately when
applied to samples suspected of containing these compounds and
having undergone anaerobic degradation.  Other workers have used
2,6-dibromophenol as an alternative Internal Standard.

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                                D13
            TABLE 2   ADDITIONAL CHROMATOGRAPHIC DATA

                                             Relative
                                             Retention
	Compound	                           Time

4-chlorophenol                                 0.415
2,5-dichlorophenol                             0.564
2,3-dichlorophenol                             0.612
5-chlorovanillin                               1.160
2,6-dibromophenol                              0.826
trichloro-3-methyl catechol                    1.877
4-chlorocatechol                               0.924
3,4-dichloroguaiacol                           0.973
3,5-dichloro-4-hydroxybenzaldehyde             1.456


     3.3  Blanks most frequently are contaminated with penta-
chlorophenol.  Generally this has been traced to the KTCC^ and
has been removed by baking the reagent at 400°C+ overnight.  All
reagents should be tested for contamination prior to use.

     3.4  All glassware should be washed with hot detergent
water, air dried and then baked at 400°C for 6-8 hours.  Volu-
metric pipets should be washed in an alcoholic - KOH bath and
then rinsed thoroughly with tap water before air drying.

4.0  Apparatus and Materials

     4.1  Glassware:

     125 mL separatory funnel
     100 mL beaker
     50 mL graduated cylinder
     Volumetric pipets (TD)
     2 dram vials with Teflon-lined screw caps
     Centrifuge tubes with Teflon-lined screw caps

     4.2  pH Meter:  Calibrated using two point procedure

     4.3  Gas Chromatograph:  Analytical system complete with
gas chromatograph suitable for splitless capillary injection,
electron capture detector, electronic integrator and recording
device.

     4.4  Chromatography Column:  15m x 0.25 mm I.D. fused
silica DB-1 (0.25 u film thickness).

     4.5  Centrifuge

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                                D14
5.0  Reagents

     5.1  Hexane:  Distilled in glass; Methanol:  Distilled
reagent grade.

     5.2  Acetic anydride:  Redistilled reagent grade.

     5.3  Reagent water:  Organic free such as produced by a
Barnstead Model D2798 NANOpure-A water purification system.

     5.4  Sodium Hydroxide:  5 percent w/w in reagent water.

     5.5  Sulfuric Acid:  Mix one part concentrated H2SO4 with
four parts reagent water.

     5.6  Potassium Carbonate:  Dissolve 150g ^003 (purified by
heating at 400°C for 6 to 8 hours in a shallow tray) in 250 mL
reagent water.

     5.7  Internal Standard Stock Solution:  Weigh (to the
nearest 0.1 mg) 25 +3 mg of 3,4,,5-trichlorophenol and dissolve
to volume with methanol in a 50 mL ground-glass-stoppered
volumetric flask.  Transfer the stock solution into an amber
bottle with a Teflon-lined screw cap and store under refrigera-
tion (4°C).

     5.8  Internal Standard Spiking Solution:  Pipet 5.0 mL of
the stock solution into a 100 mL ground-glass-stoppered volu-
metric flask and dilute to volume with methanol.  Transfer the
spiking solution into five ca 20 mL portions in separate Teflon-
lined screw capped vials, number 1-5 and store under refrigera-
tion (4°C).

     5.9  Calibration standard stock solutions:  Individual
stocks are prepared by dissolving the amounts of the analyte
indicated in either Table 3 or .4 (+3 mg weighed to the nearest
0.1 mg) in the indicated solvent in 50 mL ground-glass-stoppered
volumetric flasks.  Combined secondary dilution stocks are
prepared by pipetting the volumes of the individual stock
solutions indicated in Table 3 and 4^ into separate 50 mL ground-
glass-stoppered volumetric flasks and diluting to volume with
the solvents indicated.  The final working solution of the
calibration standard is prepared by pipetting 5.0 mL of each of
the secondary dilution stock into a 25 mL ground-glass-stoppered
volumetric flask and diluting to volume with methanol.  All
stock solutions and secondary dilutions are transferred into
amber bottles with Teflon-lined screw caps and are stored under
refrigeration  (4°C).  The working solutions are discarded after
use.

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                                D15
     5.10 Calibration Curve Standards:  The calibration curve
standards are prepared by spiking s-eparate 50.0 mL portions of
reagent water with 25 uL of the Internal Standard spiking
solution and 25, 50, 75, 100, 125, and 150 uL portions of the
final calibration working solution.  The resulting solutions are
then acetylated and extracted in a manner exactly analogous to
the samples.
               TABLE 3
  METHANOL STOCK SOLUTIONS
      Compound
  mg in
50 mL Stock
2,6-dichlorophenol           4 0
2,4-dichlorophenol           40
3,5-dichlorophenol           40
3,4-dichlorophenol           40
2,4,6-trichlorophenol        40
2,4,5-trichlorophenol        40
2,3,6-trichlorophenol        40
2,3,4,6-tetrachlorophenol    40
pentachlorophenol            10
4,6-dichloroguaiacol         4 0
4,5-dichloroguaiacol         40
3,4,5-trichloroguaiacol      40
4,5,6-trichloroguaiacol      40
tetrachloroguaiacol          40
3,6-dichlorocatechol         40
3,4-dichlorocatechol         40
4,5-dichlorocatechol         40
3,4,6-trichlorocatechol      40
3,4,5-trichlorocatechol      40
tetrachlorocatechol          40
trichlorosyringol            40
  mL in
Secondary
 Dilution

    2
    2
    2
    2
    1
    1
    1
    1
    1
    2
    2
    2
    2
    2
    2
    2
    2
    2
    2
    2
    2
Secondary
Solution
  ng/uL

  32.0
  32.0
  32.0
  32.0
  16.0
  16.0
  16.0
  16.0
   2.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
  32.0
               TABLE 4
  ACETONE STOCK SOLUTIONS
      Compound
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
   mg in
50 mL Stock

     40
     40
     40
    mL in
  Secondary
  Dilution

     2
     2
     2
   Secondary
   Solution
    ng/uL

     32.0
     32.0
     32.0

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                                D16
6.0  Sample Collection, Handling and Preservation

     6.1  Samples should be collected in glass containers and
all portions of automatic sampling equipment which come in
contact with the sample should be constructed of glass, Teflon
or stainless steel.   Composite samples should be refrigerated
during the sampling period.

     6.2  The samples must be iced or refrigerated from the time
of collection until acetylated.

     6.3  A portion of the sample should be tested for free or
residual chlorine.  Add 35 mg of sodium thiosulfate per ppm free
chlorine per liter.   Adjust the sample pH to approximately two
using sulfuric acid.  Record the volume of acid used on the
sample identification tag so the sample volume can be corrected
later.

     6.4  All samples must be acetylated within 30 days and be
completely analyzed within 30 days after acetylation.

7.0  Procedures

     7.1  Sample Preparation

          7.1.1  In Situ Acetylation:  Remove the sample from
     the refrigerator and allow it to come to room temperature.
     Shake the sample vigorously to insure it is homogeneous and
     then measure out an appropriate aliquot.  If less than 50
     mL of sample is used, bring the final volume up to 50 mL
     with reagent water.  Neutralize the sample to pH 7.0 to 7.1
     using 5 percent NaOH and 1:4 sulfuric acid.  Add 1.3 mL of
     the potassium carbonate solution and adjust the pH to 11.6
     ±0.1 with 5 percent NaOH if necessary.

          Transfer the sample to a 125 mL separatory funnel and
     spike it with 25 uL of the Internal Standard spiking
     solution.  Shake the sample to insure thorough mixing.  Add
     1.0 mL of acetic anhydride and shake the sample with
     frequent venting for 30 seconds.  Let the sample stand for
     5 minutes then shake and vent.

          Add 5 mL of hexane and shake vigorously for 1 to 2
     minutes with frequent venting.  Allow the phases to separate
     and drain and discard the aqueous portion.  If there is an
     emulsion problem, drain the organic layer into a centrifuge
     tube, cap and centrifuge for two to three minutes or until
     the emulsion is broken.  Transfer as much of the hexane as
     possible into a vial with Teflon-lined screw cap, label and
     refrigerate until analyzed.

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                                D17
     7.2  The recommended gas chromatographic column and operat-
ing conditions for the instrument are:  15m x 0.25 mm I.D. fused
silica DB-1,  0.25 micron film thickness.  Helium carrier gas
(u = 31 cm/sec at 125°C)/ 90 percent argon/10 percent methane
detector make-up gas (30 mL/min).  The injection port temperature
is 210°C and the oven is programed from an initial temperature of
45°C after a 1 minute hold at !5°C/min to 100°C and then 2°C/min
to 165°C then 20°C/min to 230°C.  The Ni63 detector is operated
at 300°C.

     The injection port is configured for a Grob type splitless
injection with a 30 second purge activation delay.

     7.3  Calibration

          7.3.1  Calibration Curve:  Establish gas chromato-
     graphic operating parameters equivalent to those indicated
     in Section 7.2.  Using 1 \iL splitless injections of the
     calibration curve standards, tabulate the ratio of the area
     of the analyte divided by the area of the Internal Standard
     data against the concentration of the analyte.  Using these
     data, calculate the linear regression and tabulate the
     slope and intercept data.

          This procedure should be repeated whenever the daily
     calibration check is out of range, the instrument has not
     been used or has been down, a new column has been installed,
     etc.

          7.3.2   Daily Calibration Check:  The working calibra-
     tion curve must be verified on each working day by the
     measurement of one or more calibration standards.  If
     the concentration of any analyte based on the current
     calibration curve varies by more than +20 percent, the test
     must be repeated at a different concentration level.  If
     this value is also out of range, a new calibration curve
     must be prepared.

     7.4  Sample Analysis

          7.4.1   Sample extracts are analyzed using the gas
     chromatographic operating conditions indicated in Section
     7.2.  Peak integration parameters and area reject thresholds
     should be set such that the sensitivities indicated in
     Table 1 (Section 2.3) can be achieved.

          7.4.2   Inject 1 uL of the sample extract using
     the Grob type purged splitless injection technique.  If the
     peak areas of the identified analytes exceed the linear
     range of the instrument, a separate smaller aliquot of the
     sample should be acetylated, extracted and analyzed.

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                                 D18
     7.4.3     Calculate the concentration of the analytes
using the following equation:
                             (As)  (Vo) (ms)

                               (AIS) x 50
Concentration =	+ bs
     where:    As  =  area of the analyte
               AIS  =  a*"ea of the internal standard
               Vo  =  volume of sample acetylated (in mL)
               ms  =  slope from calibration curve for analyte
               ^s  =  intercept from calibration curve for
                      analyte.


8.0  Quality Control

     8.1  Blanks:  Before processing any samples or whenever a
new reagent is prepared, the analyst should demonstrate through
the analysis of a reagent water blank that utilizes all glassware
and reagents required for sample analyses that all materials are
interference free.  The blank samples should be carried through
all stages of the sample preparation and measurement.

     8.2  Frequency:  Approximately 12 to 15 percent of routine
samples should be allocated for quality control.  In addition to
this, representative samples from each new or untested source or
sample matrix should be treated as a quality control sample.
Laboratory replicates and fortification should be conducted on
each QC sample to document method performance as indicated by
precision and recovery.

     8.3  Replicates:  Replicates; consist of running two or more
separate aliquots of the sample through the entire analytical
procedure.  The range and mean concentration of the replicates
are determined from the results.  The relative percent difference
is calculated as follows:
          Relative Percent Difference = 100
                                  (range\
                                  mean j
Table 5 summarizes the relative percent differences measured by
the NCASI laboratory and gives ari indication of the precision of
the method.

     8.4  Recovery:  Using the mean concentration determined by
the replicate analyses, determines a spiking level which will
give a minimum of three times the background.  Spike an aliquot
of the sample with the determined amount of the calibration
standard working solution and proceed to analyze the sample in
the normal manner.  Using the results of that analysis, calculate

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                                 D19
the percent recovery as follows:
           .  _           Level Measured - Background
     Percent Recovery =  	Level Spiked *	
                           x 100
     where the background is the mean of the replicate determina-
     tions described above.

Table 5 summarizes the percent recoveries measured by the NCASI
laboratory and gives an indication of the accuracy of the method.

      TABLE 5   SUMMARY OF THE NCASI LABORATORY QA/QC DATAa
     Compound
2,6-dichlorophenol
2,4-dichlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,4,6-trichlorophenol
2,3,6-trichlorophenol
2,4,5-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol

4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol

3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol

6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
trichlorosyringol
      Relative
 Percent Difference
 x(n)bMaximum
                  Percent
                  Recovery
                 c   Rel.S.D,
 2.1
 7.6
 2.8
10
 4.7

 5.8
10.5
 7.8

13.2
 8.2
 5.9
 7.1
 6.3

11.4

12.6
10.3
 9.5
11.5

11.7
13.4
18.9
 5.5
(5)
(22)
(3)
(2)
(26)
(1)
(4)
(26)
(18)

(12)
(12)
(32)
(28)
(33)

(4)
(1)
(21)
(12)
(29)
(24)

(14)
(17)
(5)
(31)
 8.3
27.2
 8.3
20.0
17.5

13.3
31.3
30.0

27.7
31.9
28
27
,1
 3
28.0

16.7

32.2
24.0
34.1
26.7

33.3
33.3
30.0
31.0
108
106
108
104
 98
106
114
 96
104

104
103
 95
 95
 91

 83
 91
 80
 70
 78
 76

108
 94
 98
 91
             13.3
             14.1
             10.6
             14.8
             21.7
             10.4
             17.5
             15.8
             18.5
19.0
18.6
19,
10,
  ,6
  ,6
18.1
             37.7
             35.9
             31.0
             22.3
             36.9
             36.0

             25.5
             14.6
             25.6
             24.6
*  QA/QC data up to 6/86 included in summary
b  n = number of determinations

     8.5  Where doubt exists over the identification of a peak
on the chromatograph, confirmatory techniques such as mass
spectrometry (e.g. NCASI Method CP-86.01) should be used.

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                  D20
               APPENDIX B

                  NCASI

             METHOD CP-86.01

CHLORINATED PHENOLICS IN WATER BY IN SITU
     ACETYLATION/GC/MS DETERMINATION	

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                               D21
                              NCASI

                         METHOD CP-86.01

            CHLORINATED PHENOLICS IN WATER BY IN SITU
                 ACETYLATION/GC/MS DETERMINATION	
1.0  Scope and Application

     1.1  Method CP-86.01 is used to qualitatively confirm and
semi-quantitate the concentration of chlorinated phenols,
chlorinated guaiacols, chlorinated catechols, and chlorinated
benzaldehydes (i.e. vanillins and syringaldehydes) in water
samples. Specifically, Method CP-86.01 can be used to confirm or
determine:
     Chlorinated Phenols

     2-chlorophenol
     4-chlorophenol
     3,5-dichlorophenol
     3,4-dichlorophenol
     2,6-dichlorophenol
     2,4-dichlorophenol
     2,3,6-trichlorophenol
     2,4,6-trichlorophenol
     2,4,5-trichlorophenol
     2,3,4,6-tetrachlorophenol
     pentachlorophenol

     Chlorinated Guaiacols

     4-chloroguaiacol
     4,5-dichloroguaiacol
     4,6-dichloroguaiacol
     3,4,5-trichloroguaiacol
     4,5,6-trichloroguaiacol
     tetrachloroguaiacol
 Chlorinated Catechols

 4-chlorocatechol
 3,6-dichlorocatechol
 3,4-dichlorocatechol
 4,5-dichlorocatechol
 3,4,5-trichlorocatechol
 3,4,6-trichlorocatechol
 tetrachlorocatechol

Chlorinated Benzaldehydes

6-chlorovanillin
5-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
3,5-dichloro-4-hydroxy-
  benzaldehyde

Miscellaneous Compounds

trichlorosyringol
     1.2  This method has been used to analyze untreated and
biologically treated pulp mill effluents and bleach plant process
streams.

     1.3  When CP-86.01 is used to analyze unfamiliar samples,
quality assurance duplicate and recovery samples should be
run.  Method CP-86.01 is intended to complement Method CP-85.01,
Chlorinated Phenolics In Water By In Situ Acetylation/GC-ECD
Determination,

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                                 D22
2.0  Summary of Method

     2.1  Method CP-86.01 provides in situ derivitization,
extraction and gas chromatographic conditions for the detection
of ppb levels of chlorinated phenolics. Samples are neutralized,
spiked with the Internal Standard, then buffered with potassium
carbonate in order to form the phenolate ions which are then
converted in situ (i.e. in the aqueous matrix) to their acetate
derivatives by the addition of acetic anhydride. The chloro-
phenolic acetates thus formed are extracted with hexane. A 1
to 2 uL portion of the hexane extract is injected into a gas
chromatograph using a Grob type splitless injection technique and
is chromatographed on a fused silica capillary'column using mass
spectrometric determination. The standards used to determine the
calibration curve are prepared by spiking the Internal Standard
and the appropriate levels of analytes into blank water and then
derivatizing in the same manner as the sample.

     2.2  The Internal Standard used in the method 3,4,5-tri-
chlorophenol has been identified as a persistent anaerobic
degradation product of 2,3,4,5-tetrachlorophenol and/or penta-
chlorophenol. Other workers analyzing samples containing these
compounds which have been subjected to anaerobic conditions and
are using a similar in situ acetylation GC-ECD procedure have
substituted 2,6-dibromophenol as the Internal Standard.

     2.3  The sensitivity of Method CP-86.01 depends on both the
level of interferences in the matrix and on the sensitivity of
the GC/MS.  Generally, low ppb detection limits can be achieved
in most samples.  Actual detection limits would have to be
determined on each type of matrix.

3.0  Interferences

     3.1  When a similar procedure (NCASI Method CP-85.01) was
applied to groundwater samples collected in the vicinity of a
source of creosote, (i.e. wood preservation plant) the high
levels of non-chlorinated phenols caused poor recoveries and the
method was found unsatisfactory.  It is likely that Method
CP-86.01 would be subject to the same limitation, although no
tests have been run to confirm this.

     3.2  The Internal Standard, 3,4,5-trichlorophenol, has been
shown by some researchers to be a persistent anaerobic degra-
dation product of 2,3,4,5-tetrachlorophenol and/or pentachloro-
phenol.  Thus, Method CP-86.01 would have to be modified appro-
priately when applied to samples suspected of containing these
compounds and having undergone anaerobic degradation.  Other
workers have used 2,6-dibromophenol as an alternative Internal
Standard in similar in situ acetylation GC-ECD procedures.

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                               D23
     3.3  Blanks most frequently are contaminated with penta-
chlorophenol.  Generally this has been traced to the potassium
carbonate and has been removed by baking the reagent at 400°C
overnight.  All reagents should be tested for contamination prior
to use.

     3.4  All glassware should be washed with hot detergent
water, rinsed, air dried and then baked at 400°C for 6-8 hours.
Volumetric pipets should be washed in an alcoholic KOH bath and
then rinsed thoroughly with tap water before air drying.

4.0  Apparatus and Equipment

     4.1  Glassware

          250 mL  Separatory funnel with Teflon stopcock
          250 mL beaker
          100 mL graduated cylinder
          Volumetric pipets (TD)
          Centrifuge tubes:  35 mL  with Teflon lined screw cap
          Centrifuge tube:  15 mL graduated conical with ground
                            glass stopper
          2 dram vials with Teflon-lined screw caps
          Concentrator tube, Kuderna-Danish: 15 mL
          Evaporative flask, Kuderna-Danish: 250 mL, attach to
            concentrator tube with springs
          Snyder column, Kuderna-Danish: three-ball macro

     4.2  pH Meter: Calibrated using two point procedure

     4.3  Centrifuge:  Bench top model

     4.4  Evaporation/concentration assembly:  Pierce 19797
Uni-Vap Evaporator or equivalent.

     4.5  Water bath:  Constant temperature capable of tempera-
ture control (+ 2°C).  The bath should be used in a hood.

     4.6 Gas Chromatograph/Detector System

          4.6.1  Column:  30 m x 0.25 mm bonded-phase fused
     silica DB-5 capillary column (J&W Scientific DB-5 or
     equivalent).

          4.6.2  Mass Spectrometer:  Capable of scanning from 35
     to 450 amu every 1 sec or less, utilizing 70 volts (nomi-
     nal) electron energy in the electron impact ionization mode.
     A computer system must be interfaced to the mass spectro-
     meter capable of allowing the continuous acquisition and
     storage on machine-readable media of all mass spectra
     obtained throughout the duration of the chromatographic

-------
                              D24
     program.  The computer must have software that can search
     any GC/MS data file for ions of a specific mass and that can
     plot such ion abundances versus time or scan number.  This
     type of plot is defined as an Extracted Ion Current Profile
     (EICP).  Software capabilities must also allow integrating
     the abundance in any EICP between specified time or scan
     number limits.

5.0  Reagents

     5.1  Non-spectrograde hexarie distilled in glass (Burdick and
Jackson)

     5.2  Acetic anhydride: Redistilled reagent grade

     5.3  Reagent water:  Organic free such as produced by a
Barnstead Model D2798 NANO-pure-A water purification system

     5.4  Sodium hydroxide:  5 piercent w/w in reagent water

     5.5  Sulfuric acid:  Mix one part cone. ^504 with four
parts reagent water

     5.6  Potassium Carbonate: Dissolve 150 g K2C03 (purified by
heating at 400°C for 6 to 8 hours in a shallow tray) in 250 mL
reagent water

     5.7  Internal Standard Stock Solution: Weigh (to the
nearest 0.1 mg) 25 + 3 mg of 3,4 ,5-trichlorophenol and dissolve
to volume with methanol in a 50 mL volumetric flask.  Transfer
the stock solution into an amber bottle with a Teflon-lined screw
cap and store under refrigeration.

     5.8  Internal Standard Spiking Solution:  Pipet 5.0 mL of
the stock solution into a 100 ml, ground-glass-stoppered volu-
metric flask and dilute to volume with methanol.  Transfer the
spiking solution into five ca 20 mL portions in separate Teflon-
lined screw capped vials, number 1 to 5 and store under refriger-
ation (4°C).

     5.9  Calibration Standard Stock Solutions:  Prepare stock
solutions of individual compounds by weighing (to the nearest 0.1
mg) 25 + 1 mg of each compound of a known purity.  Dissolve the
material in methanol (acetone must be used for the chlorinated
benzaldehydes) and bring to volume in a 25 mL ground-glass-
stoppered volumetric flask.  Transfer the individual stock
solutions to 25 mL scintillation vials with Teflon-lined screw
caps and refrigerate at 4°C.  Prepare the working solution by
pipeting 1.0 mL of each stock solution into a 50 mL ground-glass-
stoppered volumetric flask.  Bring to volume with methanol.  This
working solution is discarded after use.

-------
                              D25
     5.10  Calibration Curve Standards:  The calibration curve
standards are prepared by spiking separate 100 raL portions of
reagent water with 150 y.L of the Internal Standard spiking
solution and 50,  750,  1500 uL portions of the calibration
standard working solution.  The resulting solutions are then
acetylated, extracted and concentrated in a manner analogous to
a 100 mL sample aliguot.

6.0  Sample Collection, Preservation and Storage

     6.1  Collection:   Grab samples must be collected in glass
containers having a Teflon-lined screw cap.  Automatic sampling
equipment which comes in contact with the sample should be
constructed of glass,  Teflon, or stainless steel.  Composite
samples should be refrigerated during the sampling period.

     6.2  Preservation:  All samples must be preserved by
adjusting to pH two, with H2SC»4, and refrigerating.  This should
be done as soon as possible after sample collection.  Samples
must be shipped in iced containers as quickly as possible.

     6.3  A portion of the sample should be tested for free or
residual chlorine. Add 35 mg of sodium thiosulfate per ppm free
chlorine per liter.

     6.4  Storage:  Samples may be stored in the refrigerator
(4°C) for up to 30 days.  Acetylated extracts must be analyzed
within 30 days after acetylation.

  7.0 Procedures

     7.1  Sample Preparation:

          7.1.1  In Situ Acetylation: Remove the sample from the
     refrigerator and allow it to come to room temperature.
     Shake the sample vigorously to insure it is homogeneous
     and then measure out three 100 mL aliquots.  Neutral-
     ize the sample to pH 7.0 to 7.1 using 5 percent NaOH
     and 1:4 sulfuric acid.  Add 2.6 mL of the potassium carbon-
     ate solution and adjust the pH to 11.6 + 0.1 with 5 percent
     NaOH if necessary.

     Transfer the sample to a 250 mL separatory funnel and
     spike it with 50 uL of the Internal Standard spiking
     solution.  Shake the sample to insure thorough mixing.
     Add 2.0 mL of acetic anhydride and shake the sample with
     frequent venting for 30 seconds.  Let the sample stand for 5
     minutes then shake and vent.

     Add 10 mL of hexane and shake vigorously for 1 to 2 minutes
     with frequent venting.  Allow the phases to separate and
     drain off the aqueous portion into the beaker.  If there is

-------
     an emulsion problem,  drain the organic layer into a centri-
     fuge tube, cap and centrifuge for 2 to 3 minutes or until
     the emulsion is broken.   Transfer as much of the hexane as
     possible into the Kuderna-Danish (K-D) assembly.  Transfer
     the aqueous portions  back to the seperatory funnel and
     extract two more times with 10 mL hexane, combining the
     extracts in the K-D.   Repeat this process with the remaining
     two 100 mL sample aliquots, combining all hexane extracts
     and rinses into the one K-E> assembly.  Add 1 or 2 carbor-
     undum boiling chips and secure the assembly in the water
     bath.  Watch the sample carefully and remove when the K-D
     receiving tube is about 1/4 full.  Do not allow the sample
     to go to dryness.  Transfer the concentrated extract to a 15
     mL centrifuge tube using three 1 mL hexane rinses. Concen-
     trate to a final volume of ca 0.2 mL.  Cap arid store in the
     refrigerator until analyzed.  After analysis has been
     completed, transfer the sample using three 1 mL hexane
     rinses to a labeled 2-dram Teflon-lined screw cap vial and
     refrigerate.

     7.2  The recommended gas chromatographic column and operat-
ing conditions for the instrument are : 30 m x 0.2:5 mm id fused
silica DB-5, 0.25 micron film thickness.  Helium carrier gas (36
cm/sec at 200°C). Injection port temperature 210°C.  Column
temperature, isothermal at 45°C for one minute then temperature
programed at 6°C/min to 280°C holding for 25 minutes.

     7.3  The recommended mass spectrometer operating conditions
are: mass scan range m/e 42 to 336 with a scan speed of 216.7
amu/sec.

     7.4 Calibration

          7.4.1 Prior to any analysis of standards or samples,
     the mass spectrometer must be tuned in such a manner that a
     mass spectrum of DFTPP meeting all criteria in Table 1 can
     be obtained.

          7.4.2 Calibration Curve: Establish GC/MS operating
     parameters equivalent to those described in Sections
     7.2 and 7.3.  Analyze 1 uL splitless injection of the
     calibration curve standards and integrate the extracted
     ion current areas for each of the characteristic ions shown
     in Table 2.  Tabulate the ratio of the area of the analyte
     quantitation ions divided by the area of the Internal
     Standard.  Using this data and the concentrations of the
     analytes, assuming a 300 mL sample volume, calculate the
     linear regressions and tabulate the calibration slope and
     intercept data.

-------
                          D27



            DFTPP KEY MASSES AND ABUNDANCE CRITERIA*'b

                         Ion Abundance Criteria

                         30 to 60% of mass 198

       68                Less than 2% of mass 69
       70                Less than 2% of mass 69

      127                40 to 60% of mass 198

      197                Less than 1% of mass 198
      198                Base peak, 100% relative abundance
      199                5 to 9% of mass 198

      275                10 to 30% of mass 198

      365                Greater than 1% of mass 198

      441                Present but less than mass 443
      442                Greater than 40% of mass 198
      443                17 to 23% of mass 442
a J.W. Eichelberger, L.E. Harris, and W.L. Budde, "Reference
  Compound To Calibrate Ion Abundance Measurement In Gas
  Chromatography-Mass Spectrometry."  Analytical Chemistry
  £7,995 (1975).

b 50 ng DFTPP injected using a Grob type splitless injection
  and the following gas chromatographic conditions:
  Injection port temperature 210°C, oven programmed from
  160°C after a one minute hold at. 6°C/minute to 210°C.
  Mass spectrometer conditions are set to scan from 45 to
  445 amu at 216.7 amu/sec.
     7.4.3 Daily Calibration Check:  The working calibration
curve must be verified on each working day by the analysis
of one or more calibration curve standards.  If the recovery
of any analyte varies by more than +20 percent, the test
must be repeated at a different concentration level. If this
value is also out of range, a new calibration curve must be
prepared.

7.5 Sample Analysis

     7.5.1  The sample extract is analyzed using the
conditions described is Sections 7.2 and 7.3. The extracted
ion current profile areas for each of the ions listed in
Table 2 are tabulated.

-------
                               1)28
TABLE 2   CHARACTERISTIC IONS AND RELATIVE RETENTION TIMES

                                                    Relative
                              Characteristic Ions   Retention
     	Compound	     Primary   Secondary     Timea

     2-chlorophenol             128     130, 170      0.598
     4-chlorophenol             128     130, 170      0.637
     2,6-dichlorophenol         162     164, 204      0.747
     2,4-dichlorophenol         162     164, 204      0.771
     3,5-dichlorophenol         162     164, 204      0.784
     3,4-dichlorophenol         162     164, 204      0.835
     4-chloroguaiacol           158     160, 200      0.863
     2,4,6-trichlorophenol      196     198, 238      0.877
     2,3,6-trichlorophenol      196     198, 238      0.923
     2,4,5-trichlorophenol      196     198, 238      0.939
     4,6-dichloroguaiacol       192     194, 234      0.987
     3,4,5-trichlorophenol(IS)  196                   1.00
     3,5-dichloro-4-
       nydroxybenzaldehyde      189     191, 232      1.001
     4,5-dichloroguaiacol       192     194, 234      1.041
     3,5-dichlorocatechol       178     180, 262      1.053
     2,3,4,6-tetra-
       chlorophenol             230     232, 272      1.066
     5-chlorovanillin           186     188, 228      1.086
     6-chlorovanillin           186     188, 228      1.094
     3,4-dichlorocatechol       178     180, 232      1.108
     4,5-dichlorocatechol       178     180, 232      1.130
     3,4,5-trichloroguaiacol    226     228, 268      1.143
     4,5,6-trichloroguaiacol    226     228, 268      1.180
     3,4,6-trichlorocatechol    212     214, 296      1.184
     5,6-dichlorovanillin       220     222, 262      1.220
     pentachlorophenol          266     268, 308      1.231
     chlorosyringaldehyde       216     218, 258      1.231
     3,4,5-trichlorocatechol    212     214, 296      1.243
     tetrachloroguaiacol        260     262, 302      1.258
     trichlorosyringol          256     258, 298      1.272
     tetrachlorocatechol        246     248, 330      1.338
     a  Retention times of acetate derivatives relative to
        3,4,5-trichlorophenol acetate.  Under the chromato-
        graphic conditions in Section 7.2, the retention time
        for 3,4,5-trichlorophenol acetate is 20.92 minutes.

          7.5.2  Qualitative criteria: Obtain EICPs for the
     primary  ions and  the two secondary ions listed in Table
     2.  The  following criteria must be met in order to make a
     qualitative identification.  The characteristic ions of
     each compound of  interest must maximize within two scans of
     each other and  the retention time must fall within 20

-------
                              D 29
     seconds  of  the  authentic compound.   The relative peak areas
     of  the characteristic ions must fall within 20 percent
     of  the relative intensities as determined in the reference
     compound obtained from the previously analyzed calibra-
     tion standards.

          7.5.3   Quantitation: Calculate the concentration of
     the analytes using the following equation:


               Concentration =  |	j  (ms)  +  bs

          where:  As = area of the analyte ion

                  AIS = area of the internal standard ion

                  ms  = slope from calibration curve for
                         analyte ion

                  bs  = intercept from calibration curve for
                         analyte ion

          If  the sample produces an interference for the primary
          ion, use a secondary characteristic ion to quantitate.

8.0  Quality  Control

     8.1  Blanks: Before processing any samples or whenever a
new reagent is prepared, the analyst should demonstrate through
the analysis  of a blank that utilizes all glassware and reagents
required for  sample  analyses that all materials are interference
free.  The blank samples should be carried through all stages of
the sample preparation and measurement.

     8.2  Frequency:  A minimum of 5 percent of routine samples
should be allocated  for quality control.  In addition to this,
representative samples from each new or untested source or
sample matrix should be treated as a quality control sample.
Laboratory replicates and fortification should be conducted on
each QC sample to document method performance as indicated by
precision and recovery.

     8.3  Replicates:  Replicates consist of running two or more
separate aliquots of the sample through the entire analytical
procedure. The range and mean concentration of the replicates
are determined from  the results and the relative percent differ-
ence is calculated as follows:

          Rel. Percent Difference = 100 /range\
                                        I mean  I


     8.4  Recovery:   Using the mean concentration determined by

-------
                                 D30
the replicate analyses, determine the spiking level which will
give a minimum of three times the background.  Spike the sample
with the determined amount of the calibration standard working
solution and proceed to analyse the sample in the normal manner.
Calculate and record the percent recovery as follows:

     Percent Recovery =  Level Measured-Background x 100
                               Level Spiked

     where the Background is the mean of the replicate
     determinations described above.

-------
                                                         WEST COAST flEOIONAL CCMTC
                                       D 31                           po*»«a
                                                                 CervalHs. OA «na
                                                                    (909)794401
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT, INC.
  May 8,  1987



  MEMO TO:   Frank Thomas

  FROM:      Larry LaFleur

  SUBJECT:   Revised Isotopic Dilution Quantitation Procedures for
             Chlorinated Phenolics Analysis Procedures


  Attached  is  a summary of the revised quantitation procedures we
  have discussed in the past and agreed to incorporate into the
  analysis  of  the Cooperative Study chlorinated phenolics analysis
  procedures.   Essentially, stable isotope internal standards have
  been incorporated wherever possible.  The standards were obtained
  and details  were worked out before we began the analysis of the
  samples from the final three mills.  Thus,  as indicated in the
  reports I have already sent out, NCASI Method CP-86.01 was used
  for the first two mills and this revised quantification procedure
  was used  for the last three mills.

-------
                                    D32
                REVISED QUANTIFICATION PROCEDURE
               FOR CHLORINATED PHENOLICS ANALYSIS
     The compounds are quantified using multiple internal
standards, with the internal standard to be used designated as
the one closest in retention time to that of a given analyte.
When a labelled analog exists for an analyte, isotopic dilution
is the quantitation method used.  The internal standards and the
corresponding analytes are listed below:
2H4 - 4 -chlor ophenol

^3-2 , 4-dichlorophenol
   ~2 , 4 , 5-trichlorophenol

    3,4, 5-trichlorophenol
13Cg-pentachlorophenol
                                      2 -chlorophenol

                                    2 , 6-dichlorophenol
                                    2 , 3-dichlorophenol
                                    3 , 4-dichlorophenol
                                    2 , 4 -dichlorophenol

                                  2,4, 5-trichlorophenol

                                    4 , 5-dichloroguaiacol
                                  3,4, 5-trichloroquaiacol
                                  4,5, 6-trichloroquaiacol
                                      5-chlorovanillin
                                      6-chlorovanillin

                                        pentachlorophenol
                                    5 , 6-dichlorovanillin
                                        tetrachloroguaiacol
     A four-point (including the origin) calibration curve is
established by analyzing three levels of analytes using a
constant amount of the internal standards in each.  The ratios of
the EICP area of the analyte quantitation ion divided by the EICP
area of the appropriate internal standard quantitation ion are
plotted against analyte concentration.  The slope and intercept
are calculated using a linear regression equation and these
values are used to calculate sample concentrations as follows:
                               Ax
       Concentration = slope x —  + intercept
where: Ax + EICP area of the analyte primary quantitation ion
          o
       Aj + EICP area of the internal standard primary
            quantitation ion

-------
                                    D33
     For those compounds (2,4 dichlorophenol, 2,3,5-
trichlorophenol, and pentachlorophenol ) where a labeled analog is
present, quantitation is performed using the relative responses
of analyte to labeled analog to create a calibration curve as
previously mentioned for the internal standard quantitation.  The
relative responses (RR) are calculated using the equation:
           RR =
                 (Rjn-Rx)  (Ry+1)

where :

     Rx = the isotope ratio measured for the native analyte

        = the isotope ratio of an analytical mixture of the
          native analyte and  labelled analog

     The Rx and Ry values are calculated from  the EICP data of
the specified quantitation ion obtained by analyzing separate
aliquots of the native analytes  and the labelled analogs.  This
need only be done once at the beginning of the project.  The Rm
values are generated over the range of concentrations which will
be measured and are the  ratios of the EICP areas of the analyte
quantitation ion divided by the  EICP areas of  the labelled analog
quantitation ion.  The calibration curve is established by
plotting RR against analyte concentration.  As before, the slope
and intercept are calculated  and values are used to calculate
sample concentrations as follows:

     Concentration = slope  (RR)  + intercept

where:           RR = relative response factor  defined above


                 RR =
                     A!

                 Ax = EICP area of the analyte  quantitation ion

                 Aj = EICP area of the labelled analog
                     quantitation ion.


     The following table presents the pertinent data for all
compounds used to establish the  calibration curves.

-------
                           D  34

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-------
      ATTACHMENT E






RESULTS FOR 2378-TCDD and  2378-TCDF




 (Master Sample Lists)

-------
                                     25-Feb-B
                                                                                                                       Hill A
                                                                                                                       Laboratory Data
  SAMPLE
  NUMBER
SAMPLE DESCRIPTION
                                  LAE
TCDD     320/322     «EC       REPORT
(ppt)     RATIO    13C12TCDD     DATE
                                                            LAE
                           TCDF     304/306     * REC      REPORT         TCDF/TCDD
                           (ppt)      RATIO    13C12TCDF     DATE            RATIO
           A.  BACKGROUND SAMPLES

DE020801   Treated River Water
DE020802   Uater Treatient Precis.  Sludee
DE020803   Vater Treatient Sandfliter Sludee
DE02QB04   Softwood Chips
DE0208C5   Hardwood Chips
                           ND(0.00514)
61.0    11-16-87
                                               ND(0.0107)
51.9    11-16-87
ERR
ERR
ERR
ERR
ERR
           B.  PULPING PROCESS

DE020806   CoBbined Pulpine 4 Recaust WVs

           C.  CHEHICAL RECOVER? PLANT
DE020807   CoBbined Process Wastewater
DE02D80B   Lite Hud
                                                                                                                                   ERR
                                                                                                                                   ERR
                                                                                                                                   ERR
           D. BLEACH PLANT
DE020901
DE020902
DE020902

DE020903
DE020904
DE020905

DE020906
DE020907
DE020908

DE020909
DE020910
DE0209H
DE020912
DE020913
DE020914
DE020809
DE020B10
Unbleached Softwood Pulp
Bleached Softwood Pulp
Bleached Softwood Pulp
AVERAGE
Unbleached Hardwood Pulp
HVPO Hardwood Pulp
Peroxide Hardwood Pulp
Softwood Bleach Line
S-l Washer. C Staze
S-2 Uasher, Eo Stage
S-3 Washer, H Stage
Hardwood Bleach Lines
K-6 Washer. C Stage
K-4 Uasher, Eo Stage (Hypo line)
K-5 Washer, H Stage (Hypo line)
K-2 Uasher, Eo Stage (Per line)
K-3 Washer. H Stage (Per line)
K-l Washer, H Stage (Per line)
Hypo Solution
Caustic Solution
WX0.738)
15.2
16.3
15.8
NDI0.309)
4.89
2.98

0.238
1.82
0.342

0.0212
ND(0.0326)
NDI0.0168)
0.0453
0.0403
0.0247


l»
0.76
0.79

ti
0.79
0.85

0.81
0.85
0.80

0.84
m
it
0.82
0.83
0.79


69.7
76.0
82.3

70.4
64.1
77. 1

72.0
68.1
65.6

78.9
51.7
56.4
91.0
52.5
60.1


9-25-87
3-19-87
4-21-87

9-25-87
4-21-87
4-21-87

4-28-87
3-19-87
5-22-87

4-28-87
5-22-87
6-19-87
5-22-87
6-19-87
5-12-87


                                                                                                 ND(0.271)
                                                                                                        333
                                                                                                        333

                                                                                                 WHO. 231)
                                                                                                       47.3
                                                                                                       50.1
                                                                                                      3.806
                                                                                                      32.6
                                                                                                      5.778
                                                                                                      0.305
                                                                                                      0.247
                                                                                                      0.114
                                                                                                      0.318
                                                                                                      0.170
                                                                                                      0.174
                                                                                            0.78
                                                                                           it
                                                                                            0.78
                                                                                            0.67
                                                                                            0.88
                                                                                            0.82  ->
                                                                                            0.68
                                                                                            0.84
                                                                                            0.77
                                                                                            0.85
                                                                                                      57.1    9-25-87
                                                  74.8    4-21-87
                                                  64.3    9-25-87
                                                  54.6    7-17-87
                                                  54.3    7-17-87
                                       0.82 ->    37.8    4-28-87
                                       0.88       72.5    3-19-87
                                       0.82       75.3    5-22-87
                                                  50.2
                                                  39.9
                                                  61.4
                                                  59.4
                                                  53.5
                                                  57.0
                                                                                 6-15-87
                                                                                 6-15-87
                                                                                 7-17-87
                                                                                 6-15-87
                                                                                 7-17-87
                                                                                 6-15-87
                                                                               ERR
                                                                                                   21.06

                                                                                                      ERR
                                                                                                    9.67
                                                                                                   16.81
                                                                                                                                 15.99
                                                                                                                                 17.91
                                                                                                                                 16.89
                           14.39
                        UNDEFINED
                        UNDEFINED
                            7.02
                            4.22
                            7.04
                             ERR
                             ERR
DE020915   Conbined Process Wastewater
                                0.296     0.81
 106    1-16-87
                                                                            El

-------
Oi-Har-68

SAMPLE
NUHBER

DE020811

DE020812
DE020813
DE020814
DE020916
DE020917
DE020815
DE020816
DE020817
DE020822
DE020823
DE021001
DE021002

DE020818
DE020918
DE020919
DE020819
DE020820
DE020920
DE020920

DE020921
DE020922
DE020922
DEQ20922

DE020621
DE020821


DE020923
DE020824
DE020924


SAKPLE DESCRiPTSOH
E. PAPER HACH1NES
Cosbined Process Vastewaters
Process Additives
AlUB
Filler Clay
Coater Clay
Dve-1 (Helierco Blue HGV)
Dye-2 (Cartosol Brill. Paper Yellow)
Resin Size Eiulsion (Neuphon
High Brightness Filter (Hvcali
Sliiicide (Dearborn 6202)
Soda Ash
Sodiui Thiosulfate
Whitewater - Clean
Whitewater - Dirty
F. UTILITIES. yASTEWATER TREATMENT
Powerhouse Uastevater
BottoB Ash
Fly Ash
I1IITP Priiary Sludge
yVTP Secondary Sludge
k'UTP Coiposite Sludge
WTP Coiposite Sludge
AVERAGE
CoBbined Untreated Vastevater
Final Wastewater Effluent
Final Uastewater Effluent
Final Vastewater Effluent
AVERAGE
Landfill Leachate
Landfill Leachate
AVERAGE
G. OTHER
Sludge (not froi Kill A)
Thiosulfate I H2S04 Reagent Blank
Field Blank
LAE
TCDL 320/322 HREC REPORT
vpDti RATiO iaC12Tf,6b DATE

0.0205 0.81 52.4 6-19-87
















NDiO.660) »* 77.9 9-21-87
23.5 0.76 96.2 9-21-67
709 0.82 77.8 9-21-87
37.4 0.72 86.9 3-19-87
35.8 0.80 80.3 4-21-87
36.6
0.136 0.79 71.1 6-18-87
0.111 0.72 89. B 1-16-87
0.150 0.86 44.5 2-12-87
0.111 0.85 63.2 2-12-87
0.124
0.0309 0.78 59.1 7-9-87
0,0196 0.86 52.7 9-11-87
0.0253

470 0.79 64.5 4-21-87
ND(0.0102) »« -> 35.3 9-21-87

Ui
" TCDF 304/306 I REC REPORT
«< *poti RATIO 13C12TCDF DATE

0.191 0.80 52.5 3-19-87
















NDiO.345) ** 61.2 9-21-87
382 0.81 60.1 9-21-87
10S32 0.80 48.2 9-21-87
624 0.89 74.6 3-19-87
732 0,76 72.5 4-21-87
676
1.916 0,78 64.8 6-18-87
2.18 0.74 42.6 2-12-87


2.18
0.124 0,78 48.7 7-9-87
0.095 0,79 52.6 9-11-87
0.110

4186 0.72 47.4 4-21-87
WHO. 0293) H 42.7 9-21-87

                                                                                                       LdOomorv Data
                                                                                                              TCDF/TCDD
                                                                                                                RATIO
                                                                                                                   ERR
                                                                                                                   Enn
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERF.
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                   ERR
                                                                                                                 16.26
                                                                                                                 15.42
                                                                                                                 18.52

                                                                                                                 14.09
                                                                                                                  17.56
                                                                                                                  4.36
                                                                                                                   8.91
                                                                                                                    ERR
                                          E2

-------
                                   ifi-Feb-68
  SAMPLE
  NUMBER           SANPLE DESCRIPTION
Kill B
Laboratory Data

TCDD
(ppt)

320/322
RATIO

(REC
13C12TCDD
LAB
REPORT «t
DATE *«

TCDF
(ppt)

304/306
RATIO

1 REC
13C12TCDF
LAB
REPORT
DATE

TCDF/TCDD
RATIO
           A. BACKGROUND SAMPLES

86374601   Treated Intake
86374602   Filter Backwash
86374603   Softwood Chips
86374604   Hardwood Chips
66374605   Softwood Sawdust
86374671   Softwood Sawdust

           B. PULPING PROCESS

86374606   Brownstock Filtrate (Int./Eit.)
86374607   Pulp Mi 11

86374609   Recovery. Evap. Recaust
86374672   Recovery, Evap, Recaust

           C. CHEMICAL RECOVERY PLANT
                                             NDIO.00693)
                              54.5    11-16-87
                                               NDI0.00950)   if
                                                             47.1    11-16-87
                                                                              ERR
                                                                              ERR
                                                                              ERR
                                                                              ERR
                                                                              ERR
                                                                              ERR
                                                                                                                                                         ERR

                                                                                                                                                         ERR
                                                                                                                                                         ERR
86374610   Lite Hud
                                                                                                            ERR
           D. BLEACH PLANT

86374611   Unbleached Pulp

86374612   Bleached Pulp
86374612   Bleached Pulp
66374661   Bleached Pulp
           AVERAGE (612/661)

86374613   Chiorination State (C)
86374673   Chlorination Stage (C)
           AVERAGE (613/673)

66374674   Chlorination Stare (Grab)
86374614   Dioxide Stage (D)

86374615   Caustic State (E)
86374615   Caustic State (E)
           AVERAGE

86374616   First Hypo Stage (H)
66374617   Second Hypo Stage (H)
86374618   Hypo Solution
86374619   Caustic Solution
86374620   Chlorine Dioxide Solution
MH0.949)
0.0298
                 i«
0.80
                         41.4    9-25-87
                                        1.54     0.68 ->     39.0    9-25-87
10.2
11.0
12.6
11.3
NDI0.0327)
0.0463
0.0232
0.83
0.77
0.69

H
0.84

54.6
60.2
67.0

42.1
57.6

4-21-87
8-19-87
4-21-87

3-19-87
11-16-87

54.3
64.4
63.9
60.9
0.0635
0.0722
0.0679
0.65
0.73 ->
0.77

0.88 ->
0.70

67.1
10.3
55.4

30.6
48.2

4-21-87
8-19-87
4-21-87

3-19-87
11-16-87

78.6    5-12-87
                                                                                                      0.133     0.66
62.5    5-12-87
                                                                              ERR
                                                                                                           5.40

                                                                                                            ERR

                                                                                                           2.93

                                                                                                            ERR
                                                                                                           4.46
0.229
0.219
0.224
0.258
0.132
ND(0.009B)


0.61
0.81

0.63
0.78
H ->


59.8
69.2

50.9
51.4
39.9


6-19-87
7-7-87

5-22-87
6-19-87
3-19-87


1.254
0.834
1.044
1.129
0.913
ND(0.0054)


0.67
0.70

0.71
0.84
it ->


44.1
49.4

59.7
80.8
38.8


6-19-87
7-17-87

5-22-87
11-16-87
3-19-87




4.66
4.38
6.92
UNDEFINED
ERR
ERR
                                                                             E3

-------



SAMPLE
NUHBER

86374621
86374623
66374624
86374625
86374626
86374627
86374628
86374629

86374641
86374642
86374643
86374644
86374644

86374646
86374645
86374645


16-Feb-68


TCDD
SAHPLE DESCRIPTION (ppt)
E. PAPER MACHINES
Paper Hachine ND(0.00514)
Sliiicide (CB 210)
Dye (Tel low)
Sliiicide (D3TA)
Dye (Violet)
HTI 6440
Perez 631
Santo Rez
F. UTILITIES. «ASTE«ATER TREATMENT
Priiary Sludge 18.9
Secondary Sludge (No/Poly) 88.9
Secondary Sludge (U/Poly)
Untreated Vastevaters NDL0129)
Untreated Vastevaters NDiO.00644)
AVERAGE 0
Leachate ND(0.00405)
Final Effluent 0.0157
Final Effluent 0.0145
AVERAGE 0.0151
G. OTHER
Hill B
Laboratory Data
LAB LAB
320/322 U£C REPORT »« TCDF 304/306 1 REC REPORT TCDF/TCDD
RATIO 13C12TCDD DATE «» (ppt) RATIO 13C12TCDF DATE RATIO

» -> 35.9 8-19-87 0.108 0.69 -> 36.9 8-19-87 ERR








0.79 102.1 9-21-87 101 0.80 90.1 9-21-87 5.34
0.80 78.2 4-21-87 808 0.72 84.8 4-21-87 9.09
ERR
» >2.4 6-18-87 0.092 0.68 49.8 6-18-87 UNDEFINED
«i -> 27.5 9-21-87 0.124 0.67 -> 27.9 9-21-87 UNDEFINED
0.108 UNDEFINED
H 13.7 9-11-87 0.0105 0.64 40.9 9-11-87 ERR
0.86 1)9.7 7-9-87 0.133 0.65 -> 30.5 7-9-87
0.66 159.0 11-16-87 0.110 0.72 57.8 9-30-87
0.122 6. OB

86374681   Field Blank
                                                                            E4

-------
                                   16-Feh-88
  SAMPLE
  NUKBEK
DE026001
DE026101
DE026102
DE026103
DE026104
        SAMPLE DESCRIPTION

A. BACKGROUND SAHPLES

Treated Eiver Water
yater Soft.  Sludge
Sandfilter Backvash
HardHood Chips
Raw yater CMP
    TCDD      320/322     iREC
   (ppt)       RATIO    13C12TCDD
           LAB
         REPORT
          DATE
   TCDF
   (put)
                                                               304/306
                                                                RATIO
                         (REC
                       13C12TCDF
   LAB
 REPORT
  DATE
Hill C
Laboratory Data

       TCDF/TCDD
         RATIO
MHO. 00531)     «
41.9    8-19-87
ND(0.00694)   u
                                                                             41.0      11-16-87
                                                         ERR
                                                         ERR
                                                         ERR
                                                         ERR
                                                         ERR
           B. PULPING PROCESS

DE026107   Coibined Pulping CMP
DE026111   Recaust And Liie Kiln

           C. BLEACH PLANT
DE026002   Unbleached Pulp
DE026003   Bleached Pulp
DE026004   C/D Filtrate
                                  NDI0.564)
                                  ND(0.620)
                                  ND(0.00593)
                u
                ii
60.2    9-25-87
91.1    11-16-87
63.4    4-28-87
NDI0.162)
      14.9
    0.0929
                                                                 ii
                                                                  0.89
                                                                  0.73
                           44.6
                           62.5
                           53.7
9-25-87
3-19-87
4-28-87
                                                                                                                                             ERR
                                                                                                                                             ERR
            ERR
       UNDEFINED
       UNDEFINED
C/D-1
C/D-2
C/D-3
C/D-4
DE026005
DE026211

DE026212
C/D Filtrate (Grab-1)
C/D Filtrate (Grab-2)
C/D Filtrate (Grab-3)
C/D Filtrate (Grab-4)
E/0 Filtrate
E/0 Filtrate
AVERAGE (005/211)
E/Q Filtrate


NDI0.0106) »« 52.2 6-19-87
ND(0.0154) » 48.3 6-19-87
0



0.0573 0.87 -> 24.8 7-17-87
0.0543 0.83 -> 13.1 7-17-87
0.0558





UNDEFINED
ERR
E/0-1      E/0 Filtrate (Grab-1)
E/0-2      E/0 Filtrate (Grab-2)
E/0-3      E/0 Filtrate (Srab-3)
E/0-4      E/fl Filtrate (Grab-4)

DE026006   D Filtrate
DE026213   D Filtrate
           AVERAGE (006/213)

DE026214   D Filtrate

D-l        D Filtrate (Grab-1)
D-2        D Filtrate (Grab-2)
D-3        D Filtrate (Grab-3)
D-4        D Filtrate (Grab-4)

DE026114   Scrubber
DE026116
DE026117
CI02 Solution
Caustic Solution
NDfO.0112)
ND(0.00341)
     0
                                                  »
                                                              49.1
                                                              80.3
                                    3-19-87
                                    5-12-87
NDI0.0056)    H
    0.0272     0.69
    0.0136
                                                  52.1
                                                  68.3
                                    3-19-87
                                    5-12-87
                UNDEFINED

                UNDEFINED

                     ERR
                                  WHO. 00912)
                            68.4    9-21-87
                            0.429     0.76
                           54.8     9-21-87
                                                                                                           ERR
                                                                                                           ERR
                                                                            E5

-------



SAMPLE
NUMBER

DE026118
DE026123
DE026124
DE026201
DE026202
DE025203
DE026204

DE026205
DE026007
DE026008
DED26009
DE026010
DE026215
DE026011
DE026011

DE026012
DE026013
DE026014
DE026207
DED26216
DE026206
DE026206


09-Bai-Ba

LAE
7CDD 510/3:2 XREC REPORT »» TCL-F 304/306 * REC
SAHPLE DESCRIPTION Ippt) RATiQ 13C12ICDD DATE »* (opt; RATIG 13C12TCDF
D. PAPER MACHINES
CoRbined Process yater 0.0106 0.70 6C.1 6-19-37 0.197 0,7; 56.5
Dve (Hobav Pont. Brill. Blue A)
Dye (Pemsoi Ye II on BRA Extra-6)
Dve (Anthosin Red 21P-BASF)
Biocide (Betz RI-41)
Defoaier (Fleeted 3170;
Dye (Hobay Pont. Bond Yellow 303)
E. UTILITIES. yASTEyATER TREATMENT
Station 15 tfoodboiler
Coal Ash - Siuiced
Coal Ash - ESP
Mechanical Coal Ash
Uood Waste Ash Vater
liood Vaste Ash Water
CoBbined Devatered Sludje 3.37 0.80 77.7 4-21-67 42.6 0,76 53.3
Coibined Denatered Sludge 3.27 0.70 68.2 8-19-67 34.5 0.71 63.8
AVERAGE 3.32 36.6
Pri»arv Influent ND(G.D0276) » 51. i 6-16-87 0.0352 0.72 46.2
Secondary Effluent (0-24 hrs; NDI0.00281) « 62.6 7-9-87 0.0128 0,67 57.1
Landfill Leachate ND(0.00595j «« 50.8 9-11-87 ND(C.00669) *« -> 31.4
Thickened Secondary Sludge 11.2 0.81 -> 22.4 1-20-88 75.4 0.8 5E.5
Thickened Secondary Sludee
Secondary Effluent (36-72 hrs) NDI0.00339) »* 50.7 7-9-87 0.00846 0,79 54.0
Secondary Effluent (36-72 hrs) ND10.00424) «• 61.7 9-30-67 O.OiiO 0.65 42.1
AVERAGE 0 0.01124
F. OTHER
Mill C
Laboratory Data
LAE
REPORT TCDF'TCID
DATE RATIO

3-13-87 16.55
ERE
ERR
ERR
ERR
ERF,
ERR

ERR
ERF.
ERR
ERR
ERR
ERF,
4-21-67
8-19-67
11.61
6-18-67 UNDEFINED
7-9-87 UNDEFINED
9-11-87 ERR
1-20-88 6.73
ERR
7-3-87 UNDEFINED
11-16-87
UNDEFINED

DE026220   Siudje  (not froi Mil!  C)
DE026206   Reagent Blank
DE026209   Field Blank
317     0.82
63.2    9-21-87
3266     0,81
47.7     9-21-87
10.3
                                                                         E6

-------
  SAMPLE
  NUMBER
                                     16-Feb-88
         5AKPLE  DESCRIPTION
    TCDD
   (ppt)
320/322   JREC
RATIO   13C12TCDD
   LAB
 REPORT
  DATE
                                                   Hill  D
                                                   Laboratory Data

                                             LAB
i»      TCDF       304/306      * REC      REPORT         TCDF/TCDD
««     (pot)        RATIO     13C12TCDF     DATE            RATIO
           A.  BACKGROUND SAMPLES

DF024401   Unchlorinated Hater

DF024402   Chlorinated North Entry
DF02U02   Chlorinated North Entry
           AVERAGE

DF024403   Chlorinated South Entry
DF024404   SofUood Chips
                                   ND(0. 00456)
                                   ND(0.00773)
                                             0
                                                  ««
                          36.9
                          46.9
                    7-9-87
                    8-19-87
               ND(0.0052D
               NDI0.00469)
                         0
                                                                  ii
                                  28.5
                                  51.1
                     7-9-87
                     8-19-87
                             ERR

                             ERR

                        UNDEFINED

                             ERR
                             ERR
           B. PULPING PROCESS
DF024405   Brownstock Sewer
                                                                                                                                               ERR
           C. CHEMICAL RECOVERY PLANT

DF024406   Evap..Recov..Liie Kiln Sever
DF024407   Lite Hud
DF024408   Vet Lite
                                                                                                                                               ERR
                                                                                                                                               ERR
                                                                                                                                               ERR
DF024409
DF024410
D.  BLEACH PLANT

Coibined Bronnstock Pulp
Bleached Pulp - A
DF024411   Bleached Pulp - B
DF024411   Bleached Pulp - B
           AVERAGE
ND(0.695)      H
NDd.03)       ««

       3.89   0.80
       3.99   0.75
       3.94
            47.4
            54.6

            75.8
            67.6
9-25-87
4-21-87

4-21-87
8-19-87
    ND10.203)
    NDU.23)
                                                                                            7.68
                                                                                            7.90
                                                                                            7.79
H
it

 0.69
 0.81
35.2
41.4

66.4
28.3
9-25-87
4-21-87

4-21-87
8-19-87
ERR
ERR
                                                                                             1.98
DF024412   A Side Chi urination (C)
DF024605   A Side Chlorination (C)
DF024605   A Side Chlorination (C)
           AVERAGE (412/605)

DF024701   A Side Chlorination (Grab-1)
DF024702   A Side Chlorination (Grab-2)
DF024703   A Side Chlorination (Grab-3)
DF024704   A Side Chlorination (Grab-4)

DF024705   A * B Side Caustic (Grab-1)
DF024706   A * B Side Caustic (Grab-2)
DF024707   A * B Side Caustic (Grab-3)
DF024708   A * B Side Caustic (Grab-4)

DF024413   Caustic Coibined (E)
DF024413   Caustic Coibined (E)
           AVERAGE (413)
                                    HD(0.0132)
                                         0.0174
                                         0.0955
                                         0.0376
               ii
              0.77
              0.79
            80.3    4-28-87
            90.8    4-28-87
            40.3    7-7-87
                                          0.257   0.76

                                          0.257
                          45.3    6-19-87
                     0.123
                    0.0286
                    0.0542
                    0.0686
                                         0.509
                                         0.434
                                         0.472
                      0.80
                      0.77
                      0.71
                                 0.81 ->
                                 0.74 ->
             12.1    4-28-87
             55.1    4-28-87
             37.6    7-7-87
                                  34.9
                                  32.2
                                                                                                           1.82
                     6-19-87
                     11-16-87
                                                                                                           1.83
                                                                            E7

-------
  SAMPLE
  NUMBER
                                     16-Feb-88
                                                                                                                                              Hill D
                                                                                                                                              Laboratory  Data
SAMPLE DESCRIPTION

TCDD
(ppt)

320/322
RATIO

SREC
13C12TCDD
LAB
REPORT it
DATE ««

TCDF
(ppt)

304/306
RATIO

SREC
13C12TCDF
LAB
REPORT
DATE

TCDF/TCDD
RATIO
           D.  BLEACH PLANT (cont.)

DF024414   A Side Hypo (H)

DF024709   A Side Hypo (Grab-1)
DF024710   A Side Hypo (Grab-2)
DF024711   A Side Hypo (Grab-3)
DF024712   A Side Hypo (Grab-4)

DF024415   B Side Chlorination (C)

DF024713   B Side Chlorination (Grab-1)
DF024714   B Side Chlorination (Grab-2)
DF024715   B Side Chlorination (Grab-3)
DF024716   B Side Chlorination (Grab-4)

DF024418   B Side Hypo (H)
                                0.0551   0.77
 42.6    5-22-87
0.0857
0.71
50.7    5-22-87
1.56
                                 0.119   0.70
102.6    4-28-87
 0.394'
0.79
41.5    4-28-87
3.31
                                 0.331   0.82
 75.4    5-22-87
 0.602
0.80
67.3    5-22-87
1.82
DF024717
DF024718
DF024719
DF024720
DF024416
DF024417

DF024501
DF024502
DF024503
DF024504
DF024505
DF024506
DF024507
B Side Hypo (Grab-1)
B Side Hypo (Grab-2)
B Side Hypo (Grab-3)
B Side Hypo (Grab-4)
Hypo Solution
Caustic Solution
E. PAPER MACHINES
Paper Machine
Acid Regeneration
Caustic Regeneration
Size Eiulsion
Methyl Violet
Ye! Ion 96
Biocide
                                               ND(0.00590)     »*
                                                     53.1    8-19-87
                             0.0146
             0.65
            56.7    8-19-87
                                                                                                                                                           ERR
                                                                                                                                                           ERR
                             ERR
                             ERR
                             ERR
                             ERR
                             ERR
                             ERR
                             ERR
                                                                             E8

-------


SAMPLE
UMBER

;-F02451i
DFD24604

DF024512
DFG24512
DF024512

DF024513
DF024506
DF024606

DF024514
DF024515
DF02460?
DFC24516
DF024517
DF024518
DF024519
Q9-Har-88

T
3AHFLE DESCRIPTION 'p
F. UTILITIES, WSTEWATER TREATKEST
ilUTF Influent
y»TP Influent
AVERAGE i51 1/60*1
y«TP Effluent ND(0.
tflfTP Effluent ,'JDiO.
y«TP Effluent HD.'O.
AVERAGE
Centered Siud?e
['•ewatered Siud?e
Devatered Sludee
AVERAGE (513/6061
112 Clarifier Frinarv Siud?e
Secondary Siud?e Before Chlorination
Secondary Sludfe Before Chlorinstion
111 Boiler Scrubber
Sludje Laeoon ND(0.
Hi Boiier Bottoe Ash
Secondary Sludje After Chlorination


uuL
pt)


3.0283

00746i
00715)
ooaoB;
0
17.6
19.2
17.4
18.1
17.4
36.1


00317)

35.8


320,322 ttEC
RATIO 13C12TCDD


0.86 51.0

»* 50.1
n 55.6
«» 56.7

0.83 71.8
3.78 63.6
0.74 66.5

0.8t -/ 18.1
0.77 89.0


»« 42.2

0.80 33.6

LAB
REPORT
DATE


11-iB-B7

7-9-87
S-30-87
11-16-67

3-19-37
4-21-87
8-19-87

1-20-88
9-21-87


9-11-87

9-21-87


«* TCEF
** 'pot)

0.0634
0.0503
0.063*
NO (0.00688)
NIX 0.90663!

0
33.7
35.7
31.3
33.8
31.9
77.9


0.0156

73.2
Hii
Lob
LnB
;04/30t * REC REPORT
RATIO 13C127C&F DATE

0.31 -- ;5.« 6-13-57
0.76 ,'3,5 lj-16-3/

»« -> 34.6 7-9-S7
»» 49.1 S-30-37


0.38 57,5 3-19-67
0.31 55.6 4-21-37
0.71 47.8 6-19-8"?

0.79 77.2 1-20-88
0.68 62.4 9-21-57


0.67 *8.5 9-11-67

0.75 87.0 9-21-8'
i L1
oratory Data

TCDF'TCDD
RATIO

ERR
2.06

UNDEFINED
UNDEFINED





1.67
1.83
2.16
W
ERR
ERR
ESR
2.04
           G. OTHER

&F024601   Bottle Blank
DF024602   Reagent Blank
DF024603   Sludee (not fron Kill D)                   92.6   0.78        83.5    3-19-87                976       0.85       100.4    3-19-37            10.54
                                                                             E9

-------
  SAMPLE
  NUMBER
                                   lZ-Feb-88
        SAMPLE DESCRIPTION
                                  LAB
 TCDD      320/322   MEC       REPORT    t*
(ppt)      RATIO   13C12TCDD     DATE      »
                           TCDF     304/306      ( EEC
                          (ppt)      RATIO     13C12TCDF
                                                                                                                                 Mill  f
                                                                                                                                 Laboratory Data
                                                               LAB
                                                             REPORT
                                                              DATE
                                                                                                      TCDF/TCDD
                                                                                                        RATIO
           A. BACKGROUND SAMPLES

RG186355   Upstreai River Water

RG1B63S6   Chlorinated Process Vater
RG186356   Chlorinated Process Vater
           AVERAGE
 ND(0.0226)    H
ND(0.00632)    «
          0
39.1    3-19-B7
43.1    8-19-87
                       ND(0.0155)     «
                       ND(0.00660)    »»
                                 0
                                                                          36.2
                                                                          33.3
                                                                                                                       3-19-87
                                                                                                                       8-19-87
                                          ERR

                                     UNDEFINED
                                     UNDEFINED
                                     UNDEFINED
RG186389   Chlorinated Process Hater
RG186357   Filter Backwash
SGI86357   Filter Backvash
B6186390   Filter Backvash
RG186358   Hardvood Chips
RG186359   Softwood Chips
RG186360   Groundvood Pulp

           B. PULPING PROCESS

RG186361   MB Side General Severs
RG1S6362   Recaust.AfcB Pover Groups n/Evap
RG186363   Lite Hud
                                  NDd.82)
                                  HD(8.21)
            it
            n
64.9    3-19-87
33.1    11-16-87
8.61
49.6
0.81 ->
0.77
                                                                             12.8
                                                                             60.7
                                                            3-19-87
                                                            11-16-87
UNDEFINED

     ERR
     ERR
     ERR
     ERR
                                                                                                                                             ERR
                                                                                                                                             ERR
                                                                                                                                             ERR
           C. BLEACH PLANT

RG186364   Unbleached Pulp A Side
R6186391   Unbleached Pulp A Side
           AVERAGE (364/391)

RG186365   Unbleached Pulp B Side
RG186366   Bleached Pulp A Side

RG186367   Bleached Pulp B Side
RG186367   Bleached Pulp B Side
           AVERAGE
RG186368
RG186368
Combined Acid Sever
Coibined Acid Sever
AVERAGE (368)
RG1B6369   A Side C Seal Boi

RG186370   A Side E Seal Boi
RG166370   A Side E Seal Boi
           AVERAGE  (370)

RG186371   A Side D Seal Boi
KG186371   A Side D Seal Boi
           AVERAGE (371)
 RG186372
 RG186373
 BG186374
 RG186375
 RG186376
 IG186377
 K18637B
B Side C Seal Boi
B Side E Seal Boi
B Side D Seal Boi
Caustic Solution
Hypo Solution
Dioiide Solution
A Side Caustic
KD(0.
ND(0.

ND(0.

















568)
441)
0
984)
25.6
55.7
46.7
51.2
0.270
0.277
0.274
0.0449
2.292

2.292
0.910

0.910
0.0669
3.597
1.92
it
ii

it
0.77
0.79
0.78

0.84
0.80

0.80
0.77


0.81


0.85
0.80
0.77
76.0
81.9

71.7
76
68.5
59.6

71.7
73.6

77.1
64.9


67.5


60.7
66.3
77.7
9-25-87
9-25-87

9-25-87
4-21-87
4-21-87
8-19-87

9-21-87
11-16-87

4-28-87
6-19-87


5-12-B7


4-28-87
6-19-87
5-12-87
t
0.
1.
2




2.

2.
0.
10.
10.
10.
4.
4.
4.
.32
946
133
.32
139
161
183
182
693

693
173
102
526
314
993
437
715
0.326
14.128
9.158
0.
0.

0.
0.
0.
0.

0.


0.
66
65

65
85
84
73

72


78
0.74 ->
0.

0.
82

88 ->
0.81


0.86
0.75
0.80
66.7
79.4

68.6
78.3
78.5
53.7

57.0


59.3
13.6
73.2

24.7
57.9

52.6
59.1
68.1
9-25-87
9-25-87

9-25-87
4-21-87
4-21-87
8-19-87

9-21-87


4-28-87
7-17-87
11-16-87

5-12-87
11-16-87

4-28-87
6-19-87
5-12-87
ERR
ERR

ERR
5.43


3.55


9.85
3.65


4.50


5.18
4.87
3.93
4.77
                               E10
                                                                                  ERR
                                                                                  ERR
                                                                                  ERR
                                                                                  ERR

-------


SAMPLE
NUMBER

86186379
RG186379

RG18636G
RG186392

RG166381
RG166362
RG166383
RG1B6384
RG186385

RG186402
RG186402
RG186386
RG186386

RG186387
RGL86387
RG186387A
RG186387B

RG186388
RG186388
RG186368A
RG186394

RG186405
E6186395
RG186396
RG186397
RG186404
R6186398
RG186399

RG186400
RG186401
I2-Feb-88


SAMPLE DESCRIPTION
D. PAPER HACHINE5
Nos 1,2,3,4 & 5 Machines
Nos 1,2.3.4 li 5 Hachines
AVERAGE
Otis Hill Return
Otis Rill Return
AVERAGE (380/392)
Titaniuf Dioiide
Sliiicide RX-36
Sliticide RI-31
Pontaiine Brilliant Paper
Pontaiine Fast Scarlet
E. UTILITIES. UASTEUATER TREATHENT
Priiary Influent
Priiary Influent
Priiary Influent
Priiary Influent
AVERAGE (402/386)
Coibined Devatered Sludge
Coibined Devatered Sludge
Coibined Devatered Sludge
Coibined Devatered Sludge
AVERAGE (3B7/387A/387B)
Final Effluent
Final Effluent
Final Effluent
Final Effluent
AVERAGE (388/388A)
Final Effluent (Grab)
Bottoi Ash
Fly Ash
Grav, Thick. Secondary Sludge
Grav. Thick. Secondary Sludge
Landfill Leachate
Coibined Bleach Plant Eff.
F. OTHER
Reagent Blank
Bottle Blank
Hill E
Laboratory Data

TCDD
(ppt)

0.0522
0.0526
0.0525
0.0908
0.106
0.0984






0.680
0.743
0.681
0.497
0.650
193
168
191
161
178
0.0881
0.0953
0.0804

0.0879

WHO. 276)
ND(0.461)
498

ND<0.00817)





320/322
RATIO

0.84
0.62

0.75
0.78







0.78
0.84 ->
0.76
0.79

0.81
0.79
0.84
0.79

0.77
0.70
0.65 ->



»
i«
0.77

H ->





SREC
13C12TCDD

77.4
49.0

63.7
67.4







68.1
15.8
79.3
41.0

82.4
64.5
78.9
87.9

71.5
65.9
37.4



53.4
66.5
101.1

39.6




LAB
REPORT
DATE

7-9-87
8-19-87

8-19-87
8-19-87







11-16-87
6-18-87
3-19-87
6-18-87

4-21-87
8-19-87
8-26-87
8-26-87

7-7-87
9-30-87
8-26-87



9-21-87
9-21-87
9-21-87

9-11-87





H TCDF
»« (ppt)

0.170
0.176
0.173
0.332
0.361
0.346






3.117
3.228
3.530
2.267
3.036
879
670
762
713
756
0.447
0.441
0.359

0.416

WHO. 183)
ND(0.310)
2147

0.0636





304/306
RATIO

0.72
0.75

0.74
0.73







0.76
0.75 ->
0.88 ->
4.76

0.76
0.75
0.78
0.70

0.76
0.74
0.78 ->



H






SREC
13C12TCDF

60.7
65.3

63.1
66.2







73.8
15.1
31.7
46.0

70.1
79.0
75.7
106.0

65.8
65.7
30.4



42.1
56.2
92.5

37.2




LAB
REPORT
DATE

7-9-87
8-19-87

8-19-87
8-19-87







11-16-87
6-18-87
3-19-87
6-18-87

4-21-87
8-19-87
8-26-87
8-26-87

7-7-87
9-30-87
8-26-87



9-21-87
9-21-87
9-21-87

9-11-87





TCDF/TCDD
RATIO



3.3


3.52
ERR
ERR
ERR
ERR
ERR





4.67




4.24



ERR
4.73

ERR
ERR
4.31
ERR
ERR
ERR



Ell

-------
                ATTACHMENT F
MASS.FLOW RATES  OF  2378-TCDD and 2378-TCDF

-------
                           ATTACHMENT  F
                              NOTES
(1)  ND - Not detected.   Analytical detection level in parentheses.
(2)  Ave -  Concentration  used   for mass   flow determinations  is  an
          average  of  multiple analyses of the  same sample  or  of
          duplicate  field  samples.
(3)  QA  -  Percent  recoveries  of  internal   standards less  than 40%
          are indicated.   See Sections VI and  VII  for  discussion
          of the  significance of these  recoveries.

-------
Nil! A
   8-Feb-8
                                                                                                                 Nil! A
Hass Balance [ND assuied 0.0 ]
Basis  : 1 Day                       Saiple ID

Al. General Hill Inputs
   1. Treated River Vater           DE 020801
   2. Hlf Chips                      DE 020805
   3. SU Chips                      DE 020804
   4. Landfill Leachate             DE 020621
Bl. General Setter Inputs
   1. Water Treatment Sludge        DE 020802
   2. Vater Treatient Bacbash      DE 020803
   3. Bleach Plant Total
   4. Coibined Pulping              DE 020806
   5. Coibined Recovery             DE 020807
   6. Paver House                   DE 020818
   7. Coibined Paper Machines       DE 020811
                               Flo* Total

Cla.  Bleach Plant Inputs
   1. Ml Brounstock Pulp            DE 020903
   2. SV Brovnstock Pulp            DE 020901
   3. Treated River Vater           DE 020801
   4. Paperiachine Vhitewater       DE 021001

Clb.  Detailed Bleach Plant Filtrate Pious
   1. SUC Stage Filtrate           DE 020906
   2. SU Eo Stage Filtrate          DE 020907
   3. SU H Stage Filtrate           DE 020908
             Softuood Line Subtotal

   4. HWC Stage Filtrate           DE 020909
   5. HV(Hypo Line) Eo Filtrate     DE 020910
   6. HVIHypo Line) H Filtrate      DE 020911
   7. HIKPeroxide Line) Eo Filtrate DE 020912
   8. HUtPeroiide Line) H Filtrate  DE 020913
   9. HiKPeroxide Line) H Filtrate  DE 020914
             Hardwood Line Subtotal
                       Bleach Plant Total
Dla. WTP Inputs
   1. Influent To IOTP
   2. Landfill Leachate
   3. Fly Ash

Dlb. UUTP Sludge Inputs
   I. Fly Ash
   2. Priiary Sludge
   3. Secondary Sludge
DE 020921
DE 020821
DE 020919
DE 020919
DE 02DB19
DE 020820
Flov
(HGD or Dry
Tons/Day)
20
595
105
0.1B

0.8
0.8
7.6
5.5
0.17
0.5
4.3
19.7
355
160
7
1.5

1.73
1.44
0.58
3.75
1.58
0.73
0.26
0.34
0.64
0.30
3.85
7.60
20.1
0.18
20

20
55
7.2


TCDD
(PPT)
0


0.0253
TOTAL






0.0205
TOTAL
0
0
0

TOTAL
0.238
1.62
0.342

0.0212
0
0
0.0453
0.0403
0.0247

TOTAL
0.136
0.0253
0
TOTAL
0
23.5
709
TOTAL

TCDD
(Grais)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
1.724E-05
1.724E-05
O.OOOEtOO
O.OOOE^OO
1.254E-02
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.336E-04
1.287E-02
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
1.558E-03
9.920E-03
7.508E-04
1.223E-02
1.268E-04
O.OOOEtOO
O.OOOEtOO
5.830E-05
9.762E-05
2.605E-05
3.107E-04
1.254E-02
1.035E-02
1.724E-05
O.OOOEtOO
1.036E-02
O.OOOEtOO
1.174E-03
4.635E-03
5.809E-03

TCDD
(Ibs) ND AVE
O.OOOEtOO HD(0.00514)
O.OOOEtOO
O.OOOEtOO
3.797E-08 X
3.797E-08
O.OOOEtOO
O.OOOEtOO
2.762E-05
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.349E-07
2.836E-05
O.OOOEtOO ND(0.309)
O.OOOEtOO MD(0.738)
O.OOOEtOO ND(0.00514)
O.OOOEtOO
O.OOOEtOO
3.433E-06
2.185E-05
1.654E-06
2.694E-05
2.793E-07
O.OOOEtOO ND(0.0326)
O.OOOEtOO ND(0.0168)
1.284E-07
2.150E-07
6.178E-08
6.845E-07
2.762E-05
2.279E-05
3.797E-08 X
O.OOOEtOO MH0.660I
2.283E-05
O.OOOEtOO ND(0.660)
2.585E-06
1.021E-05
1.279E-05


QA
27.9 J














27.9 »
















17.6 J

17.6 t



                                                             Fl

-------
Hill A
08-Feb-88
                                                                                                                        Hill A
Hass Balance [ND assuied 0.0 J
Basis : 1 Day

A2. General  Hill Exports
   1. UUTP Effluent
   2. UUTP Coiposite Sludge
   3. HU Hypo Line Pulp
   4. HV Peroxide Line Pulp
   5. SU Line Pulp
   6. Bottoi Ash

B2. General  Hill Sever Exports
   1. Influent To UUTP

C2a.  Bleach Plant Exports
   1. Bleached HV Hypo Pulp
   2. Bleached HU Peroxide Pulp
   3. Bleached SU Pulp
   4. Coibined Process Uasteuater
      (froeCib.)

C2b. Detailed Bleach Plant Exports
   1. Cotbined Process Uastevater

D2a. UUTP Exports
   1. Effluent
   2. UUTP Coiposite Sludee

D2b. UUTP Sludge Exports
   I. UUTP Conposite Sludge

Sanple ID

DE 020922
DE 020920
DE 020904
DE 020905
DE 020902
DE 020918

DE 020921

DE 020904
DE 020905
DE 020902

Flow
i«GD or Dry
Tons/Day)
23.2
82.2
160
160
144
2

20.1

160
160
144
7.6

TCDD
(PPT)
0.124
36.6
4.89
2.98
15.8

TOTAL
0.136
TIITAL
4.89
2.98
15.8


TCDD
(Grais)
1.089E-02
2.732E-03
7. 104E-04
4.329E-04
2.066E-03
O.OOOE+00
1.683E-02
1.035E-02
1.035E-02
7.104E-04
4.329E-04
2.066E-03
1.254E-02

TCDD
(Ibs)
2.398E-05
6.017E-06
1.565E-06
9.536E-07
4.550E-06
O.OQOE*QO
3.707E-05
2.279E-05
2.279E-05
1.565E-06
9.536E-07
4.550E-06
2.762E-05

Percent
Total ND AVE QA
64.7* X
16.2* X
4.2*
2.61
12.3* X
0.0*
100.0*
100.0*
100.0*
4.5*
2.7*
13.1* X
79.6*
DE 020922
DE 020920
DE 020920
        TIITAL    1.575E-02   3.469E-05      100.0*

 7.6             1.254E-02   2.762E-05      100.0*
        TOTAL    1.254E-02   2.752E-05      100.0*

23.2     0.124   1.089E-02   2.398E-05       79.9*
82.2      36.6   2.732E-03   6.017E-06       20.1*
        TdTAL    1.362E-02   3.000E-05      100.0*

82.2      36.6   2.732E-03   6.017E-06      100.0*
                                                            TCTAL    2.732E-03   6.017E-0
                                                             100.0*
                                                              F2

-------
Kill A
08-Feb-88
Hill A
Hass
Basis

Ai.





Bl.









Balance !ND assuied D.O 1
• : 1 Day



Saiple ID


Flow
IBGD or Dry
Tons/Day)

TCDF
(PPT)



TCDF


(Grais)

TCDF
(Ibs) ND AVE


QA
General Hill Inputs
1.
2.
3.
4.

Treated River Water
Hil Chips
SB Chips
Landfill Leachate

DE
DE
DE
DE

020801
020805
020804
020821

20
595
105
0.18

0


0.110
TOTAL
0.
0.
0.
7.
7.
OOOEtOO
OOOEtOO
OOOEtOO
494E-05
494E-05
0.
0.
0.
1.
1.
OOOEtOO WHO. 00107)
OOOEtOO
OOOEtOO
651E-Q7 I
651E-07
20.8 X




General Sever Inputs
I.
2.
3.
4.
5.
6.
7.

Cla.





1.
2.
3.
4.

Clb.












1.
2.
3.

4.
5.
6.
7.
8.
9.


Dia.




1.
2.
3.

Dlb.




1.
2.
3.

Water Treatient Sludge
Uater Treatient Backwash
Bleach Plant Total
Coibined Pulping
Combined Recovery
Power House
Coibined Paper Machines
Flow
Bleach Plant Inputs
HU Brounstock Pulp
SU Brovnstock Pulp
Treated River Vater
Paperiachine Whitewater

Detailed Bleach Plant Filtrate
SVC Stage Filtrate
SW Eo Stage Filtrate
SU H Stage Filtrate
Softvood Line Subtotal
HUC Stage Filtrate
HtKHypo Line) Eo Filtrate
HViHypo Line) H Filtrate
HWtPeroxide Line) Eo Filtrate
HlHPeroride Line) H Filtrate
HUCPeroxide Line) H Filtrate
Hardwood Line Subtotal
Bleach Plant
WUTP Inputs
Influent To WITP
Landfill Leachate
Fly Ash

Ifl/TP Sludge Inputs
Fly Ash
Priiary Sludge
Secondary Sludge

DE
DE

DE
DE
DE
DE
020802
020803

020806
020807
020818
020811
Total

DE
DE
DE

020903
020901
020801
DE0201001


0.8
0.6
7.6
5.5
0.17
0.5
4.3
19.7

355
160
7
1.5







0.191
TOTAL

0
0
0

TOTAL
0.
0.
2.
0.
0.
0.
3.
2.

0.
0.
0.
0.
0.
OOOEtOO
OOOEtQO
189E-01
OOOE^OO
OOOEtOO
OOOEtOO
109E-03
220E-01

OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
0.
0.
4.
0.
0.
0.
6.
4.

0.
0.
0.
0.
0.
OOOEtOO
OOOEtOO
822E-04
OOOEtOO
OOOEtOO
OOOEtOO
847E-06
891E-04

OOOEtOO ND(0.231)
OOOEtOO ND(0.271)
OOOEtOO WHO, 00107)
OOOEtOO
OOOEtOO











20.81


Flows
DE
DE
DE

DE
DE
DE
DE
DE
DE

020906
020907
020906

020909
020910
020911
020912
020913
020914

Total

DE
DE
DE


DE
DE
DE


020921
020621
020919


020919
020819
020820

1.73
1.44
0.58
3.75
1.58
0.73
0.26
0.34
0.64
0.30
3.85
7.60

20.1
0.18
20


20
55
7.2

3.806
32.6
5.778

0.305
0.247
0.114
0.318
0.17
0.174

TOTAL

1.916
0.110
0
TOTAL

0
362
10932
TOTAL
2.
1.
1.
2.
1.
6.
1.
4.
492E-02
777E-01
268E-02
153E-01
824E-03
825E-04
122E-04
092E-04
5.
489E-05
37. 8X
3.914E-04
2.
4.
4.
1.
2.
9.
4.118E-04 9.
1.
3.
2.

1.
7.
976E-04
637E-03
189E-01

458E-01
494E-05
0. OOOEtOO
1.

0.
1.
7.
9.
458E-01

OOOEtOO
906E-02
147E-02
055E-02
4.
8.
4.

3.
1.
0.
794E-05
742E-04
018E-06
503E-06
471E-07
014E-07
071E-07
352E-07
012E-06
822E-04

211E-04
651E-07 I
OOOEtOO NDf 0.349)













23.9*
3.212E-04

0.
4.
1.
1.

OOOEtOO MHO. 349)
202E-05
574E-04
994E-04

23.9 X



                                                            F3

-------
mil A
08-Feb-88
                                                                   Hill A
Mass Balance [ND assuied 0.0 ]
Basis :  1 Day

A2.  General  Hill  Exports
   1. UUTP Effluent
   2. y»TP Coiposite Sludge
   3. HU Hypo Line Pulp
   4. HU Peroxide Line Pulp
   5. SU Line Pulp
   6. Bottoi Ash

62.  General  Hill Sever Exports
   1. Influent To UUTP

C2a. Bleach Plant Exports
   1. Bleached HU Hypo Pulp
   2. Bleached HU Peroxide Pulp
   3. Bleached SU Pulp
   4. Coibined Process Vastenater
      (froiClb.)

C2b. Detailed Bleach Plant Exports
   1. Coibined Process Uastevater
      (froiClb.)

D2a. UUTP Exports
   1. Effluent
   2. UUTP Coiposite Sludge

D2b. UUTP Sludge Exports
    1. UUTP Coiposite Sludge

Saiple ID

DE 020922
DE 020920
DE 020904
DE 020905
DE 020902
DE 020918

DE 020921

DE 020904
DE 020905
DE 020902




DE 020922
DE 020920

FlON
(HGD or Dry
Tons/Day)
23.2
82.2
160
160
144
2

20.1

160
160
144
7.6

7.6

23.2
82.2


TCDF
(PPT)
2.18
678
47.3
50.1
333

TOTAL
1.916
TOTAL
47.3
50.1
333

TOTAL

TOTAL
2.18
678
TOTAL

TCDF
(Grais)
1.914E-01
5.060E-02
6.872E-03
7.279E-03
4.354E-02
O.OOOE+00
2.997E-01
1.458E-01
1.458E-01
6.872E-03
7.279E-Q3
4.354E-02
2.189E-01
2.766E-01
2.189E-01
2.189E-01
1.914E-01
5.060E-02
2.420E-01

TCDF
(Ibs)
4.217E-04
1.115E-04
1.514E-05
1.603E-05
9.590E-05
O.OOOE+00
6.602E-04
3.211E-04
3.211E-04
1.514E-05
1.603E-05
9.590E-05
4.822E-04
6.093E-04
4.822E-04
4.822E-04
4.217E-04
1.115E-04
5.331E-04

Percent
Total
63.91
16.9S
2.3*
2.41
14. 51
0.01
100. OS
100. OS
100. OS
2.5S
2.6S
15. 7S
79. IS
100. OS
100.0S
100.01
79. IS
20. 9S
100. OS
                                                                        ND    AVE   QA
DE 020920
82.2
678   5.060E-02   1.115E-04
100.OX
                                                           F4

-------
Hill
08-Feb-88
Mill
Mass Balance
Basis : 1 Day

Al. General Hill Inputs
1. Treated Vater(River)
2. HV Chips
3. SV Chips
4. 5V Sawdust

il. General Sever Inputs
1. Combined Paper Machines
2. Caustic Sever
3. Coibined Pulping
4. Corrosive Sever
Flov
Cla. Bleach Plant Inputs
1. Brounstock Pulp
2. Process Uater

Clb. Detailed Bleach Plant Filtrate
1. C Stage Filtrate
2. E Stage Filtrate
3. H-l Stage Filtrate i
4. H-2 Stage Filtrate *
5. D Stage Filtrate *
> Recycled Flovs Flov
Dl. IfllTP Inputs
1. Influent To WVTP

Saiple ID


86374601
86374604
86374603
86374605


86374621
86374615
86374606
86374607
Total

86374611
86374601

Flovs
86374673/613
86374615
86374616
86374617
86374614
Total

86374644
Flov
(HGD or Dry
Tons/Day)

37.1
220
880
630


6.9
2.2
10.8
3.1
23

883
8.25


6.05
2.2
0.24
1.36
1.57
8.25

37.35

TCDD
(PPT)

0



TOTAL

0
0.224


TOTAL

0
0
TOTAL

0.0232
0.224
0.258
0.132
0.0298
TOTAL

0

TCDD
(Grais)

O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00

O.OOOE+00
1.665E-03
O.OOOE+00
O.OOOE+00
1.865E-03

O.OOOE+00
O.OOOE+00
O.OOOE+00

5.313E-04
1.865E-03
2.344E-04
6.795E-04
1.771E-04
2.397E-03

O.OOOE+00

TCDD
(Ibs) ND AVE QA

O.OOOE+00 ND(0.00693) 25.2 *
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00

O.OOOE+00 NDI0.00514) 35.9 X
4.108E-06 I
O.OOOE+00
O.OOOE+00
4.108E-06

O.OOOE+00 ND(0.949)
O.OOOE+00 ND(0. 00693) 25.2 X
O.OOOE+00

1.170E-06
4.108E-06 I
5.162E-07
1.497E-06
3.901E-07
5.279E-06

O.OOOE+00 ND(0. 00644) I
                                                               TOTAL
»86374614 Recycled To 86374673 [Acid Sever Assuied To Be Higher Mass)
 86374616 And 86374617 Recycled To 86374615
                                                           F5

-------
Nil! B
                                      08-Feb-88
                                                                                                                           Hill
Mass Balance
Basis : 1 Day

A2. General Hill Exports
1. UVTP Effluent
2. UUTP Priiary Sludge
3. UUTP Secondary Sludge
4. Bleached Pulp
5. Vater Treatment Backwash
6. Landfill Leachate

B2. General Hill Sever Exports
1. Influent To VUTP

C2a. Bleach Plant Exports
1. Bleached Pulp
«2. Acid Sever
*3. Caustic Sever

C2b. Detailed Bleach Plant Exports
U. Acid Sever
»2. Caustic Sever
Flov
D2. UVTP Exports
1. Effluent
2. UUTP Priiary Sludge
3. UVTP Secondary Sludge


Saiple ID


86374645
86374641
86374642
86374612/661
86374602
86374646


86374644


86374612/661
86374673/613
86374615


86374673/613
86374615
Total

86374645
86374641
86374642

Flov
(HGD or Dry
Tons/Day)

36.6
35
17
770
1.3



37.35


770
6.05
2.2


6.05
2.2
8.25

36.6
35
17


TCDD TCDD
(PPT) (Grais)

0.0151 2.092E-03
18.9 6.006E-04
88.9 1.372E-03
11.3 7.901E-03
O.OOOEtOO
0 O.OOOEtOO
TOTAL 1.197E-02

0 O.OOOEtOO
TOTAL O.OOQEtOO

11.3 7.901E-03
0.0232 5.313E-04
0.224 1.865E-03
TOTAL 1.030E-02

0.0232 5.313E-04
0.224 1.865E-03
TOTAL 2.397E-03

0.0151 2.092E-03
18.9 6.006E-04
88.9 1.372E-03
TOTAL 4.065E-03

TCDD
(lbs>

4.608E-06
1.323E-06
3.023E-06
1.740E-05
O.OOOEtOO
O.OOOE+00
2.636E-05

O.OOOEtOO
O.OOOE+00

1.740E-05
1.170E-06
4.108E-06
2.268E-05

1.170E-06
4.108E-06
5.279E-06

4.608E-06
1.323E-06
3.023E-06
8.953E-06

Percent
Total

17.51
5. OX
11.51
66.011
O.OJ
o.ox
too. o»




76. 7X
5.2*
18. U
100. OX

22. 2X
77.8X
100.04

51. 5X
14.8X
33. 8X
100. OX
                                                                                                                     AVE
QA
                                                                                                         ND(0.00405)


                                                                                                         ND(0.00644)   X


                                                                                                                       X

                                                                                                                       X
086374614 Recycled To 86374673 [Acid Sever Assuied To Be Higher Mass]
 86374616 And 86374617 Recycled To 86374615

-------
Hill
08-Feb-88
mn
Hass Balance


Al. General Hill Inputs
1. Treated Uater(River)
2. HU Chips
3. SV Chips
4. 5V Savdust

Bl. General Sever Inputs

Sanple ID


86374601
86374604
86374603
86374605


1. Coibined Paper Machines 86374621
2. Caustic Sewer
3. Coibined Pulping
4. Corrosive Sever

Cla. Bleach Plant Inputs
1. Brovnstock Pulp
2. Process Hater

Clb. Detailed Bleach Plant
1. C Stage Filtrate
2. E Stage Filtrate
3. H-l Stage Filtrate »
4. H-2 Stage Filtrate «
5. 5 Stage Filtrate »
« Recycled Flovs
Dl. UVTP inputs
1. Influent To WTP

86374615
86374606
86374607
Flov Total

86374611
86374601

Filtrate Pious
86374673/613
86374615
86374616
86374617
86374614
Flov Total

86374644

Flov
(HGD or Dry
Tons/Day)

37.1
220
880
630


6.9
2.2
10.8
3.1
23

883
8.25


6.05
2.2
0.24
1.36
1.57
8.25

37.35


TCDF
(PPT)

0



TOTAL

0.108
1.044


TOTAL

1.54
0
TOTAL

0.0679
1.044
1.129
0.913
0.133
TOTAL

0.108
TOTAL

TCDF
(Grais)

O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO

2.821E-03
8.693E-03
O.OOOEtOO
O.OOOEtOO
1.151E-02

1.235E-03
O.OOOEtOO
1.235E-03

1.555E-03
B.693E-03
1.026E-03
4.700E-03
7.903E-04
1.025E-02

1.527E-02
1.527E-02

TCDF
(Ibs)

O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO

6.213E-06
1.915E-05
O.OOOEtOO
O.OOOEtOO
2.536E-05

2.720E-06
O.OOOEtOO
2.720E-06

3.425E-06
1.915E-05
2.259E-06
1.035E-05
1.741E-06
2.257E-05

3.363E-05
3.363E-05
 i 86374614 Recycled To 86374673
 » 86374616 And 86374617 Recycled To 86374615
                                                                                                 ND    AVE   QA
                                                                                              NDI0.00950)
                                                                          13.9%
                                                                                                             36.9*
                                                                                             ND(0.00950)
                                                                         13.91
                                                                                                             30.6*
                                                                                                             22.2*
                                                                                                         X   49.8 *,  27.9
                                                        F7

-------
Hill
08-Feb-88
                                                                                                                          Kill B
Hass Balance


A2. General Hill Exports
1. WTP Effluent
2. VUTP Priiary Sludge
3. WTP Secondary Sludfe
4. Bleached Pulp
5. Water Treatment Backwash
6. Landfill Leachate

62. General Hill Sewer Exports
1. Influent To WTP

C2a, Bleach Plant Exports
1. Bleached Pulp
«2. Acid Sewer
»3. Caustic Sewer

C2b. Detailed Bleach Plant Exports
tl. Acid Sever
«2. Caustic Sewer
Flow
D2. y«TP Exports
1. Effluent
2. VUTP Priiary Sludge
3. UUTP Secondary Sludge


Saiple ID


86374645
66374641
863746+2
86374612/661
86374602
86374646


86374644


86374612/661
86374673/613
86374615


86374673/613
86374615
Total

86374645
86374641
86374642

Flow
(HGD or Dry
Tons/Day)

36.6
35
17
770
1.3



37.35


770
6.05
2.2


6.05
2.2
8.25

36.6
35
17


TCDF
(PPT)

0.122
101
808
60.3

0.010J
TOTAL

0.1W
TOTAL

60.!)
0.067SI
l.OM
TOTAL

0.067SI
1.044
TOTAL

0.122
101
80£
TOTAL

TCDF
(Grais)

1.690E-02
3.210E-03
1.247E-02
4.258E-02
O.OOOEHX)
O.OOOE+00
7.516E-02

1.527E-02
1.527E-02

4.258E-02
1.555E-03
8.693E-03
5.2B3E-02

1.555E-03
8.693E-03
1.025E-02

1.690E-02
3.210E-03
1.247E-02
3.25BE-02

TCDF
(Ibs)

3.723E-05
7.070E-06
2.747E-05
9.379E-05
O.OOOEHX)
O.OOOE+00
1.656E-04

3.363E-05
3.363E-05

9.379E-05
3.425E-06
1.915E-05
1.164E-04

3.425E-06
1.915E-05
2.257E-05

3.723E-05
7.070E-06
2.747E-05
7.177E-05

Percent
Total

22.5*
4.3X
16. 6*
56.6*
O.W
0.0X
100. OX

100. M
100, OX

80. 6X
2.9X
16.5X
100. OK

15.2X
84.8*
100. OX

51. 9t
9.911
38.3*
100.0$
                                                                                                              ND    AVE   QA
                                                                                                                          30.5 X
                                                                                                                      X   67.IX. 10.31. 55.41
                                                                                                                      X   49.8 X, 27.9 X
                                                                                                                      X   67.IX, 10.3X, 55.4*
                                                                                                                          30.61
                                                                                                                      X
                                                                                                                          30.6X
                                                                                                                          30.5X
 « 86374614 Recycled To 86374673
 i 86374616 And 86374617 Recycled To 86374615

-------
Nil! C
      8-Feb-88
                                                                                                                    Nil! C
Mass Balance
Basis : I Day                      Saiple  ID

Al. General Hill Inputs
   1. Treated Kater(Hiver)         DE 026001
   2. HU Chips                     DE 026103
   3. Landfill Leachate            DE 026014
Bl. General Sewer Inputs
   1. Coibined Paper Machines      DE 026118
   2. Misc. Boiler/Scrubber        DE 026205
   3. Sluiced Coal Bottoi Ash      DE 026007
   4. ffisc. Pulp Hi 11/Recovery     DE 026111
   5. disc. Pulping                DE 026107
  »6. Bleach Plant/Scrubber Vents  DE 026114
   7. No. 2 Softening Sludge       DE 026101
                              Flo* Total
Cla.  Bleach Plant Inputs
   1. Brownstock Pulp              DE 026002
   2. Process Vater                DE 026001
Clb. Detailed Bleach Plant Filtrate Flovs
    1. C Stage Filtrate             DE 026004
   2. Eo Stage Filtrate            DE 026005/211
    3. D Stage Filtrate*!           DE 026006/213
Dla. Ifl/TP Inputs
    1. Influent To WTP
   2. Landfill Leachate
Dlb. UUTP Sludge Inputs
   1. Secondary Sludge
DE 026012
DE 026014
DE 026207
Flow
(HGD or Dry
Tons/Day)
30
2200


8.2
5
1
1.6
3.5
0.3
19.6
1011
13

2.95
4.9
0
31.5



TCDD
(PPT)
0

0
TOTAL
0.0106



0

TOTAL
0
0
TOTAL
0
0
0
0
0
TOTAL

TCDD
(Grais)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.290E-04
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.290E-04
O.OOQEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOE+00
O.OOOE*00

TCDD
Obs)
O.OOOE*00
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.247E-07
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.247E-07
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO


ND AVE QA
WHO. 00531)

NDIO. 00595)





ND(0. 00912)


MH0.564)
ND(0. 00531)

NDI0.00593)
ND(0.0106) !
NDI0.00341) I
NDI0.00278)
ND(0.00595)

22
11.2   2.237E-04   4.928E-07
 « Mainly Saiple DE 026004(DE 026005/DE 026006 Possible)
** Interiittant Flov INonally Zero)
      DE 026005 Partially Recycled To DE 026004
                                                           F9

-------
Mill C
08-Feb-88
                                                                                                                          Hill C
Hass Balance
Basis :  1 Day                      Saiple ID

A2.  General  Hill  Exports
   1. tl«TP Effluent (36-72hr)       DE 026206
   2. Coibined Denatered Sludge    DE 026011
   3. Bleached Pulp                DE 026003
   4. Coal Ash                     DE 026007
   5. Coal Ash - ESP               DE 026008
   6. Coal Mechanical  Ash          DE 026009

B2.  General  Kill  Sever Exports
   1. Influent To WVTP             DE 026012

C2a. Bleach Plant Exports
   1. Bleached Pulp                DE 026003
   2. B.P. Effluent/Scrubber Vents DE 026114
   3. C/D Filtrate                 DE 026004
   4. Eo Stage Filtrate            DE 026005
   5. D Stage Filtrate"           DE 026006/213
     *» intenittant Fio«(Norially Zero)

D2.  WTP Exports
    1. Effluent (36-72hr)           DE 026206
   2. Coibined Denatered Sludge    DE 026011
D2b. VUTP Sludge Exports
    1. UVTP Coiposite Sludge        DE 026011

E2. Other
    1. WWTP Effluent (0-24 hrs)    DE 026013
       Recycle to Hill
Flo*
(HGD or D;-y
Tons/Day,1
29. !i
21li
930




31.ii

93(1
3.J.
2.9!>
4.E
(i
29. E
216

216

TCDD
(PPT)
0
3.32
0



TOTAL
0
TOTAL
0
0
0
0
0
0
3.32
TOTAL
3.32
TOTAL
TCDD
(Grais)
O.OOOE+00
6.511E-04
O.OOOE+00



6.511E-04
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+Ofl
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
6.511E-04
6.511E-04
6.511E-04
6.511E-04
TCDD
(Ibs)
O.OOOE+00
1.434E-06
O.OOOE+00



1.434E-06
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.434E-06
1.434E-06
1.434E-06
1.434E-06
Percent

Total ND AVE
0.0* HD(0. 00339)
100. OX
O.OX ND(0.62)
0.0*
0.0V
0.0*
100.0*
ND(0.00278)

0.0* NDI0.62)
O.QK ND(0.00912)
0.0* ND(0. 00593)
0.0* ND(0.0106)
0.0* ND( 0.00341)
0.0* NDI0.00339)
100.0*
100.0*
100.0*
100.0*
X
I











I

X


X
                            0   O.OOOE+00   O.OOOE+00
HD(0.00281)
                                                           F10

-------
Mill C
   09-Feb-88
                                                                                                                Hill C
Hass Balance
Basis : 1 Day

Al. General Hill Inputs
   1. Treated Uater(River)
   2. HU Chips
   3. Landfill Leachate
Bl. General Sever Inputs
   1. Coebined Paper Machines
   2. Misc. Boiler/Scrubber
   3. Sluiced Coal Bottoi Ash
   4. Hisc. Pulp Hill/Recovery
   5. Hisc. Pulping
 « 6. Bleach Plant/Scrubber Vents
   7. No. 2 Softening Sludge
                              Flo*
Cla.  Bleach Plant Inputs
   1. Brovnstock Pulp
   2. Process Water
Clb. Detailed Bleach Plant Filtrate Flow
   1. C Stage Filtrate
   2. Eo Stage Filtrate
   3. 0 Stage Filtrateti

Saiple ID

DE 026001
DE 026103
DE 026014

DE 026118
DE 026205
DE 026007
DE 026111
DE 026107
DE 026114
DE 026101
Total
DE 026002
DE 026001

! FlOKS
DE 026004
DE 026005/211
DE 026006/213
Flov
(HGD or Dry
Tons/Day)
30
2200


8.2
5
Inc 1.026015
1
1.6
3.5
0.3
19.6
1011
13


2.95
4.9
0

TCDF
(PPT)
0

0
TOTAL
0.197




0.429

TOTAL
0
0
TOTAL

0.0929
0.0558
0.0136

TCDF
(Grans)
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
6.114E-03
O.OOOE+OQ

O.OOOE+00
O.OOOE+00
5.683E-03
O.OOOE+00
1.180E-02
O.OOOE+00
O.OOOE+00
O.OOOE+00

1.037E-03
1.035E-03
O.OOOE+00

TCDF
(Ibs)
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.347E-05
O.OOOE+00

O.OOOE+00
O.OOOE+00
1.252E-05
O.OOOE+00
2.599E-05
O.OOOE+00
O.OOOE+00
O.OOOE+00

2.285E-06
2.280E-06
O.OOOE+00


ND AVE QA
ND(0.00694) 15.21

ND(0. 00869)









NDI0.162)
ND(0.00694) 15.21



X 25U3K
X
Dla. yUTP Inputs
   1. Influent To UUTP
   2. Landfill Leachate
DE 026012           31.5     0.0362   4.316E-03   9.507E-06
DE 026014                         0   O.OOOE+00   O.OOOE+00   WHO.
                             TOTAL    4.316E-03   9.507E-06
Dlb. VUTP Sludge Inputs
   1. Secondary Sludge
DE 026207
22
75.4   1.506E-03   3.318E-06
   Mainly Saiple DE 026004(DE 0260D5/DE 026006 Possible)
   Interiittant Flow (Mortally Zero)
     DE 026005 Partially Recycled To  DE 026004
                                                          Fll

-------
Hill C
   09-Feb-88
                                                                                                                          Hill C
Mass Balance
Basis : 1 Day

A2.  General  Hill  Exports
   1. WTP Effluent (36-72hr)
   2. Coibined De»atered Sludge
   3. Bleached Pulp
   4. Coal Ash
   5. Coal Ash -  ESP
   6. Coal Hechanical  Ash

B2.  General  Hill  Sever Exports
   1. Influent To BwTP

C2a.  Bleach Plant Exports
   1. Bleached Pulp
   2. B.P. Effluent/Scrubber Vents DE 026114
   3. C/D Filtrate
   4. Eo Stage Filtrate
   5. D Stage Filtrate"
   » Intenittent Flov (Nonally Zero)

D2. WTP Exports
   1. Effluent (36-72hr)           DE 026206
   2. Coibined Denatered Sludge    DE 026011

Saiple ID

DE 026206
DE 026D11
DE 026003
DE 026007
DE 026008
DE 026009

DE 026012

DE 026003
DE 026114
DE 026004
DE 026005
DE 026006/213
!ero)
Flow
(MGD or Dry
Tons/Day)
29.5
216
930




31.5

930
3.5
2.95
4.9
0


TCDF
(PPI)
0.01124
36.6
14.9



TOTAL
0.0362
TOTAL
14.9
0.429
0.0929
0.0573
0.0136
TOTAL

TCDF
(Grais)
1.255E-03
7.571E-03
1.258E-02



2.141E-02
4.316E-03
4.316E-03
1.258E-02
5.683E-03
1.037E-03
1.063E-03
O.OOOEKX)
2.037E-02

TCDF
(Ibs)
2.764E-06
1.668E-05
2.771E-05



4.715E-05
9.507E-06
9.507E-06
2.771E-05
1.252E-05
2.285E-06
2.341E-06
O.OOOEHX)
4.486E-05

Percent
Total
5.9*
35. 4*
58.81
0.0*
0.0*
0.0*
100. OS
100.0*
100.01
61.61
27.9*
5.1*
5.2*
0.0*
100.0*


ND AYE
X
X










I
X

                    29.5   3.01124   1.255E-03   2.764E-06        14.2*
                     216      38.6   7.571E-03   1.668E-05        85.8*

                            TOTAL    8.826E-03   1.944E-05       100.0*
                                                                                   I   25*.13*
D2b. UtfTP Sludge Exports
    1. WTP Coiposite Sludge
DE 026011
E2. Other
   1. WTP Effluent (0-24 hrs)     DE 0260L3
     Recycle to Hill
216      38.6   7.571E-03   1.668E-05      100.0*
       TOTAL    7.571E-03   1.668E-05      100.0*
                       2    0.0128   9.690E-05   2.134E-07
                                           100.0*
                                                            F12

-------
Kill D
   09-Feb-88
                                                                                                                 Hill  D
Hass Balance
Basis : 1 Day

Al. General Hill Inputs
   I. Treated UaterlNorth)
   2. Treated Mater(South)
   3. SU Chips
Bl. General Sever Inputs
   1. Coibined Paper Machines
   2. Misc. Pulping
   3. disc. Evap./Recovery/Kiln
   4. Boiler
   5. A Side Acid Sever
   6. B Side Acid Sever
   7. Conbined Caustic Sever

Cla.  Bleach Plant Inputs
   1. Coibined Brovnstock Pulp
   2. Process Uater
   1. C Stage Filtrate A Side
   2. Coibined E Stage Filtrate
   3. H Stafe Filtrate A Side
   4. C State Filtrate B Side
   5. H Stage Filtrate B Side

Dla.  UUTP Inputs
   1. Influent To MITP

Dlb.  UUTP Sludge Inputs
   1. Priiary Sludge
   2. Secondary Sludge

Saiple ID

DF 02*402
DF 024403
DF 024404

DF 024501
DF 024405
in DF 024406
DF 024516
DF 024412/605
DF 024415
DF 024413
Flov Total
> DF 024409
DF 024403

trate Flovs
DF 024412/605
:e DF 024413
DF 024414
DF 024415
DF 024418
Flov Total
DF 024604

DF 024514
DF 024515
Flov
(HGD or Dry
Tons/Day)
10.2
11.7
1712

9.6
3.5
0.25
0.06
1.42
0.95
2.72
18.5
419
5.02


1.42
2.72
1.42
0.95
0.92
7.43
18.85

54
8

TCDD
(PPT)
0


TOTAL
0



0.0376
0.119
0.257
TOTAL
0

TOTAL

0.0376
0.257
0.0551
0.119
0.331
TOTAL
0.0283
TOTAL
17.4
36.1

TCDD
(Grais)
O.OOOEtOO
O.OOOE+00
O.OOOE'OO
O.OOOE+00
O.OOOEHX)
O.OOOE+00
O.OOOEKX)
O.OOOE+00
2.021E-04
4.279E-04
2.646E-03
3.276E-03
O.OOOEtOO
O.OOOE'OO
O.OOOEfOO

2.021E-04
2.646E-03
2.96IE-04
4.279E-04
1.153E-03
4.725E-03
2.019E-03
2.019E-03
8.532E-04
2.622E-04

TCDD
(Ibs) ND AVE QA
O.OOOEKK) ND(0. 00456)
O.OOOE+00
O.OOOE*00
O.OOOE+00
O.OOOfrOO MHO. 0059)
O.OOOE+00
O.OOOEtOO
O.OOOE+00
4.451E-07 X
9.425E-07
5.828E-06
7.216E-06
O.OOOE+00 ND(0.695)
O.OOOE+00
O.OOOEfOO

4.451E-07 I
5.82BE-06
6.523E-07
9.425E-07
2.539E-06
1.041E-05
4.447E-06 X 28.4*
4.447E-06
1.879E-06
5.776E-07
   3.  Secondary Sludge
      After Chlorination
DF 024519
35.8   2.601E-04   5.728E-07
                                                           F 13

-------
Hill D
09-Feb-88
                                                                                                                              Hill  D
Flov
Saaple ID (HGD or Dry
Tons/Day)
A2. General Hill Exports
1. WvTP Effluent
2. Coibined Devatered Sludge
3. Bleached Pulp - A Side
4. Bleached Pulp - B Side

B2. General Sever Exports
I. IftiTP Influent

C2a. Bleach Plant Exports - General
1. Bleached Pulp A Side
2. Bleached Pulp B Side
3. A Side Acid Sever
4. B Side Acid Sever
5. Contained Caustic Sever

C2b. Detailed Bleach Plant Exports
1. Bleached Pulp A Side
2. Bleached Pulp B Side

DF 024512
DF 024513/606
DF 024410
DF 024411


DF 024604

Severs
DF 024410
DF 024411
DF 024412/605
DF 024415
DF 024413


DF 024410
DF 024411
3. Bleach Plant Flows Total (Clb.)

D2a. VVTP Exports
1. Effluent
2. Coibined Devatered Sludge

D2b. UVTP Sludge Exports
1. Contained Devatered Sludge

D2c. Sludge Lagoon
1. Sludge Lagoon Effluent



DF 024512
DF 024513/606


DF 024513/606


DF 024517


18.49
62
250
120


18.85


250
120
1.42
0.95
2.72


250
120
7.43


18.49
62


62


0.603

TCDD
(PPT)

0
18.1
0
3.94
TOTAL

0.0283
TOTAL

0
3.94
0.0376
0.119
0.257
TOTAL

0
3.94

TOTAL

0
18.1
TOTAL

18.1
TOTAL

0
TOTAL
TCDD
(Grais)

O.OOOEtOO
1.019E-03
O.OOOEtOO
4.293E-04
1.448E-03

2.019E-03
2.019E-03

O.OOOEtOO
4.293E-04
2.021E-04
4.279E-04
2.646E-03
3.705E-03

O.OOOEtOO
4.293E-04
4.725E-03
5.154E-03

O.OOOEtOO
1.019E-03
1.019E-03

1.019E-03
1.019E-03

O.OOOEtOO
O.OOOE+00
TCDD
Ubs)

O.OOOEtOO
2.244E-06
O.OOOEtOO
9.456E-07
3.190E-06

4.447E-06
4.447E-06

O.OOOEtOO
9.456E-07
4.451E-07
9.425E-07
5.828E-06
8.161E-06

O.OOOEtOO
9.456E-07
1.041E-05
1.135E-05

O.OOOEtOO
2.244E-06
2.244E-06

2.244E-06
2.244E-06

O.OOOEtOO
O.OOOEtOO
Percent
Total ND AVE

0.0* MD(0.00716)
70.4*
0.0* NDU.03)
29.6*
100.0*




0.0* NDU.03)
11.6*
5.5*
11.5*
71.4*
100.0*

0.0* NDU.03)
8.3*
91.7*
100.0*

0.0* NDI0.00716)
100.0*
100.0*

100.0*
100.0*

ERR ND(0, 00317)
ERR

It
X

X






X
X





X



X
X


X




                                                            F14

-------
Hill D
   09-Feb-8B
                                                      Hill D
Mass Balance
Basis : 1 Day
Al. Genera! Hill Inputs
1. Treated Vater(North)
2. Treated Hater(South)
3. SW Chips
Flow
Saiple ID (HGD or Dry
Tons/i)ay)
DF 024402 10.2
DF 024403 11.7
DF 024404 1712
TCDF
(PPT)
0
TOTAL
TCDF
(Grais)
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0.
0.
0.
0.
TCDF
(Ibs)
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
Bl. General Sever Inputs
1.
2.
3.
4.
5.
6.
-7
t ,

Cla.
1.
2.

Clb.
1.
2.
3.
4.
5.

Dla.
1.

Dlb.
1.
2.
CoBbined Paper Machines
Hisc. Pulping

Hisc. Evap, /Recovery/Kiln
Boiler
A Side Acid Sever
E Side fccid Sever



Combined Caustic Sever

Bleach Plant Inputs
Combined Browns lock
Process Hater

Flo*

Pulp


Detailed Bleach Plant Filtrate
C Stage Filtrate A
Side
Coibined E Stage Filtrate
H Stage Filtrate A
C Stage Filtrate B
H Stage Filtrate B

UUTP Inputs
Influent To «HTP

UUTP Sludge Inputs
Priiary Sludge
Secondary Sludge
Side
Side
Side
Flo*






DF
DF
DF
DF
i'F
DF
DF
024501
024405
024406
024516
02*1 12' 605
C24415
024413
Total

DF
DF


024409
024403

9.6
3
0.
u.
£ ,
0.
2.
16

.5
25
06
ti
95
72
.5

419
5.

02

0.0146



0.0636
0.394
0.472
TOTAL

0

TOTAL
5,
0.
0.
u.
;..
1.
4.
7.

0.
0.
0,
305E-04
OOOEtOO
OODEtOC
OOOE'OO
667E-04
417E-03
859E-03
175E-03

OOOEtOO
OOOEtOO
OOOEtOO
1.
0.
0.
r.
V,
8,
3.
1.
1.

0.
0.
0.
169E-06
GOOE'Gi.
OOCEtCO
iiiiOEtOO
121E-07
121E-06
070E-05
580E-05

OOOEtOO
OOOEtOO
OOOEtOO
Flovs
DF
DF
DF
DF
DF
024412/605
024413
024414
024415
024416
Total

DF


DF
DF

024511/604


024514
024515
1.
2.
1.
0.
0.
7.

18.




42
72
42
95
92
43

85


54
6
0.0686
0.472
0.0857
0.394
0.602
TOTAL

0.0634
TOTAL

31.9
77.9
3.
4.
4.
1.
2.
9.

4.
4.

1.
5.
687E-04
859E-03
606E-04
417E-03
096E-03
202E-03

523E-03
523E-03

564E-03
659E-04
8.
1.
1.
3.
4.
2.

9.
9.

3.
1.
121E-07
070E-05
015E-06
121E-06
617E-06
027E-05

963E-06
963E-06

445E-06
246E-06
                                                                                                   ND     AVE   6A
                                                                                               ND(0.00469)   X   291
                                                                                                            X   12.1%, 55.111,37.611

                                                                                                            X   34.9»
                                                                                               ND(0.203)
                                                                                                            X   12.11.55.14.37.6*
                                                                                                            X   34.91
                                                                                                            X   35.41
   3. Secondary Sludge
      After Chlorination
DF 024519
8      73.2   5.317E-04   1.171E-06
                                                                F  15

-------
Kill D
09-Feb-88
                                                                                                          Kill  D
Hass Balance
Basis : 1 Day
Flov
Saiple ID (HGD or Dry
Tons/Day)
TCDF
(PPT)
TCDF
(Grais)
TCDF
(Ibs)
Percent
Total ND AVE QA
A2. General Kill Exports
t.
2.
3.
4.

vl/TP Effluent
Coibined Devatered Sludge
Bleached Pulp - A Side
Bleached Pulp - B Side

DF
DF
DF
DF

02*512
024513/606
024410
024411

18.49
62
250
120

0
33.6
0
7.79
TOTAL
0.
1.
0.
8.
OOOE*00
903E-03
OOOEtOO
488E-04
2.752E-03
0.
4.
0.
1.
6.
OOOE+00
191E-06
OOOEtOO
870E-06
061E-06
0.
69.
0.
0* KD(0.00663) I 35*
2* X
0* NDU.23)
30.84 X 66.4.28.31
100.
Of
B2. General Sewer Exports
1.

C2a.
1.
2.
3.
4.
5.

C2b.
1.
2.
3.

D2a.
I.
2.

D2b.
1.

D2c.
1,

VUTP Influent

Bleach Plant Exports - General
Bleached Pulp A Side
Bleached Pulp B Side
A Side Acid Sever
B Side Acid Sever
Coibined Caustic Sever

Detailed Bleach Plant Exports
Bleached Pulp A Side
Bleached Pulp B Side
DF

024511/604

18.85

0.0634
TOTAL
4.
4.
523E-03
523E-03
9.
9.
963E-06
963E-06
100.0* I 35.4*
100.
0*
Severs
DF
DF
DF
DF
DF


DF
DF
024410
024411
024412/605
024415
024413


024410
024411
Bleach Plant Flovs Total (Clb.)
Flo*
VUTP Exports
Effluent
Coibined Devatered Sludge

VUTP Sludge Exports
Coibined Devatered Sludge

Sludge Lagoon
i Sludge Lagoon Effluent

Total

DF
DF


DF


DF


024512
024513/606


024513/606


024517

250
120
1.42
0.95
2.72


250
120
7.43
377.43

18.49
62


62


0.603

0
7.79
C.0686
0.394
0.472
TOTAL

0
7.79

TOTAL

0
33.6
TOTAL

33.8
TOTAL

0.0156
TOTAL
O.OOOEfOO
6.
3.
1.
4.
7.

0.
8.
9.
1.

0.
1.
1.

1.
1.

3.
3.
488E-04
687E-04
417E-03
859E-03
494E-03

OOOE+00
488E-04
202E-03
005E-02

OOOE+00
903E-03
903E-03

903E-03
903E-03

560E-05
560E-05
0.
1.
8.
3.
1.
1.

0.
1.
2.
2.

0.
4.
4.

4.
4.

7,
7.
OOOEfOO
870E-06
121E-07
121E-06
070E-05
651E-05

OOOEtOO
B70E-06
027E-05
214E-Q5

OOOEtOO
191E-06
.191E-06

191E-06
191E-06

,8421-08
.B42E-08
0.
11.
4.
18.
64.
100.

0.
8.
91.
0* NDd.23) 41.4*
3* X 66.4.26.3*
9* X 12.1.55.1,37.6*
91
8* X 34.9*
0*

01 NDd.23) 41.4*
4* X 66.4,28.3*
6*
100. OS

0.
100.

0* WHO. 00663) 35*
0* X
100.0*


100.0* X
100.

OS

100.0*
100.0*
                                                        F16

-------
Hi!! E
l6-Feb-8
Hill E
Hass Balance I ND = 0.0 Assuied 1
Basis : 1 Day
Ai.






81.












Cl.






C2.



Dl.




Saiple ID
Flow
(HGD or Dry
Tons/Pay)
TCDD
(PPT)
TCDD
(Graes)
TCDB
(!bs) ND AVE QA
General Hill inputs
1.
2.
3.
4.
5.

Treated water(River)
HV Chips
SU Chips
Groundvood Pulp
Landfill Leachate *
« Intenittant Flov(SOepi)
RG1-86356
RG1-863B8
RG1-86359
RG1-86360
RG1-86398

34.6
1218
1620
200


0



0
TOTAL
0.
0.
0.
0.
OOOEtOO
OOOEtOO
OOOEtOO
OOOE+00
0. OOOEtOO
0.
OOOEtOQ
0.
0.
0.
0.
0.
0.
OOOEtOO ND(. 00632) I
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO ND(0. 00817) 39.6J
OOOEtOO
General Sever Inputs
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

Coibined Paper Machines
Hisc, Pulping
Hisc. Power Groups
Otis Hill Return
Uater Treatnent Backwash
A Side E Staee Filtrate
A Side D Stage Filtrate
B Side E Stage Filtrate
B Side D Staee Filtrate
Bottoi Ash *
Fly Ash «
* Included in 3. Flow
RG1-86379
RG1 -86361
RG1 -86362
RG1 -86380/92
RG1 -86357
RG1 -86370
RG1-66371
RG1-86373
RG1 -86374
RG1-86395
RG1-86396
Total
18.9
4.2
2.6
2.5

1.8
1
1.6
0.75


33.35
0.0525


0.0984
0
2.292
0.91
3.597
1.92
0
0
TOTAL
3.
0.
0.
9.
0.
1.
3.
2.
5.
0.
0.
756E-03
OOOEtOO
OOOEtOO
311E-04
OOOEtOO
562E-02
444E-03
178E-02
450E-03
OOOEtOO
OOOEtOO
5.098E-02
8.
0.
0.
2.
0.
3.
7.
4.
1.
272E-06 I
OOOEtOO
OOOEtOO
051E-06 I
OOOEtOO NDd.82)
440E-05
587E-06
798E-05
201E-05
O.OOOEtOO ND( 0.276)
0.
1.
OOOEtOO NDI0.461)
123E-04
Bleach Plant Inputs
I.
2.
3.
4.
5.

HU B Side Brovnstock Pulp
SV B Side Brownstock Pulp
SU A Side Brovnstock Pulp
Process Uater
Paper Machine Whitewater

RG1-86365
SG1-86364/91
RG1-86364/91
RG1-86356
RG1-86379

289
197
525
9
With Above

0
0
0
0
0.0525
TOTAL
0.
0.
0.
0.

0.
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO

OOOE'OO
0.
0.
0.
0.

0.
OOOEtOO NDI0.964I
OOOEtOO ND(0.441)
OOOEtOO ND(0.441)
OOOEtOO ND(. 00632) X
X
OOOEtOO
Acid Sever Inputs
I.
2.

A Side C Filtrate
B Side C Filtrate
Flow
RG1-86369
8G1 -86372
Total
3
1.1
4.1
0.0449
0.0669
TOTAL
5.
2.
7.
098E-04
785E-04
884E-04
1.
6.
1.
123E-06
135E-07
737E-06
UVTP Inputs
1.
2.
3.
*
Influent To WTP
Coibined Acid Sewer
Landfill Leachate
RG1 -86386/02
RG1-86368
RG1 -86398
Intenittant Flow(SOgpi) Flow Total
37
4.03

41.03
0.650
0.274
0
TOTAL
9.
4.
0.
103E-02
179E-03
OOOEtOO
9.521E-02
2.005E-04 X 79.31, 411. 15.8*
9.
0.
2.
206E-06 X
OOOEtOO ND(0.00817) 39.6S
097E-04
Dlb. VUTP Slud?e Inputs
   I. Gravity Thick. Sec. Sludfe  RG1-86397
                 33.9     498   1.533E-02   3.376E-05
                                                                       F17

-------
Hill  E
09-Feb-BB
                                                                                                                   Kill E
Mass Balance I ND = 0.0 Assuied 1
Basis : i Day

A2. General Hill Exports
1. VWTP Effluent
2. Coibined Devatered Sludge
3. SU Bleached Pulp - A Side
4. HI/ Bleached Pulp - B Side
5. SU Bleached Pulp - B Side

62. General Sever Exports
1. UUTP Influent
2. Coibined Acid Sever

C2. Bleach Plant Exports
1. SU Bleached Pulp A Side
2. HW Bleached Pulp B Side
3. SV Bleached Pulp B Side
4. A Side C Filtrate
5. A Side E Stage Filtrate
6. A Side D Stage Filtrate
7. B Side C Filtrate
8. B Side E Stage Filtrate
9. B Side D Stage Filtrate

02. MTP Exports
1. Effluent
2. Coibined Devatered Sludge


Saiple ID


RGI-86388/88A
RG1-86387/A/B
RG1-86366
RG1-86367
RG1 -86366


RG1 -86386/402
RG1 -86368


RG1 -86366
RG1-B6367
RG1-86366
RG1-86369
RGi-86370
RGl-86371
RG1-86372
RGi-86373
RG1 -86374


RG1-86388/88A
RG1-B6387/A/B

Flow
(HGD or Dry
Tons/Day)

41
90
483
272
181


37
4.03


483
272
181
3
1.8
1
1.1
1.6
0.75


41
90


TCDD
(PPT)

0,0879
178
25.6
51.2
25.6
TOTAL

0.650
0.274
TOTAL

25.6
51.2
25.6
0.0449
2.292
0.91
0.0669
3.597
1.92
TOTAL

0.0879
178
TOTAL

TCDD
(Grais)

1.364E-02
1.455E-02
1.123E-02
1.265E-02
4.207E-03
5.206E-02

9.103E-02
4.179E-03
9.521E-02

1.123E-02
1.265E-02
4.207E-03
5.098E-04
1.562E-02
3.444E-03
2.785E-04
2.178E-02
5.450E-03
7.516E-02

1.364E-02
1.455E-02
2.819E-02

TCDD
(Ibsl

3.005E-05
3.204E-05
2.473E-05
2.785E-05
9.267E-06
1.147E-04

2.005E-04
9.206E-06
2.097E-04

2.473E-05
2.785E-05
9.267E-06
1.123E-06
3.440E-05
7.587E-06
6.135E-07
4.798E-05
1.201E-05
1.656E-04

3.005E-05
3.204E-05
6.209E-05

Percent
Total

26.2*
27.9*
21.61
24.3*
8.1*
100.0*

95.6*
4.4*
100.0*

14.9*
16.8*
5.6*
0.7*
20.8*
4.6*
0.4*
29.0*
7.3*
100.0*

48.4*
51.6*
100.0*
                                                                                                        ND    AVE  QA
                                                                                                                X  71.5U7.4l
                                                                                                                X

                                                                                                                X
                                                                                                                X   79.3.41.15.8*
                                                                                                                X
                                                                                                                X   71.5*.37.41
                                                                                                                X
                                                             F18

-------
Hill E
16-Feb-88
                                                                                                            Hill  E
Mass Balance [ ND - 0.0 Assuied 1
Basis : 1 Day
Hi. General Hill Inputs
1. Treated Vatert River)
2. m Chips
3. SU Chips



Bl.












Cl.






C2.



Dl.




4.
5.

Groundvood Pulp
Landfill Leachate f
« Interiittant Flov(50gpi)
Saiple ID
RG1 -86356
RG1-86358
RG1-86359
RGi-86360
RG1-86398

Flov
(HGD or Dry
Tons/Day)
34.6
121B
1620
200
0.072

TCOF
(PPT)
0

0.0636
TOTAL
TCDF
(Grais)
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0.
I.
1.
OOOEtOO
733E-05
733E-05
0.
0.
0.
0.
3.
3.
TCDF
(Ibs) ND AVE QA
OOOEtOO ND(0. 00660) 33.3*
OOOEtOO
OOOEtOO
OOOEtOO
818E-08
818E-08
General Sever Inputs
1.
2.
3.
4.
5.
6.
7.
8.
9.
20.
11.

Coibined Paper Machines
disc. Pulping
Nisc. Pover Groups
Otis Hill Return
Vater Treatient Backvash
A Side E Stage Filtrate
A Side D Stage Filtrate
B Side E Stage Filtrate
B Side 0 Stage Filtrate
Bottoi Ash >
Fly Ash *
* Included in 3. Flow
RG1 -86379
RGi-86361
RG1-86362
RG1-863BO/92
RG1-86357
RG1 -86370
RG1-86371
RG1-86373
RGt-8637*
BG1 -86395
RG 1-86396
Total
18.9
4.2
2.6
2.5

1.8
I
1.6
0.75


33.35
0.173


0.346
8.61
10.314
4.715
14.128
9.158
0
0
TOTAL
1.
0.
0.
3.

7.
1.
8.
2.


2.
238E-02
OOOEtOO
OOOEtOO
274E-03

027E-02
785E-02
556E-02
600E-02


153E-01
2.
0.
0.
7.

1.
3.
1.
5.


4.
726E-05 X
OOOEtOO
OOOEtOO
212E-06 11
12.8*
548E-04 X 13.6*
931E-05 X 24.7*
885E-04
726E-05
ND(0.183)
HD10.310)
743E-04
Bleach Plant inputs
1.
2.
3.
4.
5.

HU B Side Brovnstock Pulp
SU B Side Brounstock Pulp
SV A Side Brovnstock Pulp
Process Hater
Paper Machine Whitewater

RG1-86365
RG1-B6364/91
RG1-86364/91
RG1-86356
RG1 -86379

289
197
525
9
With Above

2.32
1.133
1.133
0
0.173
TOTAL
6.
2.
5.
0.
0.
1.
088E-04
027E-04
401E-04
OOOEtOO
OOOEtOO
352E-03
1.
4.
1.
0.
0.
2.
341E-06
464E-07
190E-06 1
OOOEtOO ND(0. 00660) X 33.3)1
OOOEtOO X
977E-06
Acid Sever inputs
1.
2.

A Side C Filtrate
B Side C Filtrate
Flow
RG1-86369
RG1-86372
Total
3
1.1
4.1
0.173
0.326
TOTAL
1.
1.
964E-03
357E-03
3.322E-03
4.
2.
7.
327E-06
990E-06
317E-06
UVTF Inputs
1.
2.
3.
i
Influent To WTP
Coibined Acid Sever
Landfill Leachate
RG1-86386/02
RG1-86368
RG 1-86398
Interiittant Flov(SOgpi) Flov Total
37
4.03
0.072
41.102
3.036
2.693
0.0636
TOTAL
4.
4.
1.
4.
252E-01
108E-02
733E-05
663E-01
9.
365E-04 I 31.7*.
9.048E-05
3.818E-08
1.
027E-03
Dlb. UUTP Sludge Inputs
   t. Gravity Thick.  Sec. Sludge  8G1-86397
                33.9      2147   6.609E-02   1.456E-04
                                                                 F19

-------
Hill  £
09-Feb-88
                                                                                Hill E
Nass Balance ( ND - 0.0 Assuied 1
Basis : 1 Day

A2, General Mill Exports
1. VUTP Effluent
2. Coibined Devatered Sludge
3. SU Bleached Pulp - A Side
4. HY Bleached Pulp - B Side
5. SU Bleached Pulp - B Side

B2. General Sever Exports
1. UVTP Influent
2. Coibined Acid Sever

C2. Bleach Plant Exports
1. SU Bleached Pulp A Side
2. HU Bleached Pulp B Side
3. SU Bleached Pulp 6 Side
4. A Side C Filtrate
5. A Side E Sta?e Filtrate
6. A Side D Stage Filtrate
7. B Side C Filtrate
6. B Side E Stage Filtrate
9. B Side D Stage Filtrate

D2. VUTP Exports
t. Effluent
2. Coibined Devatered Sludge


Saiple ID


RG1-86388/88A
RG1-86387/A/B
RG1-86366
RGi-86367
RG1-86366


RG1-86386/02
RG1-86368


RGl-86366
RGI-86367
RGl-86366
RG1-86369
RGi-86370
RG1 -86371
RG1-86372
RG1-86373
RG1 -86374


RG1-86388/88A
RG1-86387/A/B

Flow
(HGD or Dry
Tons/Day)

41
90
483
272
181


37
4.03


483
272
181
3
1.8
1
1.1
1.6
0.75


41
90


TCDF
(PPT)

0.416
756
139
182
139
TOTAL

3.036
2.693
TOTAL

139
182
139
0.173
10.314
4.715
0.326
14,128
9.158
TOTAL

0.416
756
TOTAL

TCDF
(Grais)

6.456E-02
6.178E-02
6.096E-02
4.495E-02
2.284E-02
2.322E-01

4.252E-01
4.108E-02
4.663E-01

6.096E-02
4.495E-02
2.284E-02
1.964E-03
7.027E-02
1.785E-02
1. 3571-03
8.556E-02
2.600E-02
3.317E-01

6.456E-02
6.178E-02
1.263E-01

TtDF
(Ibs)

1.422E-04
1.361E-04
1.343E-04
9.901E-05
5.032E-05
5.116E-04

9.365E-04
9.048E-05
1.027E-03

1.343E-04
9.901E-05
5.032E-05
4.327E-06
1.548E-04
3.931E-05
2.990E-06
1.885E-04
5.726E-05
7.307E-04

1.422E-04
1.361E-04
2.783E-04

Percent
Total

27.8*
26.61
26. 2*
19. 4)1
9.81
100. OS

91.21
8.8*
100.0*

18. 4*
13.5*
6.9*
0.6*
21.2*
5.4*
o.n
25.81
7.8*
100.0*

51.1%
48.9*
100.0*
                                                                                                           NO    AVE   QA
                                                                                                                  !   65.8.30.4*
                                                                                                                  X

                                                                                                                  I
                                                                                                                   I   31.7*,46*,15.1*
                                                                                                                   I   13.6*
                                                                                                                   X   24.7*
                                                                                                                   X  65.8,30.4*
                                                                                                                   X
                                                            F 20

-------
                      ATTACHMENT G
    ANALYTICAL  RESULTS FOR CHLORINATED  PHENOLICS,
TOTAL SUSPENDED SOLIDS,  AND BIOCHEMICAL OXYGKN DEMAND

-------
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                                                                    G  5

-------
                                                   Table 6-6




                                          Oilorophenol Analyses SuiMry




                                                    IHTAKE!!


Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichlorophenol
3,4-Dichlorcphenol
2,5-Dichlorophenol
2,4/2,5-Dichloraphenol
2,3-Oichlorophenol
2,4,5-Trichlorcphenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
M> - Mot detected





MILL A
PPb
ND
ND
ND
ND
ND
ND
ND
ND
M>
ND
10
ND
ND
ND
ND
ND

HILL A


Fit* (HGD)
PPb


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




20
Ibs/day

B
ppb
ND
KD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

B



PPb


Ibs/dav
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




37.1
Ibs/day

c
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

C



PPb


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




30
Ibs/day

D
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

D



PPb


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




11.7
Ibs/day

£
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

E



PPb


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




34.6
Ibs/day
Suirf
All Hills
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00


Sl» of
All Hills
Ibs/day
SIM of diloropbenols             0.00   0.00   0.00  0.00    0.00   0.00    0.00   0.00    0.00   0.00         0.00




Sm oi diloroquaiacols           0.00   0.00   0.00  0.00    0.00   0.00    0.00   0.00    0.00   0.00         0.00




Sui oi chlorovanillins           0.00   0.00   0.00  0.00    0.00   0.00    0.00   0.00    0.00   0.00         0.00




Sw oi all analytes              0.00   0.00   0.00  0.00    0.00   0.00    0.00   0.00    0.00   0.00         0.00
                                                            G  6

-------
                                                             Table 6-7

                                                    Chlorophenol Analyses Sumarv
                                                           HHTP INFLUENTS
HILL
Analvte
2-Chlorophenol
2,6-Didilorophenol
2,4-Dichlofophenol
3,4-OichloroPhenol
2,5-Oichlorophenol
2,4/2,5-Dichloraphenol
2,3-Didilorophenol
2,4.5-Trichlorophenol
Pentadilorophenol
4,5-Oichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-ChlorovanilIin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected in range of
NA - Not analyzed
HILL

FlOM

A
PPb
NA
ND
2.6
ND
NA
—
ND
ND
0.4
4.0
4.0
0.9
12.5
NA
3.8
0.8

B
Ibs/day ppb
0.00
0.00
0.44
0.00
0.00
0.00
0.00
0.00
0.07
0.67
0.67
0.15
2.10
0.00
0.64
0.13
ND
ND
9.8
M>
ND
—
ND
M)
ND
4.8
8.9
3.3
6.3
2.2
6.5
1.7

Ibs/day
0.00
0.00
3.05
0.00
0.00
0.00
0.00
0.00
0.00
1.50
2.77
1.03
1.96
0.69
2.03
0.53
C
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
13.8
5.2
ND
0.4
ND
13.3
2.1

Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.63
1.37
0.00
0.11
0.00
3.50
0.55
D
PPb
ND
ND
—
ND
—
6.3
ND
ND
ND
24.3
9.0
7.4
4.8
4.0
21.0
11.3

Ibs/dav
0.00
0.00
0.00
0.00
0.00
0.99
0.00
0.00
0.00
3.82
1.42
1.16
0.76
0.63
3.30
1.78
E
PPb
ND
ND
—
ND
—
11.7
ND
ND
ND
24.0
30.6
5.3
50.1
»
13.5
12.4

Ibs/day
0.00
0.00
0.00
0.00
0.00
3.61
0.00
0.00
0.00
7.41
9.45
1.64
15.47
0.00
4.17
3.83
Suiof
All Hills
Ibs/day
0.00
0.00
3.49
0.00
0.00
4.60
0.00
0.00
0.07
17.03
15.68
3.98
20.39
1.31
13.63
6.82
1 to3ug/L (ppb).

A


(H6D)
PPb




20.1
Ibs/day |

B



•Pb




37.35
Ibs/day

C



PPb




31.5
Ibs/day

D



PPb




18.85
Ibs/day

E



PPb




37
Ibs/day


SUt of
All Hills
Ibs/day
Sum of dilorophenols

Sun of chloroquaiacols

Sw of chlorovanillins

Sui of all analytes
 3.00   0.50    9.80   3.05    0.00   0.00    6.30   0.99   11.70   3.61          8.16

21.40   3.59   23.30   7.26   19.40   5.10   45.50   7.16  110.00 33.96         57.07

 4.60   0.77   10.40   3.24   15.40   4.05   36.30   5.71   25.90   8.00         21.77

29.00   4.86   43.50  13.56   34.80   9.15   88.10  13.86  147.60 45.57         87.00
                                                         G7

-------
                                                            Table 6-6

                                                   Chlcrophenol  Analyses Sunary
                                                          *TP EFai£NTS
MILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Dichlorophenol
2,3-Oichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-DichlorovaniUin
ND - Not detected in range of
NA - Not analyzed
MILL

Flo*

A
ppb
ND
ND
2.1
ND
ND
—
ND
ND
2.0
2.7
5.0
3.3
1.9
ND
ND
ND

Ibs/day
0.00
0.00
0.41
0.00
0.00
0.00
0.00
0.00
0.39
0.52
0.97
0.64
0.37
0.00
0.00
0.00
8
ppb
ND
ND
0.2
ND
ND
—
ND
ND
ND
ND
2.3
1.7
2.8
1.9
4.2
3.2
C - (36-72 MS)
Ibs/day
0.00
0.00
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.70
0.52
0.86
0.58
1.26
0.98
ppb
ND
ND
—
ND
—
ND
ND
0.7
ND
ND
ND
ND
ND
ND
ND
M>
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.17
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
D
PPb
ND
ND
—
ND
—
5.9
ND
ND
NO
3.1
10.0
7.2
4.5
W
4.8
1.0

Ibs/day
0.00
0.00
0.00
0.00
0.00
0.91
0.00
0.00
0.00
0.48
1.54
1.11
0.69
0.00
0.74
0.15
E
ppO
ND
ND
—
ND
—
ND
ND
ND
ND
ND
5.6
ND
ND
ND
ND
ND

ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.92
0.00
0.00
0.00
0.00
0.00
3UI Crf
All Hills
Ibs/day
0.00
0.0(i
0.47
0.00
0.00
0.91
0.00
0.17
0.39
1.00
5.13
2.27
1.92
0.58
2.02
1.13
1 to 3ug/L (ppb).

A

(HGD)
PI*



23.2
Ibs/day

B


ppb



C - (36-72 US)

36.6
Ibs/day


ppb

29.5
Ibs/day

D


ppb



18.49
Ibs/day

E


Pf*



41
Ibs/day


QIM ni
am or
All Hills
Ibs/day
Sw of chlorophenols            4.10   0.79    0.20   0.06    0.70   0.17    5.90   0.91    0.00   0.00         1.94

Su« of chloroquaiacols          12.90   2.50    6.80   2.06    0.00   0.00   24.80   3.83    5.60   1.92        10.32

Sua oi chlorovanillins           0.00   0.00    9.30   2.84    0.00   0.00    5.80   0.89    0.00   0.00         3.74
SIM of all analytes             17.00   3.29   16.30   4.98    0.70   0.17   36.50   5.63    5.60   1.92        15.99
                                                                         G8

-------
                                                                      Table 6-9

                                                              Oilorophenol Analyses Smurv
                                                                     BLEACH PLANT
                                                                       CSTA6ES
HILL A - a
Analvte ppb Ibs/day
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oidilorophenol
3,4-Dichlorophenol
2,5-Dicfilorophenol
2,4/2,5-Didilorcphenol
2,3-Oichlorophenol
2,4,5-Trichlorcphenol
Pentachlorophenol
4,S-Oichloro9uaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetradiloroquaicol
5-Chlomanillin
6-Qilorwanillin
5,6-Oichlorovanillin
W
ND
3.1
M>
ND
—
ND
(D
ND
*
2.6
M>
3.1
ND
ND
ND
0.00
0.00
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.04
0.00
0.00
0.00
A-NN
PPb Ibs/day
ND
ND
5.3
»
ND
—
ND
ND
ND
3.2
3.5
0.9
0.9
ND
M>
M)
0.00
0.00
0.07
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.05
0.01
0.01
0.00
0.00
0.00
8
PPb Jbs/day
ND
ND
9.7
ID
ND
—
M)
ND
0.7
4.8
14.3
7.3
14.1
ND
5.6
6.1
0.00
0.00
0.49
0.00
0.00
0.00
0.00
0.00
0.04
0.24
0.72
0.37
0.71
0.00
0.26
0.31
C
ppb Ibs/day
ND
W)
—
ND
—
ND
M)
ND
ND
54.1
20.9
6.8
4.5
5.2
56.5
14.4
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.33
0.51
0.17
0.11
0.13
1.39
0.35
D - A SIDE
ppb Ibs/day
M)
M)
—
ND
—
11.2
M)
ND
H>
14.3
3.3
3.1
ND
ND
15.3
4.8
0.00
0.00
0.00
0.00
0.00
0.13
0.00
0.00
0.00
0.17
0.04
0.04
0.00
0.00
0.18
0.06
D - B SIDE
ppb Ibs/day
ND
M)
—
ND
—
13.9
M>
M)
ND
12.9
6.6
9.9
3.7
5.1
15.6
6.7
0.00
0.00
0.00
0.00
0.00
0.11
0.00
0.00
0.00
0.10
0.05
0.08
0.03
0.04
0.12
0.05
E - A SIDE
PPb Ibs/day
ND
ND
—
ND
—
15.3
ND
ND
ND
3.7
8.4
ND
5.9
M>
4.4
0.7
0.00
0.00
0.00
0.00
0.00
0.38
0.00
0.00
0.00
0.09
0.21
0.00
0.15
0.00
0.11
0.02
£ - B SIDE
ppb Ibs/day
ND
ND
—
»
—
7.5
ND
ND
ND
3.6
7.9
ND
6.5
N>
3.5
ND
0.00
0.00
0.00
0.00
0.00
0.07
0.00
0.00
0.00
0.03
0.07
0.00
0.06
0.00
0.03
0.00
Sui oi
Ail Hills
0.00
0.00
0.60
0.00
0.00
0.69
0.00
0.00
0.04
2.01
1.70
0.66
1.12
0.17
2.12
0.79
» - Not detected
                      HILL    A - SH
A-W
                       D - A SIDE     D - B SIDE     E - A SIDE    E  - B SIDE
                      Flow (NED)    1.73
     1.58
6.05
2.95
1.42
0.95
3
1.1     All  Hills
                            ppb  Ibs/day  ppb  Ibs/day   ppb  Ibs/day   ppb  Ibs/day   ppb   Ibs/day   ppb  Ibs/day   ppb  Ibs/day  ppb  Ibs/day     Ibs/day

So of diloraphenols        3.10   0.04    5.30   0.07   10.40   0.53    0.00   0.00   11.20  0.13   13.90   0.11   15.30   0.38   7.50   0.07         1.33

St» of chloroquaiacols      5.90   0.09    8.50   0.11   40.50   2.04   86.30   2.12   20.70  0.25   33.10   0.26   18.00   0.45   18.00   0.17         5.49

SUB of dilorwanillins      0.00   0.00    0.00   0.00   11.70   0.59   76.10   1.87   20.10  0.24   27.40   0.22    5.10   0.13   3.50   0.03         3.06

StM of all analytes         9.00   0.13   13.80   0.18   62.60   3.16  162.40   4.00   52.00  0.62   74.40   0.59   38.40   0.96   29.00   0.27         9.90
                                                                       G9

-------
                                                                   Tiblt 6-10
Chlorophenol Analyses SuMary
BLEACH PLANT
E STAGS
HILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichloraphenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Dichlorophenol
2,3-Didilorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Didiloroguaiacol
3,4,5-Tricnloroguaicol
4,5,6-Trichloroguaicol
Tetrachloraquaicol
5-Qilorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected
HILL
Flow

A-SN
Ppb Ibs/day
ND 0.00
ND 0.00
16.1 0.19
ND 0.00
ND 0.00
- 0.00
ND 0.00
ND 0.00
ND 0.00
5.1 0.06
84.0 1.01
54.3 0.65
175 2.10
2.3 0.03
6.4 0.08
38.6 0.46

A-»
(HGD) 1.44
PPb Ibs/day
A-HM
ppfa Ibs/day
ND 0.00
ND 0.00
26.6 0.16
ND 0.00
ND 0.00
- 0.00
ND 0.00
ND 0.00
ND 0.00
166 1.01
123 0.75
36.5 0.22
19.8 0.12
16.2 0.10
113 0.69
13.2 0.08

A-HH
0.73
PPb Ibs/day
B
PPb
ND
ND
43.60
ND
ND
—
ND
ND
6.1
196
351
146
170
24.4
163
97.0

B

PPb

Ibs/day
0.00
0,00
0,80
0,00
0,00
0,00
0,00
0,00
0,11
160
644
2.68
112
0,45
2.99
1.78


2.2
Ibs/day
C
PPb
ND
ND
—
ND
—
7.9
ND
ND
7.5
395
86.6
39.6
30.5
15.2
209
40.2

C

PPb

Ibs/day
0.00
0.00
0.00
0.00
0.00
0.32
0.00
0.00
0.31
16.15
3.54
1.62
1.25
0.62
B.55
1.64


4.9
Ibs/day
D
PPb
ND
ND
—
ND
—
117
ND
ND
7.1
521
314
220
81.5
37.8
371
146

D

PPb

Ibs/day
0.00
0.00
0.00
0.00
0.00
2.66
0.00
0.00
0.16
11.83
7.13
4.99
1.85
0.86
8.42
3.31


2.72
Ibs/day
E - A SIDE
PPb Ibs/day
1.0 0.02
ND 0.00
- 0.00
ND 0.00
- 0.00
76.0 1.14
ND 0.00
ND 0.00
6.8 0.10
286 4.30
422 6.34
60.4 0.91
358 5.38
31.4 0.47
241 3.62
128 1.92

E - A SIDE
1.8
PPb Ibs/day
E - B SIDE
ppb Ibs/day
ND 0.00
ND 0.00
- 0.00
ND 0.00
- 0.00
33.8 0.45
ND 0.00
ND 0.00
ND 0.00
106 1.42
184 2.46
34.8 0.46
199 2.66
16.4 0.22
79.8 1.07
70.5 0.94

E - B SIDE
1.6
PPb Ibs/day
All Hills
Ibs/day
0.02
0.00
1.16
0.00
0.00
4.57
0.00
0.00
0.68
38.36
27.67
11.54
16.48
2.74
25.41
10.15


Sm of
All Hills
Ibs/day
Sw of dilorophenols




Sw of chloroquaiacols




Sun oi chlorovanillins




Sut of all analytes
 16.10   0.19   26.60   0.16    49.70   0.91    15.40  0.63   124.10   2.82    83.80   1.26   33.80   0.45         6.42




318.40   3.83  345.30   2.10   863.00  15.84   551.70 22.56  1136.50  25.80  1126.40  16.92  523.80   6.99        94.04




 47.30   0.57  142.40   0.87   284.40   5.22   264.40  10.81   554.80  12.59   400.40   6.01  166.70   2.23        38.30




381.80   4.59  514.30   3.13  1197.10  21.98   831.50 34.00  1815.40  41.21  1610.60  24.19  724.30   9.67       138.77
                                                                        G  10

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                                                     Tablt 6-11

                                            Chlorophenol Analyses Sunary
                                                    BLEACH PLANT
                                                      OSTAEES


Aiulyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichloropbenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Didtlorophenol
2,3-Dichlorophenol
2,4,5-Trichloropbenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloro9uaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected





Mill B
PPb
NO
ND
ND
ND
ND
—
ND
ND
ND
1.4
6.6
0.9
4.B
ND
ND
ND

HILL B


RON (HGD)
Pf*


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.09
0.01
0.06
0.00
0.00
0.00




1.57
Ibs/day

C
PI*
ND
ND
—
ND
—
ND
ND
ND
ND
4.6
2.1
ND
ND
ND
2.8
0.7

C



PI*


Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00




0
Ibs/day

E-A
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
1.7
4.2
ND
ND
ND
1.6
ND

E-A



PI*

SIDE
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.04
0.00
0.00
0.00
0.01
0.00

SIDE


1
Ibs/day

E-S
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
KD
ND
ND
ND
ND
ND
ND

E-E



PPb

ISIDE
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

IS10E


0.75
Ibs/day
Sturi
All Hills
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.12
0.01
0.06
0.00
0.01
0.00


Suaof
All Hills
Ibs/day
St» of chlorophenols            0.00   0.00    0.00   0.00    0.00   0.00    0.00   0.00         0.00

Sw of chloroquaiacols          13.70   0.18    6.70   0.00    5.90   0.05    0.00   0.00         0.23

Sl» of dilorovanillins           0.00   0.00    3.50   0.00    1.60   0.01    0.00   0.00         0.01
Sm of all aulytes            13.70   0.18   10.20   0.00    7.50   0.06    0.00   0.00         0.24
                                                     Gil

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                                             Table 6-12

                                     Chlorophenol  Analyses Sundry
                                            BLEAm PLANT
                                              H STAGES

Analvte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2, 4/2, 5-Dichloraphenol
2,3-DichlorophenoI
2,4,5-Tridilorophenol
Pentachlonphenol
4,5-Dichloroguaiacol
3,4,5-Trichloroquaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Oichlorovanillin
ND - Not detected




HILL B
ppb
ND
ND
3.7
ND
ND
—
ND
NO
4.0
15.9
31.5
68.5
81.4
15.0
19.6
64.8

HILL B

Flow (HED)
Ppb
(H-l)
Ibs/day
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.03
0.06
0.14
0.16
0.03
0.04
0.13

(H-l)

0.24
Ibs/day
B (H-2)
Pf*
ND
ND
ND
ND
ND
—
ND
ND
1.3
S.6
11.3
11.8
21.0
4.6
£.9
14.7

B


ppb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.06
0.13
0.13
0.24
0.05
0.10
0.17

(tt-2)

1.36
Ibs/day
D - A SIDE D
ppb
M)
ND
—
ND
—
ND
ND
ND
ND
22.5
5.7
9.7
1.0
2.4
23.6
4.9

Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.26
0.06
0.11
0.01
0.03
0.27
0.06

D - A SIDE D


PPb

1.42
Ibs/day
-BSIDE
PPb
ND
ND
—
ND
—
4.9
ND
ND
ND
19.3
10.7
22.7
6.1
2.8
22.7
.12.4

Ibs/day
0,00
0.00
0,00
0.00
0,00
0,06
0..00
0,00
0,00
0.22
0,12
0.26
0,07
0.03
0.26
0.14

All Hills
Ibs/day
0.00
0.00
0.01
0.00
0.00
0.06
0.00
0.00
0.03
0.57
0.38
0.64
0.48
0.14
0.67
0.49

- B SIDE


PPb

0.92
Ibs/day
CllB ffrf
aw VT
All Hills
Ibs/day
Sw of dilorophenols            7.70   0.02    1.90   0.02   0.00  0.00   4.90   0.06         0.09

Sui 
-------
        Tiblt 6-13

Chloroptenol Analyses SuMiry
     UWFILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichlorophenol
3,4-Dichlorcphenol
2,5-Dichlorophenol
2,4/2,5-Dichlorophenol
2,3-Oichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected
HILL B
PPb
ND
ND
ND
M)
ND
ND
ND
ND
ND
ND
ND
ND
M>
M)
ND
ND

Ibs/day
0.00
O'.OO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

HILL B (H-U


Sw of chlorophenols
Su oi chloroquaiacols
SIM erf chlorovanillins
Su« of all analytes
Flow (HBO)
W*
0.00
0.00
0.00
0.00

Ibs/day
0.00
0.00
0.00
0.00
          G13

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                             TABLE  G-14

                   BOD5  and TSS  RESULTS  SUMMARY
                               MILL A
Sample                     TSS                          5 Day
 I.D.                      ppm                          BOD ppm

OE 020818                   6                              0
(Powerhouse Wastewater)

DE 020801                  10                              0
(Treated river water)

DE 020921                  654                            175
(combined untreated wastewater)

DE 020821                   94                            400
(Moonlight Leachate)

DE 020807                   16                            119
(Recovery #9)

DE 020915                   66                            212
(Bleach Plant #5)

DE 020806                  1402                           291
(Kraft Mill #6)

DE 020811                  1132                           214
(Paper Mill #2)

DE 020922                   104                            29
(Secondary Clarifier)
                                G 14

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                          TABLE  G-15

               BOD5 and  TSS RESULTS  SUMMARY
                            MILL B
SAMPLE              SAMPLE                     TSS           BOD
 CODE               DESCRIPTION               (ppm)         (ppm)
 A-l                Treated Water              11            0.5

 B-la               Brown  Stock Filtrate Tank  64            115

 B-lb               Brown  Stock Filtrate Tank  51            253
                    o'flow outside Kraft Mill

 B-2a               Corrosive sewer-recovery  144            337
                    evaporator, recaust, refiners

 B-3                Kraft  sewer - Kraft pulping
                    and Alkaline Bleach        70            226

 D-3a               C12 Seal Tank o'flow       40            253

 D-4a               E-l Seal Tank o'flow       36            240

 E-l                Tissue Machine sewer      204             16

 F-3a               Combined Acid sewer        49            142

 F-3b               Combined Process sewer    193            158

 F-4                Secondary Effluent         40              5

 F-5                Landfill Leachate         312             71
                                G15

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         TABLE G-16

BOD5 and TSS RESULTS SUMMARY
           MILL C
Sampl e
ID
DE026
OE026
06026
OE026
DE026
DE026
OE026
06026
D6026
OE026
OE026
06026
OE026
06026
D6026
OE026
OE026
001
105
106
108
109
110
112
113
119
120
121
122
012
013
014
205
206
Sample Description
Treated River Hater
Untreated Groundwater
Untreated River Water
Station 7
Station 8
Station 28
Station 9
Station 13
Station 1
Station 3
Station 4
Station 5
Primary Influent (Sta 20)
Secondary Effluent (C-24)
Sludge Landfill leachate
Wood Boiler and Boilerhouse (Sta 15)
Secondary Effluent (36-72)
TSS
(mg/1 )
10
6
21
397
1134
25
99
2016
1684
330
768
616
540
16
66
1084
36
BOO
(mg/1 )
2











301
11
10

9
            G L6

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                       TABLE G-17

Sample
ID
Bl
B2
Cl
C2
C3
D4
D5
D6
D7
D9
El
Fl
F2
F7
8005 and TSS RESULTS SUMMARY
MILL D
Sample Description
Brownstock decker sewer
Dreg wash sewer
Evaporator sewer
Recovery boiler sewer
Lime kiln sewer
Chlorination stage - A-side
Caustic stage - A-side
Hypo stage - A-side
Chlorination stage - B-side
Hypo stage - B-side
Ground wood mill/paper machines
WWTP influent
WWTP effluent
Sludge lagoon effluent

TSS B005
(mg/L) (mg/L)
26 180
1250
<1 120
4.5
253
10.5
12.7
12
17.5
13
1490 305
875 232
14.5 13.2
102a
NOTE:  (a)  COD value presented.
                           G 17

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                               TABLE G-18
                     BOD5  and TSS  RESULTS SUMMARY
                                 MILL E
Stnplt 1
A-l
A2
B1.2
CIS
m i *>< <
Di , I VVV*
02
El
B3
17
BOD ag/1
1
1
220
375
120
200
340
16
1,400+
TSS M/l
2
*
230
600
1,100
350
680
89
160
                                                        Upstream River Water
                                                        (Chlorinated Process Water
                                                        A Side General Sewer
                                                        A Side.Caustic
                                                        B Side General Sever
                                                        Otis Mill Return
                                                        Primary Influent
                                                        Final Effluent
                                                        landfill Leachate
* A2 - All •••pi* ustd for •*•*.  Ho TSS,
                                    G 18

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