EPA-660/4-75-005
JUNE 1975
                               Environmental  Monitoring  Series
Analysis of  Organic  Compounds  in
Two  Kraft  Mill  Wastewaters
                                    National Environmental Research Center
                                      Office of Research and Development
                                     U.S. Environmental Protection Agency
                                            Corvallis, Oregon 97330

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                        RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series.  These five broad categories were established to
facilitate further development and application of environmental
technology.  Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields.  The five series are:

          1.   Environmental Health Effects Research
          2.   Environmental Protection Technology
          3.   Ecological Research
          4.   Environmental Monitoring
          5.   Socioeconomic Environmental Studies

This report has been assigned to the ENVIRONMENTAL MONITORING STUDIES
series.  This series describes research conducted to develop new
or improved methods and instrumentation for the identification and
quantification of environmental pollutants at the lowest conceivably
significant concentrations.  It also includes studies to determine
the ambient concentrations of pollutants in the environment and/or
the variance of pollutants as a function of time or meteorological
factors.

                         EPA REVIEW NOTICE

This report has been reviewed by the National Environmental
Research Center--Con/allis, and approved for publication.  Mention
of trade names or commercial products does not constitute endorsement
or recommendation for use.

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                                 EPA-660A-75-005
                                 JUNE 1975
             ANALYSIS  OF ORGANIC
  COMPOUNDS IN TWO KRAFT MILL WASTEWATERS
                       By
              Lawrence H.  Keith
Southeast Environmental Research Laboratory
   National Environmental Research Center
            Athens,  Georgia  30601
            Program Element  1BA027
          ROAP/Task No.  07ABL-02,  03
   NATIONAL ENVIRONMENTAL RESEARCH CENTER
      OFFICE OF RESEARCH AND  DEVELOPMENT
   U.  S.  ENVIRONMENTAL PROTECTION AGENCY
           CORVALLIS, OREGON   97330
           For Sale by the National Technical Information Service,
           U.S. Department of Commerce, Springfield, VA 22151

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                          ABSTRACT
Wastewaters from two Jcraft paper mills in Georgia were
sampled at various points in the waste treatment systems.
Gas chromatography of the organic extracts and
identification of many of the specific chemical components
by gas chromatography-mass spectrometry provided a "chemical
profile" of the effluents.  The mills, in different
geographical locations, have very similar raw wastewater
compositions but different wastewater treatments.  In spite
of these differences, the treated effluents are
qualitatively similar in composition although the quantities
of the various components differ.  After two years the raw
and treated effluents of both mills were re-sampled.
Analyses showed that although concentrations of the organics
varied, the same compounds are still present.  This report
was submitted in fulfillment of ROAP 07ABL, Tasks 02 and 03
by SERL, Athens, Georgia.  Work was completed as of April
1974.
                                 IJL

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                          CONTENTS





Sections





I      conclusions                                      1



II     Recommendations                                  4



III    Introduction                                     6



IV     Analytical Procedures                           12



V      Identification of Acids and Phenols             26



VI     Identification of Terpenes                      73



VII    References                                      92



VIII   Appendices                                      9 7
                                111

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                          FIGURES


                                                      Page

 1    EPA Regional Districts                              8

 2    Waste treatment diagram of Mill "A"                9

 3    Waste treatment diagram of                        11
     Interstate Paper Corporation,
     Riceboro,  Georgia

 H    Kuderna-Danish concentrator                       13

 5    Gas chromatograms of the extracts                 14
     of Mill "A" aerated lagoon effluent
     from (A)  carbon chloroform extract
     (CCE)  and (B)  liquid-liquid chloro-
     form extract

 6    Apparatus for diazomethane methyla-               17
     tion

 7    Apparatus for dimethyl  sulfate                    19
     methylation

 8    Chromatograms of the methyl                       20
     derivatives from a kraft paper
     mill wastewater sample  using (A)
     dimethyl sulfate, (B) diazomethane,
     (C)  Methyl-8, and (D) MethElute
     as methylating reagents

 9    Chromatograms of control samples                  21
     treated with (A) dimethyl sulfate,
     (B)  diazomethane, (C) Methyl-8,
     and (D) MethElute as methylating
     reagents

10    Computer reconstructed  (A) gas                    30
     chromatogram, (B) LMRGC using
     m/e 149 and (C)  LMRGC using
     m/e 74 and 87 superimposed on
     the same axis

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                    FIGURES (continued)
No..                                                   Page

11   Mass spectra of  (A) methyl stearate                33
     without impurity and background
     subtraction and  (B) methyl
     stearate after computer subtrac-
     tion of mass fragments from inter-
     fering compounds on either side of it

12   Mass spectra of  (A) methyl palmitate               37
     and (B) tentatively identified methyl
     10-methyltetradecanoate

13   Mass spectra of ethyl palmitate                    38
     found in (A) the methylated
     lagoon effluent extract of Mill
     A and  (B) the neutral raw effluent
     extract of Mill "A"

14   LMRGC of the methylated extract                    40
     from Mill "A" lagoon effluent

15   Mass spectra of  (A) methyl 2-                      41
     methylhexadecanoate and (B) ethyl
     palmitate (ethyl hexadecanoate)

16   (A) Gas chromatogram and  (B) RGC                   44
     of fatty acid methyl esters from
     chlorella algae

17   Mass spectrum of  (A) methyl abie-                  48
     tate and (B) methyl dehydroabietate

18   Mass spectrum of  (A) methyl pimarate               49
     and (B) methyl isopimarate

19   Mass spectrum of  (A) methyl sandaraco-             50
     pimarate and  (B) methyl neoabietate

20   Mass spectrum of  (A) methyl 13-                    51
     abieten-18-oate and  (B) methyl
     6,8,11,13-abietatetraen-18-oate

21   Chemical profile of acids and                      55
     phenols from Mill  "A"; sample points 1-4

22   Chemical profile of acids and phenols from        55
     the Interstate mill at Riceboro, Georgia;
     sample points 1-4

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                      FIGURES (continued)

No.                                                    Page

23   Print-out of the computer program used             61
     to analyze the raw effluent extract
     from the Interstate mill at Riceboro

24   Computer print-out of the normalized               62
     peak areas from the chromatogram of
     the raw effluent extract from the
     Interstate mill at Riceboro

25   Computer analysis of the chromatogram              63
     of Interstate's raw effluent acid and
     phenol extract

26   Gas chromatogram of the acid and                   64
     phenol extract of Interstate's
     (A) raw effluent and (B) treated effluent

27   Computer analysis of the chromatogram              65
     of Interstate's treated effluent acid and
     phenol extract

28   Computer analysis of the chromatogram              66'
     of Mill "A's" raw effluent acid and
     phenol extract  (A) run no. 1 and  (B)
     duplicate run

29   Computer analysis of the chromatogram              67
     of Mill "A's" outfall acid and phenol
     extract

30   Gas chromatogram of the acid and phenol            68
     extract of Mill "A's" (A) raw effluent —
     run no. 1 and (B) treated effluent

31   Chemical profile of neutral volatiles              75
     from Mill "A"; sample points 1-4

32   Chemical profile of neutral volatiles from         76
     the Interstate mill at Riceboro; sample
     points 1-4

33   Gas chromatogram of neutral volatile extract       77
     in Mill "A's" raw effluent (A) and  (B)
     treated effluent
                              VI

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                      FIGURES (continued)


No.
34   Gas chromatoqram of neutral volatile extract       78
     from Interstate's raw effluent  (A) and (B)
     treated effluent

35   Gas chromatograms of Mill "A" neutral              80
     volatile extracts analyzed by GC-IR; sample
     points 3 and 4

36   GC-IR spectra of peaks 3-7; sample point 3         82
     with inset of the corresponding portion of
     the gas chromatogram

37   GC-IR spectra of peaks 8-11; sample point 3        83
     with inset of the corresponding portion of
     the gas chromatogram

38   GC-IR spectra of peaks 11-14; sample point 3       84
     with inset of the corresponding portion of
     the gas chromatogram

39   GC-IR spectra of peaks 16-19; sample point 3       85
     with inset of the corresponding portion of
     the gas chromatogram

40   GC-IR spectra of peaks 20-24; sample point 3       86
     with inset of the corresponding portion of
     the gas chromatogram

41   GC-IR spectra of peaks a-e.; sample point 4         87
     with inset of the corresponding portion of
     the gas chromatogram

42   GC-IR spectrum of camphor and corresponding        88
     GC-IR spectrum from sample peak

43   GC-IR spectrum of borneol and corresponding        89
     GC-IR spectrum from sample peak

44   GC-IR spectrum of 2-acetylthiophene and            90
     corresponding GC-IR spectrum from sample
     peak

45   GC-IR spectrum of 2-propionylthiophene and         91
     corresponding GC-IR spectrum from sample
     peak
                              vii

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                           TABLES
No.
     Percent methylation and recovery                  22
     of model phenols and acids using
     dimethyl sulfate

     Acids and phenols identified in                   27
     both kraft paper mill effluents
     with approximate concentrations

     Fatty acids in the extract of                     43
     Chlorella algae culture

     Percent removal of phenols                        47
     versus their structural
     complexity

     Collective-pollution-parameter                    70
     measurements and total concentrations of
     the volatile components in the acid/
     phenol extracts

     Volatile acidic components as                     71
     percentages of TOC

     Neutral volatiles identified in                   74
     both kraft paper mill effluents
     with appropriate concentrations
                               Vlll

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                      ACKNOWLEDGMENTS
All sample preparations and gas chromatographic separations
were done by Terry Floyd.  Mass spectral data were provided
by Ann Alford and Mike Carter.  Infrared data were provided
by Leo Azarraga and Ann McCall.

Charles Davis, Lloyd Chapman, and William J. Verross
provided valuable assistance and wastewater samples from the
Interstate Paper Corporation at Riceboro, Georgia.
Officials at Mill "A", which prefers to remain anonymous,
were also very helpful in providing both samples and
information.  Without the cooperation of the staff from
these two mills this study would not have been possible.

Duane F. Zinkel  (U.S.D.A. Forest Products Laboratory,
Madison, Wisconsin) kindly supplied us with reference
standards of the resin acids.

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                         SECTION I

                        CONCLUSIONS
Computer-assisted GC-MS is the best method of identifying
unknown volatile organics in wastewaters.

It is now possible to obtain routinely by GC analysis much
pertinent data concerning the quantities of specific
chemicals being discharged into environmental waters from
kraft paper mills.

The efficiency of various types and combinations of existing
treatment facilities can now be measured and compared as to
their removal of undesirable compounds from kraft paper mill
wastewaters.

In mill laboratories, computer-assisted GC analysis can save
much time and expense over manual GC.

The GC-MS techniques and extraction/concentration methods
employed permitted identification of some compounds in less
than 1 part per billion in the wastewaters.

A number of general conclusions can be drawn from this
study:

     •  Raw effluents from kraft pulp mills producing paper
        from the same raw materials contain essentially the
        same volatile organics.

     •  The volatile organic composition of kraft
        wastewaters remains relatively constant over the
        years as long as the raw materials remain the same
        and the process is not changed.

     •  When peaks in the GC of a pulp mill wastewater have
        been identified, routine GC analyses on a mill
        laboratory basis are feasible.

     •  The relative quantities of the volatile organics in
        pulp mill wastewaters can fluctuate rapidly.

     •  Because of rapid fluctuations in the quantities of
        organics in the wastewaters, composite samples are
        needed for representative quantitative results.

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The wastewaters of the two mills were similar in several
respects:

     •  The raw effluents were very similar qualitatively
        with regard to volatile organic chemical content.
        This was expected since both mills produce a kraft
        linerboard by the same process and from the same raw
        materials.

     •  Significant BOD reductions occurred in both
        treatment systems.

     •  Total chromatographable organics were significantly
        reduced by both treatment systems.

     •  Both treated effluents showed large reductions in
        resin acid, phenolic, and neutral volatiles content.

Only one point of difference was noted.  Total fatty acid
content was decreased in Interstate*s treated effluent but
not in that of Mill "A".  Fatty acids in the oxidation of
Mill "A" may be biological metabolites from aquatic life in
these ponds.

Conclusions can also be reached from a comparison of the
effects of biological treatment  (Mill "A's" trickling filter
and aerated lagoon) versus chemical/biological treatment
(Interstate1s lime flocculation/stabilization lagoon)  on the
volatile organic compounds in these wastewaters.  All values
used in these comparisons came only from the January 1974
composite samples.
        BOD reductions were in the range of 85-90X with both
        treatments.

        TOC reductions were in the range of 80-85% with
        chemical/ biological treatment and 60-65% with only
        biological treatment.

        Total volatile acids and phenols were reduced by 75-
        80% in both treatments.

        Total resin acids were reduced in concentration by
        87% with biological treatment but were still present
        at about 1.4 mg/liter in the treated effluent.
        Total resin acids were reduced in concentration by
        74% with chemical/biological treatment but were
        still present at about 6.4 mg/liter in the treated
        effluent.

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•  Total phenols were reduced in concentration by 73%
   with biological treatment and were present at 0.6
   mg/liter in the treated effluent.  They were reduced
   by 94% with chemical/ biological treatment and were
   present at 0.2 mg/liter in the treated effluent.

•  Total fatty acids increased 17% in concentration
   with biological treatment and were present at 1.6
   mg/liter in the treated effluent.  They decreased by
   86% with chemical/biological treatment and were
   present at 0.2 mg/liter in the treated effluent.

•  Biologically treated wastewaters from both mills
   contained a greater number of fatty acids than did
   the raw wastewaters.  The new fatty acids were
   branched and oddnumbered carbon compounds.

•  Total volatile materials ranged from 1-10% of the
   TOC.

•  Terpenes were reduced by 90% or more by both
   treatments.

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                         SECTION XI

                      RECOMMENDATIONS
We recommend that further studies by Federal and university
laboratories, and especially laboratories associated with
the paper mills or  the National Council for Air and Stream
Improvement, be conducted to build up a reliable body of
knowledge on the amounts of specific volatile organics being
discharged from pulp mill wastewaters and to determine the
waste treatment systems that most effectively remove them.
In particular, the following questions must be answered:

     •  Does the chemical composition of kraft paper mill
        wastewaters remain fairly consistent across large
        geographic areas or only within smaller geographic
        areas such as within the Southeast?

     •  How does the composition of  these wastewaters vary
        with changes in wood and changes in the pulping
        process?

     •  Does the chemical composition of these wastewaters
        vary with season?

     •  What types of compounds are  likely to build up in
        concentration if the wastewater is recycled?

     •  Can the in-plant source of the more refractory com-
        pounds be determined so that one or more small
        volume wastewater streams can be selected for
        special intensive treatment  before they are combined
        with other in-plant wastewaters?

We recommend that other wastewater treatment systems be
evaluated using the techniques developed for this study.  In
particular, the effectiveness of activated sludge and of
activated carbon filters for reducing the concentrations of
these organics would be useful information.

We also recommend that the information on specific organic
pollutants contained in this report  be used for developing
programs to monitor for evidence of  kraft paper mill
pollution in receiving waters.  Furthermore, some of the
more abundant and/or resistant compounds  (such as
dehydroabietic acid, pimeric acid, isopimeric acid,
sandaracopimeric acid,  13-abieten-18-oic acid, guaiacol,
vanillin, stearic acid, oleic acid,  margaric acid, alpha-
terpineol, and camphor) should be considered as additions to
measured parameters in future EPA effluent guidelines.

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Often chronic and acute toxicity data are lacking for most
of these compounds.  We recommend that toxicologists examine
these compounds for possible detrimental effects.  We also
recommend that taste and odor thresholds be determined,
especially for the phenolics, where this information is
lacking.

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                        SECTION III

                        INTRODUCTION


A substantial body of knowledge exists concerning the
identities of specific chemical compounds in various types
and physical sections of trees and, to a lesser degree, in
the wastewaters of paper mills.  But little is known about
what happens to these chemicals as they pass through
wastewater treatment systems and enter into receiving
waters.  To our knowledge this study represents the first
attempt to chemically characterize a wastewater, trace the
dissolved volatile organics through a treatment system, and
correlate this information with the traditional collective
pollution parameter measurements  (BOD, TOC).  The results
detailed in this report were gathered over a six-year period
and portions of them have been presented or published
previously.l~5

By tracing the chemicals through the treatment system one
can identify which compounds are being effectively removed
and which are resistant to the treatment in use.  Any new
chemicals produced during treatment are readily apparent.
Once identifications are made, the approximate concentration
of each compound can be calculated at each stage of the
treatment.  By comparing two or more different types of
treatment, their effects on the individual compounds, or on
the various classes of compounds in the wastewaters, can be
ascertained.  This knowledge will be particularly useful for
advanced wastewater treatment and control studies,
especially those involving wastewater recycling.  A build-up
in concentration of compounds resistant to the proposed
treatment could be detrimental to closed-loop systems.  If
the segregated wastewater streams are analyzed before they
are combined for treatment, the main sources of compounds
resistant to treatment can be identified and singled out for
more economical, specialized treatment, if desired or
needed.

Knowledge of the specific chemical composition of treated
wastewaters is also basic to the evaluation of the
environmental impact of these wastewaters and to the problem
of analyzing and controlling their discharge.  Once these
"refractory" compounds are identified, studies involving
their  fate and ecological effects can commence.  Acute and,
possibly more significant, chronic effects of these
chemicals on aquatic life can be determined.

Ultimately, when more statistical data have been gained on
the occurrence of specific "refractory" compounds in kraft

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paper mill wastewaters, and their environmental effects have
been evaluated, recommendations relative to some of these com-
pounds may be incorporated into the effluent guidelines for
paper mill wastewater discharges.  Information gained from
these studies concerning specific organic contaminants has
already been used by Region IV Surveillance and Analysis
Division  CSAD) in enforcement conferences^'7 and is currently
being used by Region VIII SAD8 to determine if the source of
some pollution problems lies with paper mill contaminants
 CFig. 1J.  In the summer of 1972, we provided the Organic
Analysis Unit of the Lower Mississippi River Field Facility
with evidence that contaminants from paper mills in that area
contributed measurably to the organic pollution of the
Mississippi River.*  Identification of specific resin acids
and certain phenols in polluted waters provide strong evidence
for contamination by paper mills.

This study should raise many questions and stimulate further
work that will result in an accumulation of data from many
other mills with other types of wastewater treatment.  The
report should be used as a tool by other laboratories that
desire to study the composition of kraft pulp mill wastewaters
and the effects of waste treatment on them.  Although we
relied heavily on gas chromatography-mass spectrometry (GC-MS)
for compound identification, once the identifications are made
and GC retention times are established, GC-MS is not absolutely
necessary.  A great deal of useful work can be accomplished
with GC and standards of the compounds identified in this
report.  Most paper mill laboratories and college forestry or
ecology laboratories have gas chromatographs available and the
column packings used Ccarbowax 20M/TPA and SE-30) are very
common ones.
PAPER MILL TREATMENT FACILITIES
Two mills, having similar processes but different waste treat-
ments, were used in this study.  The first, Paper Mill "A",
daily produced about 1400 tons of containerboard in March 1972
when the samples were taken.  Approximately 13 million gallons
of water passed through the treatment system daily.  Treatment
consists of a primary clarifier, trickling biofilter, secondary
clarifier, and 5 aerated lagoons with a total retention time of
2-2 1/2 days  (Fig. 2).  The trickling biofilter is 30 feet high,
and 80 feet in diameter, and is packed with a vinyl core
material having 97% void space.  It handles an average daily
load of 56,000 Ib BOD and provides 50% BOD removal.  The
total BOD reduction through the whole system is reported to be
in excess of 70%.  In 1972, grab samples for chemical

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00
              IX
     San Francisco\
                              Figure 1   EPA Regional  Districts

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 Kraft Paper Mill  "A"
 Sample point No. 1
   (Grab sample)
	e	
      Primary clarifier
(Retention time about 5 hours)
                                            Sample point No. 2  / \
                         (Grab sample 5 hours after Sample No. 1)
          Sample point No. 3
(Grab sample 3 hours after Sample No. 2)
                        Secondary Clarifier
                    (Retention time about 3 hours)
                               Trickling Biofitter
                                (Retention time
                                about 2-4 min)
                                      1   M/
            Aerated Lagoon
                 Sample point No. 4
                 (Grab sample 2 days
                 after Sample No. 3)
       (Retention time about 2 days)
                Figure  2     Waste treatment  diagram of  Mill  "A"

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characterization were taken at various stages of the
treatment system and time delays were programmed so that a
"slug" of the effluent would be followed through the
treatment facilities.  However, quantitative analysis
indicated that the slug was missed at the outfall.  A second
sampling period, in January 1974, used 3-day composites.
Daily composites of the raw effluent from January 16-18
were combined.  The quantitative results of these "average
slugs" were much more satisfactory.

The second mill. Interstate Paper Corp. at Riceboro, Ga.,
daily produced about 540 tons  of containerboard in March
1972 when the samples were taken.  Approximately  5.5 million
gallons of water passed through the  treatment system daily.
Treatment consists of lime addition  at  0.1%, a 40-minute
flocculation period followed by gravity clarification and a
650-acre  (3-6 month retention) stabilization lagoon  (Fig.
3) .  The highly alkaline effluent  (pH 12) first undergoes
partial neutralization to pH  10 by surface absorption of
atmospheric carbon dioxide, accompanied by precipitation of
nearly all the remaining calcium in  the inlet section of the
stabilization basin.  Lime treatment removes about 905S of
the color from the effluent.   Overall BOD reduction is
reported to be 93X, with a concentration of about 6 mg/1 in
the lagoon effluent.10'11      The 1972 sampling  consisted
of 24-hour composites or grab  samples at various  stages of
the treatment system as indicated in Figure 3.

During a second sampling period, in  January 1974, 3-day
composites were collected.  Daily composites of the raw
effluent and the outfall were  collected from January 16-18.
The raw effluent samples were  combined, the outfall samples
were combined, and the composites of each were analyzed.
                               10

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         Interstate Paper Corp.
            Riceboro, Ga.
                                   Sample point No. 1
                                   (24-hr composite)
       Sample point No. 3
        (24-hr composite)
               \
            —e—
                               I
           Lime Flocculation Tank
        (Retention time about 40 min.)
                                             Lime
                                            Addition
                    Clarifier
         (Retention time about 6-8 hours)
                                                            Sample point No. 2
                                                              (Grab sample)
          vy
     i   i   i   i  /i\
Quiescent Storage Basin
               I
                                        r\
 Sample point   j)
   No. 4      jf
(Grab sample) (r  C
               (Retention time 3-6 months)
                                          I
Figure  3  Waste  treatment  diagram of  Interstate  Paper Corp.,  Riceboro,  Georgia

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                         SECTION IV

                   ANALYTICAL PROCEDURES
SOLVENT EXTRACTION EFFICIENCIES

To determine the best of several common solvents used for
liquid-liquid extractions, 1-liter portions of the Mill "A"
aerated lagoon effluent were extracted with UOO-ml portions
of low boiling petroleum ether, diethyl ether, chloroform,
and ethylacetate.

Each of the extracts was concentrated in a Kuderna-Danish
evaporator  (Fig. 4) and chromatographed under identical
conditions.  Chloroform was the best of the four solvents
for these extractions.
CHLOROFORM VS CARBON CHLOROFORM EXTRACTS

Adsorption of organics on granulated carbon followed by
extraction with chloroform provides a large amount of sample
with which to work.

Accordingly, 1800 gal. of the Mill "A" aerated lagoon
effluent was passed through a bank of 8 carbon filters in
parallel.  The carbon was dried and extracted with
chloroform.  The resulting extract was concentrated in a
Kuderna-Danish apparatus, and chromatographed under
conditions identical to those used for the  1-liter
chloroform extract.  Figure 5 shows a comparison of the two
chromatograms.  Most of the same peaks are present in both
chromatograms.  Although the relative intensity differs
somewhat, the chromatograms are similar enough that, from a
qualitative aspect, the two methods of sample concentration
were essentially equivalent.

However, the carbon adsorption method has numerous
disadvantages:

     •  Extent of adsorption varies with size of carbon
        particles, contact time with carbon (flow rate), and
        turbidity of the water.

     •  Carbons from various sources differ markedly in
        their adsorptive ability.

     «  A carbon column can go septic, causing biological
        degradation of the adsorbed organics.
                              12

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                 J
Figure 4   Kuderna-Danish concentrator
                   13

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                                    Lagoon Chloroform Extract
       B
                                         CCE
Figure 5  Gas  chromatograms of the  extracts of Mill  "A"  aerated lagoon effluent
from  (A) carbon chloroform extract  (CCE)  and (B) liquid-liquid chloroform extract.

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     •  Even with the greatest practical contact times, not
        all organic matter in water will be adsorbed; highly
        polar compounds are not removed by carbon columns.

     •  it is more time-consuming to set up the pumps and
        equipment than it is to simply "grab" a sample for
        solvent extraction.

     •  Some compounds may be only partially desorbed from
        the carbon.

     •  A greater possibility of chemical change (iso-
        merization, hydrolysis, etc.)  exists when carbon
        with its large, active surface area is used.

We therefore elected to obtain the rest of our samples by
the simpler technique of extraction with chloroform followed
by Kuderna-Danish concentration.

Papermill wastewater extracts contain two types of con-
pounds:  neutrals  (predominately terpenes and their
derivatives) and acidic compounds that are converted to
their methyl derivatives to facilitate gas chromatographic
(GC)  separation.
COMPARISON OF METHYLATION TECHNIQUES

After the pH is raised to 11 and the neutrals are extracted,
the aqueous solution can be methylated directly with
dimethyl sulfate and sodium hydroxide, followed by
extraction of the methyl derivatives with chloroform.  This
method has the advantage of being an in situ procedure;
however, it is complex and time consuming.  Alternatively,
after extraction of the neutrals at a high pH, the solution
can be made strongly acidic with concentrated hydrochloric
acid, and the free acids and phenols extracted with
chloroform.  Methyl derivatives of the acids and phenols can
then be made in a separate step using diazomethane, on-
column GC methylation techniques, or several other common
methylation procedures.  An evaluation of each method was
made using representative standard compounds and also using
samples of kraft mill wastewater.
                              15

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Methylation of Standards with Diazgmethane

Ten milligrams each of guaiacol  (I), vanillin  (II), palmitic
acid (III) and dehydroabietic acid (IV)  (2 phenols, a
saturated fatty acid, and a resin acid, respectively) were
dissolved in 600 ml of water made to pH 11 with sodium
hydroxide.  The solution was placed in a separatory funnel,
made acidic with concentrated hydrochloric acid, and
extracted with three 133-ml portions of chloroform.  After
the combined extract was dried by passing it through a
column of anhydrous sodium sulfate (previously baked at
600°C. for 2 hours to remove phthalate ester impurities) , it
was evaporated to near dryness in a Kuderna-Danish
concentrator.  Two ml of 10% methanol in ether was added and
the sample was methylated by the standard procedure  with
diazomethane  (Fig. 6).  After methylation, chloroform was
added to  bring the volume to 10.0 ml, providing a
theoretical 1,000 ppm solution of each of the  four methyl
derivatives based on 100X extraction and methylation.
Duplicate injections into a gas  chromatograph  were made  and
the areas of the peaks  (calculated by multiplying the peak
height times the peak width at half height) were compared to
the peak  areas from standards of veratrole  (V),
veratraldehyde  (VI), methyl palmitate  (VII) and methyl
dehydroabietate  (VIII)  (10 mg each) in 10 ml of chloroform
 (1,000 ppm).  The calculated percent conversions were as
follows:  I-»V,  18%; II-+VT, U7%; III—>-VII,  70X; IV—*
VIII, 96%.
         .OCH3
                     .OCHj
                   CHO
 CH3

(CH,)14
 COOR
H3C
                                         H3C  COOR
 I: R = H      II: R = H       III:  R = H
V:R = CH3    VI:R = CH3    VII:R=CH3
                                              IV: R = H
                                             III:R = CH3
Methy.lation of  Standards with Dimethyl Sulfate

The  reaction with dimethyl sulfate is dependent on tem-
perature  control,  addition time,  and reaction time,  and on
                                16

-------
REDUCTION  VALVE
         METERING
           VALVE
                   '11'
 NITROGEN TANK
    GLASS OR
  STAINLESS STEEL-
    0.7mm I D
                          RUBBER STOPPER
                        0.7cm 0 D
                   TUBE I
                 (I6x ISOmm)
        RUBBER STOPPER


      0.7cm OD
      O.I cm 0 D
 TUBE 2
(15 x 85mm)
GENERATOR
                                                  RUBBER STOPPER


                                                0.7cm OD
                                                O.lcm OD
                                            T.UBE 3
                                          (15* 85mm)
                                            TRAP
                                 0.1 cm 0 D
                                                       TUBE 4
                                                      (I5x 85 mm) or
                                                    KD CONCENTRATOR TUBE
                                                    SAMPLE
         Figure  6    Apparatus  for diazomethane  methylation

-------
how vigorously the reaction mixture is stirred.  The
procedure we use1* is a variation of that described by Bicho
et al.17> is   Figure 7 shows a diagram of the apparatus.  To
determine the average yield and recovery of methylated model
compounds from this reaction, four mixtures of I through IV
were subjected to the same reaction and work-up procedures.
Three mixtures containing 10 mg of each compound and a
fourth mixture containing 25 mg of each compound were
compared.  After methylation, the products were extracted
with chloroform, dried over sodium sulfate, and concentrated
to less than 10 ml in a Kuderna-Danish apparatus.  The
volume was adjusted to 10.0 ml with chloroform.  Comparision
of GC peak areas with peak areas of standards V through VTII
allowed calculation of the percent methylation and recovery.
The results are summarized in Table I.
       tion of Wastewater Samples with Dimethyl Sulfate
A 500-ml portion of the Mill "A" wastewater from sample
point 2  (primary clarifier effluent) was made alkaline to pH
1 1 with  sodium hydroxide and extracted with chloroform to
remove the neutral compounds.  Methylation of the aqueous
layer with dimethyl sulfate was followed by re-extraction
with chloroform to remove the methylated organics.  After
concentration in a Kuderna-Danish apparatus to 0.5 ml, 1.2
yl of the extract was chromatographed on a 50 ft support
coated open tubular  (S.C.O.T.) column coated with Carbowax
20 M/TPA and programmed from 100 to 200°C. at 4°/minute with
an initial 2 minute hold at 100°.  The chromatogram is shown
in Figure 8-A.  A control sample was prepared exactly the
same way using 500 ml of distilled water; its chromatogram
is shown in Figure 9-A.
Methylation of Wastewater Samgles with Diazgmethane

A 1-liter portion of the same wastewater was extracted with
chloroform at pH 11 to remove neutral compounds and then
made acidic to pH< 2 with cone, hydrochloric acid.  The
aqueous layer was re-extracted with four 200-ml portions of
chloroform to remove the acids and phenols.  The extracts
were combined and divided into two equal portions, each
representing 500 ml of the wastewater extract.

One portion was concentrated to near dryness in a Kuderna-
Danish apparatus and methylated with diazomethane as
previously described; the final volume was adjusted to 0.5
ml.  The chromatogram of 1.2 pi of this sample under
conditions identical to those of the previous sample is
shown in Figure 8-B.  A control sample was prepared from 100
                                18

-------
                      Nitrogen Out
                   Heater-Stirrer
Figure 7  Apparatus  for dimethyl sulfate methylation
                         19

-------
Figure 8   Chromatograms of the methyl derivatives from
           a kraft paper mill wastewater sample using
           (A) dimethyl sulfate,  (B) diazomethane, (C)
           Methyl-8, and (D) MethElute as methylating
           reagents
                       20

-------
  B
DIAZOMITHANI

 ILANK
                    OIMITHTL
                    IIHIATI
Figure 9    Chromatograms of control samples treated
            with (A) dimethyl  sulfate, (B) diazomethane,
            (C)  Methyl-8, and  (D)  MethElute as methylating
            reagents
                        21

-------
                             Table  1









  PERCENT METHYLATION AND RECOVERY  OF MODEL PHENOLS  AND ACIDS




                     USING DIMETHYL SULFATE
Reaction
No.
I
•> V
II
->• VI
III
•*• VII
IV -
»• VIII
#1  (10 mg each)    74%
#2  (10 mg each)     91%
#3  (10 mg each    100%
#4  (25 mg each)    96%
          60%






          76%






          81%






          69%
            47%






            64%






            66%






            53%
            39%






            57%






            84%






            60%
AVERAGE
90%
72%
58%
60%
                               22

-------
ml of chloroform subjected to the same prodecure; the
chromatogram of 1.2 yl of the control is shown in Figure 9-
B.
Methvlation of Wastewater Samples with On-Column Reagents

The second portion of the chloroform extract was
concentrated in a Kuderna-Danish apparatus to near dryness
and MethElute (trimethylanilinum hydroxide in methanol;
Pierce Chemical Co.) was added to bring the volume to 0.5
ml.  The chromatogram of 1.2 yl of this sample under
conditions identical to those of the previous two samples is
shown in Figure 8-D.  MethElute provides on-column
methylation of the sample.  A control sample was prepared
from 100 ml of chloroform subjected to the same procedures.
The chromatogram of 1.2 yl of the control is shown in Figure
9-D.

Another 500-ml portion of the wastewater, after extraction
of neutral compounds at pH 11, was made acidic and extracted
with four 100-ml portions of chloroform.  The extracts were
combined, dried, and concentrated to near dryness as before
in a Kuderna-Danish apparatus.  Enough Methyl-8 (DMF
dimethyl acetal in pyridene; Pierce Chemical Co.)  was added
to bring the volume to 0.5 ml and the solution was heated at
60°C for 15 minutes in a reacti-vial.  The chromatogram of
1.2 //I of this sample, under conditions identical to those
of the other three, is shown in Figure 8-C.  A control
sample was prepared from 400 ml of chloroform subjected to
the same procedure.  The chromatogram of 1.2 yl of the
control is shown in Figure 9-C.
Methvlation Evaluation

Comparison of the chromatograms in Figure 8 shows that
dimethyl sulfate and MethElute are better reagents for
methylating these samples than diazomethane or Methyl-8.
Phenols, especially guaiacol, were not methylated well with
diazomethane or Methyl-8.  Although extraction of guaiacol
and other phenols with chloroform is not 100%, incomplete
extraction can be eliminated as a major contributor to the
smallness of the guaiacol peak in the diazomethane sample
because the samples for diazomethane and MethElute treatment
came from the same extract, which was divided into two
portions, and the MethElute sample shows a large veratrole
peak.

The dimethyl sulfate appears to be equivalent to MethElute
with respect to methylation of the resin and fatty acids.


                               23

-------
However, the larger phenolic peaks in the dimethyl sulfate
sample and absence of the MethElute reagent peak favored use
of dimethyl sulfate for all remaining methylations involved
in analysis of these wastewaters.
INSTRUMENTATION

Gas Chromatograph

Most of the chromatograms shown in this report were obtained
with a Varian 1400 gas Chromatograph  (GC)  equipped with a
flame ionization detector (FID).  Because helium is usually
used as a carrier gas with gas chromatographs interfaced
with mass spectrometers  (GC-MS), we used helium as a carrier
gas routinely in developing our chromatographic conditions.
Generally, a commercially prepared (Perkin-Elmer) 50-ft
support coated open tubular (S.C.O.T.) capillary column
coated with carbowax 20M/terephthalic acid (K 20 M/TPA) was
used for separation.  The optimum carrier gas flow for our
GC-MS systems operating under a vacuum and using a Gohlke
jet separator is 16 to 18 ml/minute.   If a helium flow of
about half this is used for optimizing conditions with an
auxiliary GC  (operating under atmospheric pressure), the
other chromatographic variables (temperature program rate,
initial temperature, initial hold) will hold true when the
same column is transferred to the GC-MS system.
GC-MS-Computer System

From 1968 to 1971, a Perkin-Elmer/Hitachi RMU-7 double
focusing mass spectrometer connected to a Perkin-Elmer 900
GC through a Watson-Bieman separator was used to analyze the
sample extracts from kraft papermi11 wastewaters.  Spectra
acquisition, data reduction, and spectral interpretation had
to be done manually.  Despite these limitations, much of the
early work reported in this project1-*»6*7 was accomplished
with this system.

Now, a semi-automatic GC-MS-computer system is used for
pollutant identification.  The GC is a modified Varian 1400
Chromatograph with a temperature-controlled oven that can be
programmed from 50° to 500° C.  It has no independent
detector and serves only as a specialized inlet to the mass
spectrometer.  An all-glass, single-stage Gohlke jet
separator enriches organic samples by utilizing differences
in diffusion rates of sample and carrier gases in a
turbulent jet.
                               24

-------
The Finnigan 1015 quadrupole mass spectrometer with three
mass ranges extending to m/e 750 is capable of unit
resolution throughout the range.  At a scan speed of 120
amu/sec, sensitivity is adequate to give identifiable
spectra for 20 ng of material introduced into the GC inlet.
The liquid inlet is used for introduction of calibration
compounds, the direct probe for solid materials.

A System Industries interface (analog-to-digital converter,
and the digital-to-analog converter) permits the Digital
Equipment Corporation (DEC) PDP8/e computer to control the
mass spectrometer during calibration and data acquisition;
to accept data from the mass spectrometer; and to control a
Houston plotter during data reduction.

The DEC PDP8/e computer has a 4096 word core and an ASR33
teletypewriter.  Programs, raw data, and reduced data are
stored on either two DECtape units or a Diablo disc.  Output
of the reduced data is achieved under computer control via
the plotter, the teletypewriter, or an acousticoupler.  The
coupling device connects the PDP8/e to the CDC 6UOO computer
at Battelle Laboratories, Columbus, Ohio, and permits semi-
automatic spectrum identification by a matching program,
fully described elsewhere.19 /2<>

Using this system, data reduction times are much less than
for the manual reduction methods formerly used.  About 2
hours of operator time is required to output reduced data
for an 80-peak chromatogram.  Data output time ranges from
slightly more than four hours for the disc system to more
than eight hours for the tape system.  Manual data reduction
and spectral plotting of the same 80 chromatographic peaks
would require several weeks.
                                25

-------
                         SECTION V

            IDENTIFICATION OF ACIDS AND PHENOLS


The acids and phenols in each wastewater were analyzed as a
group for both the 1972 samples and the 1974 samples.
Results were then compared.  The neutral extractable
organics (mostly terpenes) were analyzed separately and are
discussed in the next section.


GC-MS ANALYSES

Each of the 8 samples (4 from each mill at various sampling
points) was methylated with dimethyl  sulfate as previously
described.  Following this, each of the 8 extracts was
analyzed by GC-MS using the Finnigan  1015 GC-MS computer
system.  After a sample is injected into the GC, the mass
spectrometer automatically scans its  pre-set mass range
every five seconds (or other pre-set  interval).  As it does
so, the plotter draws a trace that is equivalent to a GC
signal.  Since our samples were pre-analyzed on an auxiliary
GC, the auxiliary chromatograms were  used to determine when
to terminate the GC-MS runs.  When each run is complete, the
computer plots a reconstructed gas chromatogram  (RGC).  The
RGC peaks are all normalized to the amplitude of the largest
peak, arbitrarily plotted at 100.  Each point on the
spectrum number scale under the RCG represents a complete
mass spectrum.  Figure 10-A shows the RGC of the methylated
acids and phenols from the lagoon wastewater of Mill "A".
Any of the spectra can be displayed individually; therefore,
by choosing the appropriate spectrum  numbers, the analyst
can see the composition of each peak  in the chromatogram.

Specialized techniques of MS or data  reduction can be used
to detect a specific material or class of materials in a
mixture.  The most common technique is the generation of the
limited mass reconstructed gas chromatogram  (LMRGC) .  For
example, in Figure 10-A, the RGC shows as peaks those
spectra that contain significant numbers of any ion
fragments of m/e 33 to 450.  Below the RGC is the LMRGC in
which the computer was instructed to  respond only to those
spectra that contain the m/e 149 fragment  (Figure 10-B) .
This fragment is usually due to protonated phthalic
anhydride  ( IX), found in the spectra of phthalate esters.
The LMRGC, therefore, indicates that  two of the sample
peaks, 44 and 61, are phthalates.  The numbers 44 and 61
refer to the compound designations listed in Table 2.
                                26

-------
              Table 2.  ACIDS  AND  PHENOLS  IDENTIFIED IN BOTH  KRAFT  PAPER MILL EFFLUENTS WITH APPROXIMATE CONCENTRATIONS
to
Approximate
Cone, in mg/1
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13

14
15
16
17

18

1 9
20
21
22
23

24

25

26

Compound Identified as Methyl Confirmed
Derivative (Parent Compound) By
Furfuryl methyl ether
(furfuryl)
Anisole (Phenol)
1 , 3-Dimethoxy-2-propanol
Methyl trisulfide
Unidentified — apparent MW=103
Benzaldehyde
Dime thy Isulf oxide
Ethyl carbamate
Borneol
a-Terpineol
Veratrole (Guaiacol)
o-Nitrotoluene
Methyl o-hydroxybenzoate
(o-hydroxybenzoic acid)
Methyl mandelate (mandelic acid)
Dime thylsulf one
Unidentified aromatic MW=166
Methyl isomyristate
(Ci4 fatty acid)
p-Methoxybenzaldehyde
(£-hydroxybenzaldehyde)
Eugenol
Methyl myristate (CIA fatty acid)
Unidentified aromatic, MW=196
Unidentified nonaromatic, MW=196
Methyl anteisopentadecanoate
(C15 fatty acid)
Methyl 10-methyltetradecanoate
(C15 fatty acid)
p-Methoxyacetophenone
(£-hydroxy acetophenone )
Methyl pentadecanoate
(Cj5 fatty acid)
GC


GC
GC
GC
MS,GC
MS, GC
MS,GC
MS,GC



GC

GC




MS,GC

MS,GC



GC

MS,GC


0.
0.
-
0.
0.
-
0.
-
0.
2.
-
0.

-
0.
0.
-

0.

0.
_
-
-

-

0.

-

1
010
008
-
035
002
-
010
-
020
700
-
010

-
240
130
-

055

025
_
-
-

-

020

-

Mill "A"
Sample Points
2 3
0.005
0.005
0.035
—
—
0.015
—
0.002
2.400
—
0.005

—
0.400
0.090
—

0.050

0.025
	
—
—

—

0.025

—

—
—
0.040
—
0.055
0.025
—
0.001
0.360
—
—

—
0.400
0.050
—

0.020

0.025
0.045
—
0.010

—

0.030

—

4
—
—
0.035
—
—
0.020
—
—
0.170
0.015
—

0.025
0.055
0.005
0.003

0.025

	
0.020
0.035
—
0.020

0.030

—

0.020

1
0.010
0.005
—
0.025
0.005
0.010
—
0.010
0.005
2.200
—
—

—
0.240
0.050
—

0.090

	
::
0.170
—

—

0.060

—

Approximate
Cone, in mg/1
Sample Points
2 3
0.005
0.010
—
0.055
—
0.080
0.080
0.020
0.020
3.200
—
—

—
0.540
0.030
—

0.240

— —
	
0.175
—

—

0.130

—

—
—
0.020
—
0.020
0.020
0.060
0.115
3.700
—
—

—
0.400
0.160
—

0.190

—
	
0.245
—

—

0.080

—

4
~
—
0.015
—
0.020
0.010
—
0.002
0.035
—
—

—
0.130
—
0.001

0.005

— —
0.010
0.065
0.005

0.002

0.010

0.010


-------
         Table  2   (continued) .   ACIDS AND PHENOLS IDENTIFIED  IN  BOTH KRAFT PAPER MILL EFFLUENTS  WITH APPROXIMATE CONCENTRATIONS
00
Approximate
Cone, in mg/1
Peak
No.
27

28
29

30
31

32

33
34

35
36
37
38

39

40

41

42

43
44
45

46

Compound Identified as Methyl Confirmed
Derivative (Parent Compound) By
Methyl isopalmitate (C, , fatty
acid) lb
Methyl palmitate (C,, fatty acid)
Methyl palmitelaidate (Cifi trans-
9-unsaturated fatty acid)
Ethyl palmitate (C^g fatty acid)
Methyl anteisomargarate (C^7
fatty acid)
Methyl 3,4-dimethoxyphenylacetate
(Homovanillic acid)
Veratraldehyde (Vanillin)
2-Methylthiobenzothiazole
(2-Mercaptobenzothiazole)
Methyl vanillate (Vanillic acid)
Acetoveratrone (Acetovanillone)
Methyl stearate (Cla fatty acid)
Methyl oleate (C^8 cis-9-
unsaturated fatty acid)
3 , 4 , 5-Trimethoxybenzaldehyde
( Sy r ingaldehyde )
Methyl linoleate (C18 cis,cis-9,
12-diunsaturated fatty acid)
3 , 4-Dimethoxypropiophenone
( 3-Methoxy-4 -hydroxypropiophenone )
3 , 4-5-Trimethoxyaeetophenone
(Acetosyringone)
Methyl Arachidate
a Dihexylph thai ate
Unidentified resin acid "A" methyl
ester
Unidentified resin acid "B" methyl
ester
MS,GC

MS,GC
MS,GC

MS,GC
MS,GC



MS,GC
GC

GC
GC
MS,GC
MS,GC

MS.GC

MS,GC

GC

GC







1
	

0.070
0.005

—
0.020

0.050

1.500
0.035

—
0.420
0.025
0.470

0.070

0.350

0.060

0.055

0.030
—
—

0.030

Mill "A"
Sample Points
2 3


0
0


0

0

1
0


0
0
0

0

0

0

0

0



0

	

.190
.020

—
.025

.075

.700
.025

—
.490
.065
.600

.070

.470

.080

.060

.035
—
—

.055

0.015

0.180
0.025

—
0.040

0.090

0.450
0.030

0.005
0.450
0.045
0.430

0.070

0.230

0.025

0.050

0.030
—
—

0.095

4
0.030

0.430
0.125

0.030
0.050

0.080

0.410
0.025

0.005
0.370
0.110
0.400

0.040

0.100

—

0.050

0.025
—
—

0.100

1
	

0.140
—

—
0.030

0.090

2.100
—

—
0.820
0.100
0.570

0.070

0.450

—

0.090

0.035
—
0.070

—

Approximate
Cone, in mg/1
Interstate
Sample Points
2 3
	

0.160
—

—
0.120

0.365

4.400
—

—
1.600
0.100
0.510

0.100

0.920

—

0.200

0.025
—
0.075

—

	

0.035
—

—
0.040

0.150

2.600
—

—
0.860
0.020
0.120

0.070

0.160

—

0.130

—
—
0.130

—

4
0.003

0.017
0.010

—
0.001

0.003

0.070
—

—
0.120
—
0.080

0.020

—

—

0.005

—
—
0.020

—


-------
Table 2   (continued).  ACIDS AND  PHENOLS IDENTIFIED IN BOTH KRAFT PAPER MILL EFFLUENTS WITH APPROXIMATE  CONCENTRATIONS
Appropriate
Cone, in mg/1
Peak
No.
47
48
49

50
51

to 52
10
53

54


55
56
57

58

59
60

61
Total
Compound Identified as Methyl
Derivative (Parent Compound)
Unidentified resin acid "C"
methyl ester
Unidentified resin acid "D"
methyl ester
Unidentified unsaturated fatty
acid methyl ester
Methyl pimerate (resin acid)
Methyl sandaracopimerate (resin
acid)
Unidentified resin acid "E"
methyl ester
Methyl-13-Abieten-18-oate
(resin acid)
Unidentified unsaturated fatty
acid methyl ester similar to
araconidate
Methyl isopimerate (resin acid)
Methyl abietate (resin acid)
Methyl dehydroabietate (resin
acid)
Methyl 6,8,11,13-Abietatetraen-
18-oate (resin acid)
Methyl neoabietate (resin acid)
Methyl lignocerate (C24 fatty
acid)
a Dioctylphthalate

Confirmed
By


MS,GC
MS,GC



MS,GC




MS,GC
GC
MS,GC

MS,GC

MS,GC
MS,GC



1
0.100

0.245
0.050

0.025

—

0.035


0.430
0.370
1.500

0.065

0.105
—

—
9.380
Mill "A"
Sample Points
2 3
0

0
0



0




0
0
1

0

0



10
.055

.475
.060

—

.430

—


.660
.430
.300

.070

.125
—

—
.692
0.010
0.005

0.570
0.125

—

0.800

—


0.770
0.420
4.000

0.170

—
0.055

—
10.246
4
0.035

0.800
0.045

—

1.400

—


0.780
0.050
1.000

0.095

—
0.030

—
7.123
1
—

1.270
0.340

—

0.100

0.075


4.400
3.300
3.300

0.160

1.300
—

—
21.690
Approximate
Cone, in mg/1
Interstate
Sample Points
2 3
	

0.825
0.245

—

0.035

—


1.700
1.500
2.700

0.115

1.200
—

—
21.480
—

0.610
0.275

—

0.050

—


1.200
1.900
3.600

0.280

0.450
—

—
17.700
4
0.145

0.500
0.110

—

1.050

—


0.800
—
3.900

0.180

—
—

—
7.243

-------
B
    100



    1M


     20

     0

    100-
           LMRGC   m/e 149
C   !-
    I«
     20
           LMRGC  m/e 74 & 87
                                23
                                        CI?
                                                ""
                                                         <„
                                                                        60
                 100
                            200
                                       300          400
                                          SPECTRUM NUMBER
                                                                        600
                                                                                    TOO
        Figure 10   Computer  reconstructed  (A)  gas chromatogram,
                     (B)  LMRGC using m/e 149 and (C)  LMRGC using
                     m/e 74 and 87 superimposed  on the same axis

-------
Similar characteristic fragments exist for other classes of
compounds.  The most useful ones in this study were m/e 74
and 87, which come from fragments  x   and XI respectively
and are characteristic of long-chain saturated fatty acid
methyl esters.21
                                OH
                               -C =
      IX
     0
     h
CH30—C —(
                                                       XI
                                                           — CH
The LMRGC corresponding to these fragments for the lagoon
wastewater from Mill "A" is shown in Figure 10-C.  The
numbers above the shaded peaks correspond to the
identifications in Table 2.  The 3 shaded peaks probably
correspond to methyl margarate (C-17), methyl arachidate  (C-
20), and methyl behenate (C-22), but, because these were all
minor components of unresolved peaks, the mass spectra were
not definite enough to confirm their identification.
Margarate and arachidate were later confirmed in a 1974
sample of these wastewaters.  Arachidate is assigned peak
number 43 in Table 2.

We have found that using the m/e 74 and 87 characteristic
fragments together results in a more reliable indication of
long-chain saturated fatty acid methyl esters than either
one by itself.  The two LMRGC's are superimposed and
different colored pens are used for each trace.  The peaks
at spectrum number 6  (m/e 87 search) and at spectrum number
51 (m/e 74 search) contain only one of the characteristic
fragment ions and are therefore not long-chain fatty acid
methyl esters.

From the RGC and/or LMRGC traces, spectra of interest are
chosen for output.  The mass spectrum can be either plotted
or tabulated.  This spectrum will be that of the sample
compound plus various fragments from GC column bleed, traces
of air, oil, and moisture, and possibly residual material
from a previously eluted compound.  In the worst cases the
GC peaks may be incompletely resolved so that the mass
spectrum contains not only the fragments of interest but
also fragments from other compounds comprising the peak
envelope.
                                31

-------
An example of this situation is shown in Figure 11-A.  Some
of the background fragments, from acetoveratrone and methyl
oleate, mask fragment peaks of the fatty acid methyl ester
mass spectrum.  Computer subtraction of the appropriate
quantities of these impurities, indicated by an examination
of the RGC (0.6 of the mass spectrum of acetoveratrone and
0.2 of the mass spectrum of methyl oleate), produced the
mass spectrum shown in Figure 11-B.  This spectrum is now
clearly recognizable as that of a saturated fatty acid
methyl ester, since the base peak is at m/e 74 and the
second most intense fragment occurs at m/e 87.

The mass spectrum is a chemical fingerprint that is
characteristic of a compound and can be interpreted to give
the structure of an unknown compound.  Another way to
identify an unknown compound is to match its mass spectrum
with that of a known compound from a library of mass
spectra.  We employ both methods; but to minimize the time
spent identifying the hundreds of spectra resulting from the
GC-MS data output from complex mixtures such as these
extracts, we first execute computer matching of the spectra.
This is followed by a manual comparison of the computer
matched spectra with the unknown mass spectra.

Widespread use of GC/MS/spectra-matching in pollutant
identification requires easy access to a central spectra
library,19 rapid matching, and an indication of the
similarity of the unknown spectrum to the reference spectrum
for each match.  An EPA program that provides such
information was developed using the algorithm of a matching
program described in the literature.22  This rapid program
was developed jointly by Battelle and the Southeast
Environmental Research Laboratory, and utilizes a CDC 6400
time-shared computer.23

An application of the matching program is shown in Figure
11-B.  The computer match output, inset on the spectrum,
shows that there were a total of 62 hits.  The five best
matches are printed with the best match  (correctly
identified as methyl stearate) listed first and the others
in descending order.  The "similarity index"  (SI) gives the
user an immediate indication of the quality of the matches.
The SI will show whether it is a poor match (<0.2 if the
data base does not contain any closely related compounds),
one of several fair matches  (0.2-0.35 if the correct
compound is not in the data base but related ones are), or a
good match  (>0.35 if the SI of the second best hit is
significantly lower).

Additional information provided with the match shows  (in
sequence after the chemical name) the source of the mass
                                32

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-------
spectral data (SERL indicates the Southeast Environmental
Research Laboratory), the Wiswesser Line Notation, the
molecular weight, the empirical chemical formula, the
Battelle spectrum number, and the file key.  A computer
print-out of the spectral data used for the match can be
obtained with the file key number.  The spectral data from
file key 8773 is also inset on the spectrum in Figure 12-B.
The match of these data  (the 2 most intense fragments every
1U mass units) with the  plotted spectrum is good.  The other
matches, in decreasing order of SI number  and in groups of
5, would also be printed out if desired.
ANALYSIS OF THE  1972 SAMPLES

All compounds identified in the acidic fractions of both
mills' wastewater  samples in  1972 are listed in Table 2.
The peak numbers assigned are used throughout this report.
The approximate  concentrations for each compound are
calculated in milligrams per  liter  (mg/1) based on the
sample peak area relative to  the peak area and flame
response of four representative compounds:  veratrole, 3,4-
dimethoxybenzaldehyde, methyl palmitate, and methyl
dehydroabietate.   Corrections were not made for inefficiency
in methylation and recovery  (70-90X with phenols; 60X with
fatty and resin  acids) in the calculated concentrations.
Consequently, these values are lower than they may actually
be.
Fattv Acjds

A total  of  17  different  fatty acids were found in the waste-
waters of both mills;  15 were identified and two unsaturated
acids remain unidentified.

The fatty acid content of both  raw wastewaters  (sample point
1) were  qualitatively  similar.   Seven of the eight  fatty
acids present  in  the raw wastewaters were  found at  both
mills  (palmitic,  anteisomargaric, stearic,  oleic, linoleic,
arachidic,  and unidentified unsaturated acid f54).

More dissimilarity  existed  in the fatty acid content of the
two lagoon  effluents  (sample point 4).  Ten acids were found
in both  effluents—isomyristic,  myristic,
anteisopentadecanoic,  10-methyltetradecanoic, pentadecanoic,
isopalmitic, palmitic, palmitelaidic, anteisomargaric, and
oleic.   Six others  were  found in the  lagoon effluent of one
mill but not the  other—ethyl palmitate  (as the ester),
stearic, linoleic,  lignoceric,  arachidic,  and unidentified
unsaturated acid  f5U.  In both  mill wastewaters a greater
                                34

-------
number of fatty acids was found in the lagoon effluent than
in the influents.  The majority of these new compounds are
saturated low molecular weight (C-1U, C-15, C-16)  branched
and straight-chain fatty acids.  They are probably
metabolites of aquatic life in the lagoons.
Significance of Fatty Acids—

Fatty acids are the main components of the parenchyma cell
resin of both hardwoods and softwoods and occur mainly as
glyceride esters.2*  Although those with even numbers of
carbons are present in larger amounts than those with odd
numbers of carbons, all the fatty acids from C-12 to C-21
have been found.  Recent work identified 30 fatty acids in
tall oil from pine and birch including odd-numbered carbon
fatty acids and one branched fatty acid.25  Fatty acids are
therefore expected to be in abundance in the raw effluents
from kraft mills.

Fatty acids are not generally considered to be very toxic
although the California "Water Quality Criteria" lists the
minimum lethal dose  (MLD)  for several of them at 5.0 mg/1
for fish.26  Recent work by Leach and Thakore27 has
indicated that the sodium salts of unsaturated fatty acids
are more toxic to fish than those of saturated fatty acids.
Furthermore, among the C^g unsaturated fatty acids, the
toxicity of the sodium salts increased with increasing
unsaturation in the order oleic
-------
The mass spectrum of the peak identified as methyl palmitate
is a good example of this fragmentation  (Figure 12-A).
                           CH30-C-(CH2)n

                                0
                               XII
Introduction of a methyl group in the carbon chain causes
changes in the fragmentation pattern because of easy
cleavage alpha to the tertiary carbon atom.28  This results
in a gap of 28 mass units when the CH3-CH- moiety is
cleaved.  Figure 12-B shows the mass spectrum of the
compound tentatively identified as methyl 10-
methyltetradecanoate.  A gap of 28 mass units occurs between
m/e 171 and 199.  This corresponds to cleavage on each side
of the number 10 carbon.  The mass spectrum of methyl 10-
methyltetradecanoate is not in the mass spectral data base;
however, all of the first five matches were fatty acid
methyl est ers.
Ethyl Palmitate—

The computer unexpectedly matched two mass spectra with
ethyl palmitate  (ethyl  hexadecanoate).  To compound the
confusion, one spectrum was  from a peak that  only occured in
the methylated acid  fraction of the  Mill  "A"  lagoon effluent
(Fig. 13-A) and  the  other spectrum occured in the neutral
fraction only of the Mill "A" raw effluent  (Fig. 13-B).

The base peak  (m/e 88)  and second largest fragment  (m/e  101)
are shifted 14 mass  units higher than their counterparts in
the mass spectra of  saturated fatty  acid  methyl esters.
These fragments  would correspond toxil and xiv respectively.
'25
      I
      OH
                XIII
                                         C0HcO—C—CHo —CH0
                                          2 ->   n    t.   L
                                               0
                                               XIV
                                36

-------
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                                 ',» iz i« iz IB \n i» » ao aci M b>"Jn SB
       Figure  12    Mass  spectra  of  (A)  methyl palmitate  and  (B)  tentatively
                      identified methyl  10-methyltetradecanoate

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    However, they could also be rationalized as coming from
    structures  XV  and XVI .  corresponding to the compound
    methyl 2-methylhexadecanoate.  The mass spectrum of the 2-
    methylhexadecanoate was not in the computer data bank.
                 CH 0 —C=CH
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    An LMRGC generated for each sample using m/e 88 and m/e  101,
    indicated that no more compounds of this type were present
    in the extracts.  The LMRGC of the methylated extract from
    Mill "A" lagoon wastewater is shown in Figure 1t.  Only  one
    peak (shaded) contains both fragments.
    
    The mass spectrum of methyl 2-methylhexadecanoate, (Fig.  15-
    A) closely resembles those of the sample spectra  (Figs.   13-
    A and 13-B) with only some small variations.  However, the
    methyl 2-methylhexadecanoate eluted from the GC much earlier
    than the unidentified compound in the samples.
    
    The mass spectrum of a standard of ethyl palmitate (Fig.  15-
    B) also closely resembles the mass spectra of the sample
    peaks (Figs. 13-A and 13-B).  However, methyl 2-
    methylhexadecanoate  (Fig. 15-A) shows a fragment at m/e  253
    (loss of OCH ) and ethyl palmitate  (Fig. 15-B) shows a
    fragment at m/e 239  (loss of OC2H5).  Figure 13-B contains
    the m/e 239 fragment and no m/e 253 fragment.  Figure 13-A
    does not show a m/e 239 fragment, but it shows no fragment
    at m/e 253 either.  The m/e 239 peak was probably deleted
    during background subtraction since it is quite small.
    
    The GC retention time of ethyl palmitate was identical to
    the peak in question.  Spiking the samples with ethyl
    palmitate increased the size of this peak in the sample
    extracts, confirming the identity.
    Unsaturated Fatty Acids—
    
    Six unsaturated fatty acids were detected in the acid/phenol
    fraction of which three were identified  (oleic, linoleic,
    and palmitelaidic acids).  Most of the unsaturated fatty
                                    39
    

    -------
     100-
                                                30
    I»1
    LMRGC      m/e 88 & 101
     20-
    
                             \hk.
                    100
                             200
    300
                                                              400
    500
    600
                   Figure 14   LMRGC of the methylated extract from
                                Mill  "A" lagoon  effluent
    

    -------
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            Figure 15
                                         90  IBB 110 120 l»  110 ISO 160 170  160 190 200 210 Z20 230 210 2S) 2GO 2TO a» 290 300 310 32
                                            Mass  spectra of  (A)  methyl  2-methylhexadecanoate
                                            and  (B)  ethyl palmitate  (ethyl hexadecanoate)
    

    -------
    acid concentration is contributed by oleic and linoleic
    acids.
    
    Two additional unsaturated fatty acid methyl esters were
    found in the neutral extracts.  These have been tentatively
    identified as a monounsaturated and a diunsaturated
    derivative of nonadecanoic acid (C-19).  Their isomeric
    identities were not determined.
    Fatty Acid Content of Chlorella Algae—
    
    The increase in numbers of branched and odd-numbered carbon
    fatty acids in the lagoon effluents of both mills led us to
    consider that they could be metabolites of the aquatic life
    in the lagoons.  Algae appeared to be a likely source of
    these compounds.
    
    Accordingly, 1 liter of a culture of Chlorella algae common
    to the mill area was made basic with sodium hydroxide and
    extracted with chloroform to remove the neutrals.  The
    alkaline solution was then made strongly acidic with
    hydrochloric acid and re-extracted to remove the acids.  The
    acid extracts were evaporated almost to dryness in a
    Kuderna-Danish concentrator.  A 0.10 ml aliquot of the
    concentrated extract was mixed with 0.03 ml MethElute and
    injected into a gas chromatograph for on-column methylation
    and analysis.
    
    The gas chromatogram and the RGC are shown in Figures 16-A
    and 16-B respectively.  The peak designated "R" in Figure
    16-A is from the MethElute reagent.  The peak designated
    with an asterisk in Figures 16-A and 16-B is di-n-
    butylphthalate, a contaminant.  There was no evidence of
    branched fatty acids in this species of algae, and
    pentadecanoic acid was the only odd-numbered carbon fatty
    acid present.  The acids identified and their relative
    abundances are listed in Table 3.  This evidence does not
    invalidate the hypothesis that the odd-numbered and branched
    fatty acids originate as metabolites from aquatic life in
    the lagoons.  Different species with different food sources
    can produce different compounds.
    Resin Acids
    
    A total of 13 different resin acids were found in the waste-
    waters of both mills in the 1972 samples; 8 were identified
    and confirmed and 5 were not identified.  The resin acid
    content of the finished wastewaters were qualitatively
    similar for the two mills.  Seven resin acids were common to
                                    42
    

    -------
                                 Table 3
         FATTY ACIDS IN THE EXTRACT OF A CHLORELLA ALGAE CULTURE
    CO
    Fatty
    Acid
    12:0
    14:0
    15:0
    16:0
    16:2
    16:3
    18:0
    18:1
    18:2
    Relative
    0.
    1.
    0.
    19.
    17.
    23.
    4.
    6.
    13.
    4
    6
    7
    0
    0
    2
    9
    2
    8
    Found in Paper
    Mill Wastewater
    No
    Yes
    Yes
    Yes
    No
    No
    Yes
    Yes
    Yes
    
    
    
    
    
    
    
    
    
        18:3
    13.2
    Sometimes
    Compound Name & Comments
    Laurie acid
    Myristic acid
    Pentadecanoic acid
    Palmitic acid
    cis or trans not determined
    cis or trans not determined
    Stearic acid
    Oleic or elaidic acid
    Linoleic or linolelaidic
      acid
    Linolenic or gamma-
      linolenic acid
    

    -------
                                         I6»
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       Ss.
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               1KO
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                                        I ,
         0  13  M 30 « SO 60 70 BO 30 iOOII01ZOI30l«lS016fll7O180l3020e2tOZ20230Z«2SOZ60?T02a023D3
    
           3*£-TftH MJttP
                                                       15:3
                                                  IKO
                                              1KO
                     »    a    /*
                                                      "   »<   lit   M
        Figure  16    (A)  Gas chromatogram and  (B)  RGC of  fatty
                       acid methyl esters  from chlorella algae
                                     44
    

    -------
    the raw wastewater extracts of both mills and six of these
    were found in both finished wastewater extracts.
    Differences were primarily found among the small,
    unidentified resin acid GC peaks.
    Significance of Resin Acids—
    
    Resin acids have long been known to be toxic to various
    degrees to aquatic life.  In addition, resin acid salts or
    "soaps" are responsible for much of the foaming in kraft
    mill effluents.  The foam causes additional expense in the
    treatment of these effluents because defoamers must be
    added.  If the foam is discharged to the receiving waters it
    can float long distances before it is dispersed or
    degraded.3
    
    Dr. I. H. Rogers29 has recently reported that bioassays
    using sockeye salmon have shown the lethal effects of a
    mixture of resin acids isolated from Douglas fir oleoresin
    to occur at concentrations as low as 2.0 mg/1.  Others have
    found resin acid soaps to be toxic to minnows at 1.0 mg/130
    or to the water flea, Daphnia pulex,, at 2.0 mg/131.  Resin
    acids have been reported toxic to various fish at
    concentrations of 1 mg/132 to 5 mg/1.33
    
    Leach and Thakore34 recently reported that 80% of the
    toxicity of unbleached white water (the major waste stream
    from the pulping operation of a kraft mill)  to juvenile coho
    salmon was caused by the sodium salts of three resin acid
    soaps: sodium isopimarate (55%), sodium abietate (22%), and
    sodium dehydroabietate  (5%).  The acute toxicity of free
    resin acids was much less than that of the sodium salts.
    The pimaric-type acids were also found to be more toxic than
    the abietic-type resin acids.  The remaining toxicity  (18%)
    was contributed by sodium salts of the unsaturated fatty
    acids:  sodium palmitolate, sodium oleate, sodium linoleate,
    and sodium linolenate.
    Identification of Resin Acids—
    
    In addition to the isopimaric, abietic, dehydroabietic and
    sandaracopimaric acids mentioned by Leach and Thakore3*, we
    found pimaric, 6,8,11,13-abietatraen-18-oic, neoabietic, 13-
    abieten-18-oic and several unidentified resin acids.  To our
    knowledge neoabietic, 13-abieten-18-oic, and 6,8,11,13-
    abietatraen-18-oic acids have not been reported before in
    kraft pulp mill wastewaters.  All of these resin acids  (as
    their methyl esters) were initially identified by comparison
    of their mass spectra with published mass spectra.33 They
                                    45
    

    -------
    were all confirmed by comparison of gas chromatographic
    retention times and GC-mass spectra from our instrument with
    standards obtained from Dr. Duane F. Zinkel, D.S.D.A. Forest
    Products Laboratory, Madison, Wisconsin.
    
    The mass spectra and fragmentation patterns of these resin
    acid methyl esters are covered in the literature36 and will
    not be discussed here.  The plotted spectra, however are
    shown in Figures 17-20 because some of them have ion
    abundances different from those reported in literature
    references.35  These differences are primarily the
    incorporation of masses between m/e 41 and 70 in our plots,
    and may be due to the GC mode of introduction (versus direct
    insertion probe35 3* ) with our samples and to our using a
    quadrupole mass spectrometer instead of a magnetic
    instrument.
    
    The unidentified resin acid methyl esters may be
    decomposition products or rearranged molecular structures
    from a parent resin acid.  The mass spectra of some may also
    be contaminated with mass spectra of other unresolved
    compounds or may be resin acids not previously identified
    and studied.
     Phenols
    
     Eleven different phenols were identified in the kraft mill
     wastewaters  (Table  2).  Guaiacol  (identified as its methyl
     ether, veratrole) varied in concentration from 0.5 to 2.7
     mg/1  in  the  raw effluents and was very effectively reduced
     in  concentration by both treatments.  Vanillin  (identified
     as  its methyl  ether,  veratraldehyde) varied in concentration
     from  0.8 to  2.1 mg/1  in the raw effluents but was not as
     effectively  reduced in concentration as guaiacol.  The other
     nine  phenols occured  in lesser concentrations and varied in
     simplicity from phenol to acetosyringone  (3,5-dimethoxy-4-
     hydroxyacetophenone).
    
     Based upon data obtained in 1974, some correlation can be
     made  between the percent removal of the phenols in these
     waste treatment systems and the complexity or degree of
     substitution of the phenol molecules.  Table 4 lists the
     removal  data for these phenols and shows their structures.
     The analytical data for the calculations were obtained from
     3-day composite samples, quantitated with the aid of a
     Perkin-Elmer PEP-1  computer system.   (The details of these
     analyses are described in a later section.) The phenols are
     generally more resistant to treatment as the complexity of
     the molecule increases.  This is especially true with Mill
     "A",  which has only biological treatment, with the single
    

    -------
                                Table  4
    
    
    PERCENT REMOVAL OF PHENOLS  VERSUS THEIR STRUCTURAL COMPLEXITY
    Parent Compound
    Guaiacol
    p_-Hydroxybenz aldehyde
    
    
    Vanillin
    
    
    Ace tovani Hone
    
    
    Homovanillic Acid
    
    
    Syringaldehyde
    
    Identified As Structure
    Veratrole j*
    OH
    p_-Methoxybenzaldehyde .,**.
    0
    CHO
    OH
    Ve r at r aldehyde (f\*\ 3
    CHO
    OH
    Acetoveratrone fi^]" 3
    COCH3
    OH
    Methyl Homovanillate [fil 3
    CHjCOOH
    OH
    3 , 4 , 5-Trimethoxy- CH3° "Y/'VY^"3
    benz aldehyde K 	 j \
    CHO
    % Removed
    Mill "A" Inter-
    state
    96% 98%
    21% 75%
    
    
    65% 93%
    
    
    77% 90%
    
    
    50% ?
    
    
    62%
    
    Acetosyringone
                                                 OH
                      3,4,5-Trimethoxy-   CH3°
                           acetophenone
                                                                   57%      67%
                                 47
    

    -------
                          SPECTHHIUBER 1
    
    
                          «mVL flBIETHIE SID. XS, XB.iaB-SVlS,
    00
                          SPECTHLH HfBER 39
    
    
                          (ETHYL DEHVCFDfBIETfnE, X5,. «J-.fi. laj-BYlS
                  B
                      (SB.
       XOOCHj
    
    B. 11. 13,-AeffiTATRIEN-le^ATE
      IDEHVDIHMfilETATE!
                        20 3B H
                           M^ E
                                 ...|,.l,|l,.l|,,l.|,l,l	lll|llll|,,,l|lll,l	llll|l,M|,lll
    
                                 50 6B TB  8B  9B  Iffi  111
                                                    110  120  130  1«  19 160 170 IBB 131
                                       lll|.,,,|i lll,,.ll|llll|l	nlllll,	I	
                                        ie0 170 tag tat an 210
    'i	'I	i""i""i	i	i	I'"
                                  Figure  17     Mass  spectrum  of  (A)  methyl  abietate  and
                                                      (B)  methyl  dehydroabietate
    

    -------
           SPECTTU1 HJttB 1
        a.
        a_
    
        a.
               ...I...,	I!,
                                                                    •••i1	i	i'"
    »-c	s	e	c	a1"
       H/ E
                                             is.  a> ™
                                                                                    300 310 320 330 34i
           SPECTFU1 K1CER 1
                "COOCH,
    o
    
    °
              .1,1.1	lill	lluJJIli	^.rlllllnillL^iligiiH.,^!!,,,,.,!!!	I	Ill	II,	II	
               «  se  eg  7B  ae SB  IBB 110  28 iae i-w ise IBB ITB iaa 13B 2BB 2ia 22B 23)
         20 30  •«  SB 80  Ttt
    
            KS £
                  Figure  18     Mass  spectrum  of  (A)  methyl  pimarate  and
    
                                    (B)  methyl  isopimarate
    

    -------
                   3TORH fOGER 1
                           0?
                                                                                   _L	L
                    38  v sa ee  it et se  MB
                    M^ E
                                                     ne lee ise
    U1
    O
                   SPECTHJ1 RKER 2B9
              B
       "COOCH,
    4). 13(15)-ABIETADIEN-18-OATE
      (NEOABIETATE)
                           m  IB at 30  1» llfl 120 130 1« 1SB J8B 1TB 190 130 2BB Zlfl ZZB 230 Z1B 2S 280 2TB
                          Figure  19    Mass  spectrum  of  (A) methyl sandaraco
                                         pimarate  and  (B) methyl neoabietate
    

    -------
    srErm* MMEK lit - IBB
    FCTHtL 6.e.ll.l3-feiETH1ETHEN-lB-ORIE
          Figure  20   Mass spectrum of  (A)  methyl 13-abieten-18-
                       oate and  (B)  methyl  6,8,11,13-abietatetraen-
                       18-oate
    

    -------
    exception of E-hydroxybenzaldehyde, which may be produced in
    the aerated lagoons by biological degradation of lignin or
    vanillin.  Most of these phenols are probably involved in
    complex equilibria, and their concentrations depend upon
    their initial concentrations in the wastewater, their rates
    of degradation in the lagoons, and their rates of formation
    from degradation of lignin and other molecules in the
    lagoons.
    Significance of Phenols—
    
    Phenols have long been associated with kraft paper mill
    wastewaters and many studies of their effects have been
    made.  Chopin37 reported that phenolic compounds extracted
    from various pulping processes are slightly toxic but much
    less so than phenol or cresols.  Concentrations of phenol
    that have been reported as lethal or damaging to fish range
    from 0.079 to 1900 mg/1 but the most reliable information
    relating to pure phenol under carefully standardized
    conditions indicates that the 24-, 48- and 96-hour TLm
    concentrations are in the general range of 10-20 mg/1 at
    20°C.38
    
    Probably a greater problem caused by the phenolic
    constituents of kraft mill wastewaters is the impairment of
    the flavor of fish, shrimp, and other edible aquatic life.
    A table in a recent report39 lists the highest
    concentrations of various organics in water that will not
    impair fish flavor.  Values for phenolics range from 0.005
    mg/1 for cresol to 5.6 mg/1 for phenol.  The only compound
    in the table that was found in the treated mill wastewaters
    is guaiacol.  The highest concentration of guaiacol that
    would not impair the flavor of resident fish was listed as
    0.1 mg/1.
    
    An earlier investigation*0 showed that the flavor of cooked
    coho salmon was impaired after exposure of the fish to
    untreated kraft pulp mill effluent for 72-96 hours at
    concentrations of 1-2% or more by volume.  No flavor
    impairment was noted when these fish were exposed to 2-9% by
    volume of biologically-treated effluent.  These results are
    in agreement with our findings that, in general, the
    phenolic constituents of kraft paper mill wastewaters are
    reduced in concentration from 50 to 98% by biological
    treatment.
    
    In some kraft paper mills, the pulp is bleached with
    chlorine.  Analyses of several wastewater extracts from
    bleached kraft mills in collaboration with Dr. I. H. Rogers,
    Environment Canada, Pacific Environmental Institute, West
                                    52
    

    -------
    Vancouver, B.C., have led to the identification of 3,4,5
    trichloroveratrole  XVII and tetrachloroveratrole XVIII .4
    Since the samples were methylated prior to analysis, the
    parent compounds were chlorinated guaiacols.
                                              OCH,
                      OCH,
                                                   OCH,
                 XVII
                                             XVIII
    Phenols are known to be highly susceptable to chlorination
    under the conditions employed in the bleaching operations of
    most mills.  Guaiacol was subjected to chlorination under
    conditions approximating those used in the mill from which
    the samples were taken and a series of chlorinated isomers
    resulted.  The only trichloroisomer found was 3,4,5-
    trichloroguaiacol, identified and confirmed as its methyl
    derivative (XV) by GO MS, NMR, and GC-IR.  The only possible
    tetrachloro isomer  (XVI) was also found.  The results of
    these and other related analyses are fully described in a
    separate report.41
    
    Generally, chlorinated phenols are more toxic than the
    parent compounds and the concentrations at which flavor in
    fish is impaired or at which taste and odor can be detected
    in drinking water is much lower for the chlorinated
    compounds.  For example, the highest concentration of 2,4-
    dichlorophenol that does not impair fish flavor is 1/560,000
    that of phenol for trout and 1/56,000 that of phenol for
    bass.39  The upper limit for isomeric 2,3-dichlorophenol for
    trout is 1/175 that of phenol for trout.  A great deal of
    research must be done with the phenols identified to
    determine their chlorinated derivatives produced in mill
    bleaching operations, and the effects of these chlorinated
    phenolics on aquatic life and in drinking water.
    CHEMICAL PROFILES OF ACIDS AND PHENOLS
    
    A "chemical profile" is a vertical display of the gas
    chromatograms of samples taken at consecutive points in a
                                    53
    

    -------
    waste treatment system.  The compounds present and their
    relative concentrations are therefore shown as a function of
    the treatment.
    
    This display allows one to see at a glance the effectiveness
    (or lack of it) of each step in the treatment process with
    respect to an individual compound, to a class of compounds,
    or to all chromatographable compounds in the wastewater,
    whether they are identified or not.
    
    This information in conjunction with the traditional
    collective pollution parameters  (e.g., BOD and TOC) provides
    a much better understanding and evaluation of the effluent
    composition and its possible environmental effects than the
    chemical profiles or collective parameters alone.
    
    Figure 21 shows the chemical profile of the acids and
    phenols from the wastewater grab samples of Mill "A".
    Figure 22 shows the chemical profile of the acids and
    phenols from the grab  samples of the Interstate mill at
    Riceboro, Georgia.  The peak numbers correspond to the
    compounds listed in Table 2.
    
    The compositions of the raw effluents from the two mills
    were similar.  The treated effluent samples from the two
    mills exhibited more differences.  In general, most
    compounds decreased significantly in concentration as the
    wastewater passed through the treatment system.
    
    One exception  appeared to be the resin acid content.  Some
    of the peaks appeared  to increase in concentration.  This
    apparently was the result of large variances in the
    concentration  of the organics in the mill wastewaters with
    time and our failure to have precisely sampled the "slug" of
    effluent we tried to follow through the treatment systems.
    Another factor could be that the biological parts of one or
    both of these  systems  was not working at usual efficiency
    when the samples were  taken.  In any event, the quantitation
    of the compounds in 1972 samples was not accurate.  The
    major effort was directed at the identification of these
    compounds and  their verification with standards.
     REPEAT ANALYSES  OF THE ACIDS AND  PHENOLS
    
     Additional samples from both mills were obtained in January
     1974—almost  2 years after  the previous samples  were  taken.
     The analyses  were repeated  for two reasons:
                                    54
    

    -------
                                        G-la
                                          4a
    Figure 21   Chemical profile  of acids and phenols from
               Mill "A"; sample  points 1-4.
                          55
    

    -------
           xfl.22
            'S
    
        viu
       i	r
    
                                     \
        3a
    f   I
                             1	1	r	1	1	r
           xO.33
    Figure  22   Chemical profile of acids and phenols from
               the Interstate mill at Riceboro, Georgia;
               sample points 1-4
                          56
    

    -------
         •  to ascertain whether the same compounds were still
            present and, if so,  if they were present in
            approximately the same concentrations.
    
         •  to obtain reliable,  representative, quantitative
            data on the concentrations of these compounds.
    
    The first objective is important if the information obtained
    from these studies is to be  of general use.  A radical
    change in the wastewater composition with time would require
    each analysis to be a research project—an impractical
    situation.  However, if the  composition of the wastewaters
    is essentially the same over a two-year time span, then the
    assumption that the wastewater composition will remain the
    same is basically valid, unless major changes in raw
    materials, production practices, or treatment processes
    occur.
    
    The second objective is important if the information
    obtained from these studies  is to be used to assess the
    effectiveness of the treatments towards reducing the
    concentration of a class of  chemicals or even of a specific
    compound.
    Sampling
    Samples from both mills were collected by automatic sampling
    devices at the mills.  All samples were collected during the
    same week.  Samples of the raw wastewaters and of the
    outfalls, collected over 24-hour periods, were frozen each
    day.  A 3-day composite composed of equal volumes from the
    Monday, Tuesday, and Wednesday raw wastewater samples of
    Mill "A" was prepared.  A second 3-day composite was
    composed of equal volumes from the Wednesday, Thursday and
    Friday treated wastewater samples of Mill "A".  This
    provided samples of a slug of wastewater, with a 3-day
    averaged composition, both before and after it had passed
    through the 2.5-day treatment system.
    
    Three-day composites of equal volumes from the Monday,
    Tuesday and Wednesday raw wastewater and of the treated
    wastewater samples of the Interstate Mill at Riceboro were
    prepared.  Because the stabilization pond retention time is
    at least 3 months, no attempt was made to obtain samples of
    the same slug of this wastewater.
    
    Samples were not taken at intermediate points in the
    treatment system of either mill because automatic sampling
                                    57
    

    -------
    devices were not available there and because analyses time
    was limited.
    Method of Analysis
    A one-liter aliquot of each of the four composite samples
    was taken and was prepared in essentially the same manner as
    were the 1972 samples:
    
         •  After the pH was raised to 10.5 with 50% sodium
            hydroxide, the terpenes and neutral compounds were
            extracted with chloroform.
    
         •  The aqueous sample was divided into two 500-ml
            portions and each portion was methylated using
            dimethyl sulfate.
    
         •  After extraction of the methylated portions with
            chloroform, the extracts of each sample were
            combined and concentrated to 1.0 ml.  By utilizing
            two separate methylation reactions for each sample,
            some averaging of either a low- or a high-yield
            methylation reaction is gained.
    
    The samples were spiked with acenaphthene as an internal
    standard and chromatographed on a 50-ft SCOT column packed
    with carbowax 20M/TPA.  Retention time and peak area data
    were collected on a Perkin Elmer PEP-1 computer interfaced
    with the gas chromatograph.  Computer analysis of these data
    allowed identification and quantitation of the compounds
    based on information gained from the 1972 samples.  PEP-1
    computer identifications were verified by obtaining mass
    spectra of the compounds in these samples and comparing them
    with the mass spectral data of the identified compounds from
    the 1972 samples.
    COMPUTER ASSISTED GAS CHROMATOGRAPHIC ANALYSES
    Based on the  compound  identifications from the  1972
    analyses, a computer-assisted gas chromatographic analysis
    was used to analyze the  1974 wastewater samples.  GC-MS was
    used to verify compound  identifications and showed that,
    once identified, computer-assisted GC analysis  was
    sufficient for additional analyses.
                                    58
    

    -------
    Response Factors of Model Compounds
    A standard solution consisting of 5.75 mg/1 veratrole, 1.12
    mg/1 acenaphthene, 2.82 mg/1 methyl palmitate, and 8.96 mg/1
    methyl dehydroabietate was prepared and chromatographed
    using the PEP-1 computer system.  From the known
    concentrations and the measured peak areas, response factors
    were calculated relative to that of acenaphthene, which, as
    the internal standard, is assigned a value of 1.00.  The
    response factors were as follows:
      Acenaphthene            1.00
      Veratrole               1.49
      Methyl palmitate        2.05
      Methyl dehydroabietate  2.32
    (internal standard)
    (phenols)
    (fatty acid methyl esters)
    (resin acid methyl esters)
    Assuming all compounds in the same chemical class have the
    same response factor, the above factors were assigned to the
    various phenols and fatty and resin acid methyl esters so
    the computer could calculate the concentrations of these
    compounds in the samples.
    Analyses of the .1.924 Samples
    A 300-^1 aliquot of each extract was spiked with 30 /
    -------
    the Single Reference Peak program because the time required
    for each chromatogram approaches 50 minutes.  Peaks
    corresponding to veratrole, veratraldehyde and methyl
    dehydroabietate were chosen as retention time reference
    peaks.
    
    An example of the computer program used to analyze the raw
    effluent extract from the Interstate mill at Riceboro is
    shown in Figure 23.  The raw effluent reduced data, showing
    peak areas normalized to the sum of all the peak areas in
    the run, is shown in Figure 24.  The product of the computer
    analysis of the data in Figure 24 using the program in
    Figure 23 is shown in Figure 25.  The peak number
    designations, the notation of the presence or absence of the
    compound in the corresponding 1972 sample, and the total
    from the sum of all the concentration values in Figure 25,
    were manually added to the data printed out by the computer.
    
    The gas chromatogram of the extract from the Interstate
    mill's raw wastewater is shown in Figure 26-A.  Peak number
    designations match those in Figure 25 and are consistent
    with identifications made with the 1972 samples.  The letter
    "A" designates the acenaphthene spike used for the internal
    standard.  The letter *M" designates methyl margarate, which
    was not included in the list of identifications in the 1972
    samples because the peak resolution was not as good and the
    confirmation was doubtful.
    
    The gas chromatogram and computer analysis of the extract
    from Interstate's treated effluent (sample point #4 in
    Figure 3] are shown in Figures 27 and 26-B respectively.  A
    comparison of either Figures 25 and 27 or of 26-A and 26-B
    shows significant reductions in the concentrations of these
    compounds after treatment.
    
    Similar comparisons can be made from the computer analyses
    of Mill "A" raw effluent and treated effluent extracts
    (Figs.  28 and 29} or from the gas chromatograms of these
    same extracts (Figs. 30-A and 30-B).  Analyses of the raw
    effluent were run in duplicate  (Fig. 28) to determine the
    range of agreement found using the PEP-1 system.  Twenty of
    the values were within a 1% to 10% range of agreement with
    each other.  Three of the values were greater than the 10%
    range of agreement  (35%, 38% and 53%).
                                  60
    

    -------
    PSOt
    «TO   INTERSTATE RAW EFFLUENT-ACIDS AND PHEN0LSI
    
    INST    1   , METH0D   50   , FILE     40    3l
    
    STD C0NC       l.OOOOl
    
    TIMES   48.00,     9.00,    23.55,    26.55,    30.20,   33.75,
    
    THRESHOLDS     16,     32,
    
    IKK/AIR   1.0000,      .00,
    
    T0L   .140,     .010,     5.0,
    
    REF
       1.000,    9.50,    10.50,   20.00,
    
       2.450,   24.00,    25.00,   30.00,
    
       4.100,   40.50,    42.00,   48.00,  I
    
    STD NAME   ACENAPHTHENEl
         NAME
        VERATR0LE:
        DIMETHYLSULF0NEI
        METH0XYBENZALDEHYDE»
          I
          I
          I
        AR0MATIC MV 182I
        ACENAPHTHENEl
          I
        PALMITATEl
          I
        ANTEIS0MARGARATEt
        ME H0M0VANILLATEI
        MARGARATE:
        VERATRALDEKYDEs
        VERATR0NEI
        STEARATE AND 0LEATE1
        M0STLY LIN0LEATEI
        3,4,5-TMAJ
          !
        ARACHIDATEt
        ME RESIN ACIDi
        ME RESIN ACIDi
        ME RESIN ACID MV 314l
        PIMERATEl
        SANDARAC0PIMERATEI
        13-ABIETEN-I8-0ATE!
          I
        IS0PIMERATEI
          I
        AB-  AND DEHYDR0AB-s
          I
        6,8,11,13-AB, NE0AB-I
        LIGN0CERATEI
    RRT
    .000,
    .350,
    .650,
    .760,
    .770,
    .817,
    .850,
    .890,
    .980,
    2.190,
    2.260,
    2.330,
    2.350,
    2.430,
    2.450,
    2.620,
    2.650,
    2.750,
    2.870,
    2.930,
    2.990,
    3.030,
    3.080,
    3.148,
    3.240,
    3.360,
    3.400,
    3.410,
    3.560,
    3.880,
    4. 100,
    4.170,
    4.350,
    4.600,
    RF
    1.4900,
    2.0500,
    1.4900,
    1.0000,
    1.0000,
    1.0000,
    1.4900,
    1.0000,
    1.0000,
    2.0500,
    1.0000*
    2.0500,
    1.4900,
    2.0500,
    1.4900,
    1.4900*
    2.0500,
    2.0500,
    1.4900,
    1.0000,
    2.0500,
    2.3200*
    2.3200,
    2.3200,
    2.3200,
    2.3200*
    2.3200,
    1.0000,
    2.3200*
    1.0000*
    2.3200*
    1.0000*
    2.3200*
    2.0500*
    C
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    1.0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
    .0000*
                                            -P
                                            C
                                            0)
                                             I
                                            0)
                                            A
                                            -P
                                            0)
                                            N
                                            fS
                                            g o
                                            (3 M
                                              o
                                            O .Q
                                            CO
                                            W
                                                                             Cn-H
                                                                             & 0)
                                                                               •p
                                                                             b a
                                                                             0) -P
                                                                             4J M
                                                                             3 H
                                                                             ft 
    -------
            N35I
            RUN INTERSTATE RAW EFFLUENT
            MST
                  , METH8D
                              ACIDS AND PHEN0LS
    
                             FILE   35  3t
    TIME
    6.48
    7.35
    8.40
    8.84
    9.50
    10.10
    11.56
    11.89
    12.47
    12.79
    13.13
    13*37
    13.65
    14.27
    14.63
    15.38
    15.60
    16.24
    16.66
    17.39
    17.85
    18.36
    18.72
    19.07
    19.77
    20.05
    20.60
    20.82
    20.99
    21.33
    21.59
    22.05
    22.49
    22.80
    23.30
    23.68
    23.97
    24.37
    24.66
    25.67
    26.41
    26.71
    27.57
    28.49
    28.88
    29.37
    29.61
    29.96
    30.47
    31.01
    31.73
    32.78
    33.60
    33.98
    34.54
    36.23
    37.00
    38.77
    41.98
    42.80
    44.62
    45.92
    47.13
    AREA
    .0631
    .1066
    .0188
    .1778
    .1666
    8.3184
    .0902
    .4989
    .0310
    .0878
    .0373
    .0521
    2.7822
    .0687
    .0437
    .1452
    .2228
    .0688
    .5923
    .3927
    .5308
    1.6764
    .6656
    9.0883
    .0555
    .4136
    .0518
    .0247
    .0230
    .0737
    .0378
    .8961
    .1292
    .2664
    .3619
    .7918
    .0738
    .2071
    7.7353
    .0644
    3.8972
    2.2447 !
    1.9567
    .0262
    .4292
    .2510
    .0847
    .2554
    .4545
    .5225
    1.1206
    7.8243
    2.1625
    .9214
    .6673
    24.6361
    .0222
    .8480
    50.9977
    .7900
    6.8304
    .3696
    .0180
    RRT
    .642,
    .735,
    .840,
    .884,
    .950,
    .010,
    .156,
    .189,
    .247,
    .279,
    .313,
    .337,
    .365,
    .427,
    .463,
    .538,
    .560,
    .624,
    .666,
    .739,
    .785,
    .836,
    .872,
    .907,
    .977,
    2. DOS,
    2.060,
    2.082,
    2.099,
    2. 133,
    2.159,
    2.20S.
    2.249,
    2.280,
    2.330,
    2.368,
    1.397,
    2.437,
    5.466,
    2.567,
    2.641,
    2.671,
    2.757,
    2.849,
    2.888,
    2.937,
    2.961,
    2.996,
    9.047,
    J.101,
    3.173,
    3.278,
    3.360,
    i.398.
    3.454,
    3.623,
    3.700,
    1.877,
    .198,
    .280,
    .462,
    .592,
    .713,
    RF
    .0000,
    . 0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    . 0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    . 0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000.
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    . 0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    . 0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000,
    .0000.
    c
    .0437,
    •0738,
    .0130,
    .1230,
    .1153,
    5.7582,
    .0624,
    .3453,
    .0215,
    .0608,
    .0258,
    .0361,
    I. 9259,
    .0475,
    .0302,
    .1005,
    .1542,
    .0476,
    .4100,
    .2718,
    .3674,
    1.1605,
    .4607,
    6.2912,
    .0384,
    .2863,
    .0358,
    .0171,
    .0159,
    . OS I 0,
    . 0262,
    .6203,
    .0894,
    .1844,
    .2505,
    .5481,
    .0510,
    .1433,
    5.3546,
    .0445,
    2.6978,
    1.5538,
    1.3545,
    .0181,
    .2971,
    .1737,
    .0586,
    .1768,
    .3146,
    .3617.
    .7757,
    5.4162,
    1.4970,
    .6378,
    .4619,
    17.0536,
    .0153,
    .5870,
    35.3024,
    .5468,
    4.7282,
    .2558,
    .0125,
    Figure  24    Computer print-out  of the normalized peak
                 areas  from the chromatogram of  the raw
                 effluent extract from the Interstate mill
                 at Riceboro
                              62
    

    -------
                                   INTERSTATE RAW EFFLUENT-ACIDS AND PHEN0LS
    U)
    
    
    
    
    
    
    CD H
    !x! 3
    rS t— '
    rt rt
    H (D
    PI H
    O DJ
    ft rt
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    5.
    
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    3
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    c
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    to
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    hj
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    rt
    O
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    i-i
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    §
    
    O
    Hi
    
    
    INST 4
    TIME
    10.
    11.
    13.
    15.
    16.
    17.
    17.
    18.
    18.
    19.
    20.
    22.
    22.
    23.
    23.
    24.
    24.
    26.
    26.
    27.
    28.
    29.
    29.
    30.
    31.
    31.
    32.
    33.
    33.
    34.
    36.
    38.
    41.
    42.
    44.
    45.
    10
    89
    65
    60
    66
    39
    85
    36
    72
    07
    05
    05
    80
    30
    68
    37
    66
    41
    71
    57
    88
    37
    96
    47
    01
    73
    78
    60
    98
    54
    23
    77
    98
    80
    62
    92
    , METK0D
    AREA
    8.3184
    .4989
    2.7822
    .2228
    .5923
    .3927
    .5308
    1.6764
    .6656
    9.0883
    .4136
    .8961
    .2664
    .3619
    .7918
    .2071
    7.7353
    3.8972
    2.2447
    1.9567
    .4292
    .2510
    .2554
    .4545
    .5225
    1.1206
    7.8243
    2.1625
    .9214
    .6673
    24.6361
    • 8480
    50.9977
    .7900
    6.8304
    .3696
    50 ,
    RRT
    •
    •
    •
    •
    •
    •
    •
    •
    •
    000,
    177,
    351,
    544,
    649,
    721,
    767,
    817,
    853,
    .888,
    •
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    3.
    3.
    3.
    3.
    3.
    3.
    3.
    3.
    3.
    4.
    4.
    4.
    4.
    985,
    186,
    262,
    312,
    351,
    420,
    450,
    626,
    656,
    743,
    875,
    925,
    984,
    031,
    081,
    148,
    246,
    322,
    357,
    409,
    566,
    802,
    too.
    176,
    345,
    465,
    FILE 35
    RF
    1.4900,
    1.
    2.
    1.
    1.
    1.
    1.
    1.
    1.
    1.
    1.
    2.
    1.
    2.
    0000,
    0500,
    0000,
    4900,
    0000,
    0000,
    0000,
    4900,
    0000,
    0000,
    0500,
    0000,
    0500,
    1.4900,
    2.
    0500,
    1.4900,
    1.
    2.
    2.
    1.
    1.
    2.
    2.
    2.
    2.
    2.
    2.
    2.
    1.
    2.
    1.
    2.
    1.
    2.
    2.
    4900,
    0500,
    0500,
    4900,
    0000,
    0500,
    3200,
    3200,
    3200,
    3200,
    3200,
    3200,
    0000,
    3200,
    0000,
    3200,
    0000,
    3200,
    0500,
    3i
    1.
    •
    •
    •
    •
    •
    •
    •
    •
    1.
    •
    •
    •
    •
    •
    •
    C
    3637,
    0548,
    6275,
    0245,
    0971,
    0432,
    0584,
    1844,
    1091,
    0000,
    0455,
    2021,
    0293,
    0816,
    1298,
    0467,
    1.2681,
    .6389,
    •
    •
    •
    •
    •
    •
    •
    •
    1.
    •
    •
    •
    6.
    •
    13.
    •
    5063,
    4413,
    0703,
    0276,
    0576,
    1160,
    1333,
    2860,
    9973,
    5520,
    2352,
    0734,
    2888,
    0933,
    0176,
    0869,
    1.7436,
    •
    0833,
    NAME
    VERATR0LEI
    1
    DIMETHYL SULF0NEI
    I
    M ETH0 XYBEN Z AL DEH YDE 1
    I
    l
    1
    AR0MATIC MV 182 l
    ACENAPHTHENEt
    l
    PALMITATEl
    l
    ANTEI S0MARGARATE!
    ME H0M0VANILLATEI
    MARGARATEl
    VERATRALDEHYDEl
    VERATR0NES
    STEARATE AND 0LEATEI
    MB STL Y LIN0LEATEI
    3,4,5-TMAl
    l
    ARACHIDATEl
    ME RESIN ACIDt
    ME RESIN ACIDl
    ME RESIN ACID MV 3I4l
    PIMERATEl
    SAN DARAC0 PIM ERATE l
    13-ABIETEN-18-0ATEI
    l
    IS0PIMERATEI
    t
    AB- AND DEHYDR0AB-S
    t
    6,8, 11,13-AB, NE0AB-I
    L I GN0 CERATE 1
                                                                                                    PEAK
                                                                                                    11
    
                                                                                                    15
    
                                                                                                    18
    31
    32
    M
    33
    36
    37,38
    40
    42
    
    43
    
    45
    
    50
    51
    53
    
    55
    
    56,57
    
    58,59
    60
            IN «72
             YES
    
             YES
    
             YES
                                                                                                              N0
    YES
    
    YES
    YES
     N0
    YES
    YES
    YES,YES
    YES
    YES
    
    YES
     N0
    YES
     N0
    YES
    YES
    YES
    
    YES
    
    YES,YES
    
    YES,YES
     N0
                                                       TOTAL:
                                                                30.7714 MG/L
    

    -------
                         20
      B
                    IS
                                        56,57
    Figure 26   Gas chromatogram of the acid and phenol
                extract of  Interstate's (A)  raw effluent
                and  (B) treated effluent
                             64
    

    -------
       RUN
                   INTERSTATE TREATED EFFL-ACIDS AND PHENOLS
       DJST
                   METH0D
                           50
                                ,  FILE
                                         41
                                              3:
    TIME
    10.12
    
    16.65
    18.41
    19.06
    20.07
    22.07
    22.74
    24.41
    24.67
    26.45
    26.89
    
    28.96
    29.51
    30.02
    31.06
    31.72
    32.74
    33.91
    35.98
    41.39
    43.54
    
    AREA
    .1315
    
    .1423
    .1368
    8.8748
    .1581
    .2320
    .2390
    .2475
    .5476
    .3995
    .3413
    
    . 1394
    .2972
    .2021
    1.6762
    1.3443
    2.9344
    3.6459
    2.8126
    11.7420
    .2298
    
    RRT
    I. 000,
    1.350,
    1.645,
    1.819,
    1.883,
    1.983,
    2.186,
    2.254,
    2.423,
    2.450,
    2.630,
    2.675,
    2.720,
    2.885,
    2.941,
    2.991,
    3.093,
    3. 157,
    3.257,
    3.371,
    3.572,
    4. 100,
    4.309,
    4.460,
    RF
    1.4900,
    2.0500,
    1.4900,
    1.0000,
    1.0000,
    1.0000,
    2.0500,
    1.0000,
    2.0500,
    1.4900,
    1.4900,
    2.0500,
    1.4900,
    1.4900,
    1.0000,
    1.0000,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    2.0500,
    C
    .0220,
    
    .0239,
    .0154,
    1.0000,
    .0178,
    .0535,
    .0269,
    .0571,
    .0919,
    .0670,
    .0788,
    
    .0234,
    .0334,
    .0227,
    .4381,
    .3514,
    .7670,
    .9530,
    .7352,
    3.0694,
    .0600,
    
                                                         NAME
                                                       VERATR0LEI
                                                      DIMETHYL SULF0NE:
                                                       METH0XYBENZALDEHYDEJ
                                                       I
                                                       ACENAPHTHENEt
                                                       I
                                                       PALMITATEt
                                                       :
                                                       MARGARATEs
                                                       VERATRALDEHYDE:
                                                       VERATR0NE!
                                                       STEARATE AND 0LEATEI
                                                      ME  SYRINGALDEHYDE:
                                                       3,4, 5-TMAl
                                                       l
                                                       t
                                                       ME RESIN ACID;
                                                       ME RESIN ACID:
                                                       PIMERATEt
                                                       SAND-P AND J3-AB-18-:
                                                       IS0PIMERATE!
                                                       AB- AND DEHYDR0AB- :
                                                       6,8, 11, 13-AB, NE0AB-:
                                                      L I GN0 CERATE:
    PEAK
    11
    15
    18
    A
    28
    M
    33
    36
    37,38
    39
    42
    45
    48
    50
    51,53
    55
    56,57
    58,59
    60
    IN '72
    YES
    YES
    YES
    --
    YES
    N0
    YES
    YES
    N0,YES
    YES
    YES
    YES
    YES
    YES
    YES, YES
    YES
    N0,YES
    YES,N0
    N0
                                      T0TAL:
                                               6.9079 MG/L
    Figure 27    Computer analysis  of the  chromatogram of  Interstate's
                  treated  effluent acid and phenol extract
    

    -------
    HIST
                1   MILL A RAW EFFLUENT-ACIDS AND PHENILS
    
                METHID   SO  , FILE   37   3|
    TIME
    10.14
    13.66
    16.70
    18.48
    19.10
    10.08
    28.10
    
    £3.75
    24.73
    26.51
    26.88
    27.47
    27.66
    27.94
    28.98
    30.59
    31.13
    31.88
    32.86
    34.10
    36.20
    41.92
    44.11
    44.59
    45.81
    AREA
    3.1384
    1.7237
    .2877
    .4908
    9.2566
    .3537
    1.3317 !
    1
    .4753 1
    5.2457 1
    3.0875 t
    3.5064 1
    .9110
    .7588
    .2840
    .9289
    .5729
    .5133
    .4960
    4.0798
    6.7065
    3.8577
    26.4614
    .3482
    .5035
    .4653 4
    RRT
    .000*
    .347.
    • 646*
    .822.
    .883.
    .980.
    i. 184.
    !.220.
    8.350,
    8.450,
    !.629.
    i.661.
    .726.
    .746.
    .774.
    • 879.
    .037,
    .087,
    .152.
    • 250.
    .366.
    .563.
    .100,
    .305,
    • 350,
    t.464.
    RF
    1.4900,
    2.0500.
    1.4900.
    1.0000.
    I. 0000,
    1 . 0000.
    2.0500,
    2.0500.
    1.4900.
    1.4900.
    1.4900.
    2.0500.
    1.4900.
    2.0500.
    1.4900.
    1.4900.
    1.0000.
    2.3200.
    2.3200.
    2.3200.
    2.3200.
    2.3200,
    2.3200.
    8.3200,
    2.3200,
    2.0500.
    C
    .5051.
    .3817.
    .0463,
    .0530,
    1.0000.
    .0382.
    .2949,
    
    .0765,
    .8443,
    .4969,
    .7765,
    .1466,
    . 1680,
    .0457,
    . 1495,
    . 06 1 8,
    .1286,
    . 1243,
    1.0225,
    1.6808,
    .9668,
    6.6320,
    .0872,
    .1262,
    . 1030,
                                                     NAME
                                                  VERATMLCl
                                                  DIMETHYL SULFCNEl
                                                  H ETH« XYBEMIAL DEHYDEI
                                                  I
                                                  AC EM A PH THE* El
                                                  I
                                                  PALMlTATCl
                                                 PALM IT EL AI DATE I
                                                  HE HfHfVAMlLLATEl
                                                  VERATRAL DEHYDEl
                                                  VERATRCMEl
                                                  STEARATE AMD ILEATEl
                                                  ME SYRIMOALDEMYDEl
                                                  LIMSLEATEi
                                                  3,4-ENPl
                                                  3. 4,5-TM AI
    
                                                  HE RESIN AClDl
                                                  HE RESIN ACIDS B,C|
                                                  PlHCRATEt
                                                  SAMD-P  AND I3-AB-18-I
                                                  IStPlHCRATEl
                                                  AB- AND DEHYDRCAB-I
                                                  6.8. II. I3-AB-I
                                                  MECABIETATEl
                                                  LI Mi CERATE I
     II
     19
     18
    29
    38
    33
    36
    37,38
    39
    40
    41
    46,47
    50
    51.93
    59
    56.97
    98
    9»
    60
                                  IN '71
                                  YES
                                  rts
                                  res
                                  TES
                                  YES
                                  YIS
                                  YtS
                                  YIS
                                  YES.YIS
                                  YES
                                  YES
                                  YES
                                  YES
                                  YES.YtS
                                  YES
                                  YES.M
                                  YES
                                  YES.YTS
                                  YES
                                  YES
                                  TOTAL I
                                          14.9834 MG/L
    KM
    WST 4
    TIME
    10.07
    13.60
    16.63
    18.43
    19.05
    20.02
    22.04
    
    23.70
    24.69
    26.46
    26.76
    27.42
    27.62
    27.90
    28.93
    29.50
    30.54
    31.08
    31.76
    32.78
    34.00
    36.08
    38.76
    41.63
    44.26
    45.43
    2 HILL
    . HETHID
    AREA
    3.2236
    1.8019
    .3241
    .4818
    9.7027
    .3204
    1.3312
    
    .4879
    5.3897
    3.1908
    3.4873
    .9637
    .7164
    .2862
    .9194
    .3288
    .6329
    .7586
    .8566
    4.4606
    6.9305
    3.9542
    .3831
    26.4755
    .8086
    .3379
    A RAV
    50 ,
    RRT
    .000,
    .350,
    .651.
    .830,
    .891,
    .987,
    2. 187,
    2.220,
    2.352,
    2.450,
    2.625.
    2.654.
    2.720,
    2.739,
    2.767,
    2.869,
    2.925,
    3.027,
    3.079.
    3.145,
    3.243.
    .1.361.
    3.563,
    3.822,
    4. 100,
    4.354.
    4.467,
    EFFLUTMT-
    riLE
    RF
    1.4900,
    2.0500,
    1.4900.
    1.0000.
    1.0000.
    1.0000,
    2.0500.
    2.0500.
    1.4900.
    1.4900.
    1.4900.
    2.0500.
    1.4900.
    2.0500.
    1.4900.
    1.4900,
    1.0000,
    1.0000,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    2.3200,
    1.0000,
    2.3200,
    2.3200,
    2.0500,
                                             C
                                            .4950,
                                            .3807,
                                            .0497,
                                            .0496,
                                           1.0000,
                                            .0330,
                                            .2812,
    
                                            .0749.
                                            .8276,
                                            .4899,
                                            .7368,
                                            .1479,
                                            .1513,
                                            .0439,
                                            .1411,
                                            .0338,
                                            .0652,
                                            .1814,
                                            .2048,
                                           1.0665,
                                           1.6571,
                                            .9454,
                                            .0394,
                                           6.3304,
                                            .1933,
                                            .0714,
       NAME
     VCRATRfLEl
     DIM ETHYL SULFCN El
     HETHIXYBENEALDEHYDEl
       t
     ACENAPHTHENEl
     I
     PALM I TAT El
    PALMITELAIDATEl
     HE H»MiVAMILLATEl
     VCRATRALDERYDEl
     VERATRMEl
     STEARATE AMD •LEATKl
     HE SYRIMaALDEMYDEl
     LINfLEATEl
     3. 4-DNPl
     3,4. 5- THAI
     ME RESIN ACIDl
     HE RESIN ACIDS  B.CI
     PIHERATEt
     SAMD-P AMD I3-AB-I8-I
     1S4PIMERATEI
     I
     AB-  AMD DEHYDRCAB-I
     6.8. II, 1 3- A3. HUABI
     LIONtCERATEl
     ||
     15
     lg
     37,
     3*
     46,47
     SO
     51.53
     55
     _
     56.97
     98,9*
     6O
    IN -72
     YtS
     YES
     YES
    Y*S
    YE5
    •*es
    YIS
    YtS
    YtS. YtS
    YtS
    YES
    YtS
    YtS
    YtS, YES
    YES
    YXS.N8
    YtS
    
    YtS, YtS
    YtS, YtS
                                  T»TALl
                                          14.6913 HQ/L
     Figure  28     Computer  analysis  of the chromatogram of  Mill
                       "A's"  raw effluent acid  and  phenol  extract  (A)
                       run  no.  1 and  (B)   duplicate  run
                                            66
    

    -------
    RUN          MILL A TREATED EFFLUENT-ACIDS AND PHENOLS
    
    INST   4   , METH0D   50   , FILE    36   3i
    c
    b
    
    [si
    ID
    
    
    !> O
    • 3
    ra_lo
    " rt
    O (D
    rt
    Hi fu
    fa 3
    H H
    
    P> W
    O H-
    H- 01
    Oi
    O
    p) (-h
    3
    DJ rt
    f
    T3 (D
    !?
    (D O
    O H
    H O
    (D QJ
    X rt
    rt 0
    H IQ
    (U hj
    0 Q)
    rt 3
    O
    Hi
    3
    H-
    TIME
    10.12
    13.64
    16.70
    17.42
    18.39
    18.71
    19.11
    19.79
    20.12
    21.03
    22.11
    22.57
    23.66
    24.44
    24.72
    26.48
    26.93
    27.44
    27.64
    27.92
    28.55
    28.98
    29.54
    30.53
    31.04
    31.78
    32.78
    33.96
    35.48
    36.06
    41.43
    44.17
    45.48
    49.59
    I
    N0TEs
    AREA
    . 1291
    .1732
    .2452
    . 1129
    .1112
    .2002
    9.9590
    . 1403
    . 1804
    .1711
    1.8876
    1. 1136
    .2549
    .2631
    1.9480
    .7781
    2.2860
    .3729
    .1832
    .1779
    .3314
    .4289
    .2222
    .6486
    • 4631
    .2201
    .8428
    1.4073
    .2199
    .7912
    2.5728
    .2192
    .2818
    .1314
    
    RRT
    .000,
    .347,
    .650,
    .721,
    .817,
    .848,
    .888,
    .955,
    .988,
    2.079,
    2.187,
    2.234,
    2.343,
    2.421,
    2.450,
    2.626,
    2.671,
    2.723,
    2.743,
    2.771,
    2.834,
    2.877,
    2.934,
    3.031,
    3.081,
    3.154,
    3.252,
    3.368,
    3.516,
    3.573,
    4. 100,
    4.368,
    4.496,
    *******,
    
    RF
    1.4900,
    2.0500,
    1.4900,
    2.0500,
    1.4900,
    2.0500,
    1.0000,
    2.0500,
    1.0000,
    2.0500,
    2.0500,
    2.0500,
    1.4900,
    2.0500,
    1.4900,
    1.4900,
    2.0500,
    1.4900,
    2.0500,
    1.4900,
    1.0000,
    1.4900,
    1.0000,
    2.0500,
    1.4900,
    2.3200,
    2.3200,
    2.3200,
    2.0500,
    2.3200,
    2.3200,
    2.3200,
    2.0500,
    1.0000,
    TOTAL I
    C
    .0193,
    .0356,
    .0366,
    .0232,
    .0166,
    .0412,
    1.0000,
    .0288,
    .0181,
    .0352,
    .3885,
    .2292,
    .0381,
    .0541,
    .2914,
    .1164,
    .4705,
    .0558,
    .0377,
    .0266,
    .0332,
    .0641,
    .0223,
    . 1335,
    .0692,
    .0512,
    .1963,
    .3278,
    .0452,
    .1843,
    .5993,
    .0510,
    .0580,
    .0131
    3.8114
    10-METHYLTETRADECAN0ATE UNDER ACENAPHTHENE
    1
    VERj
    DIM
    MET!
    MYR
    AR01
    ANT
    ACD
    PEN
    t
    IS0
    PALI
    PALI
    ME
    MAR
    VER
    VER
    STE
    ME
    LINI
    PHT1
    <
    3,4
    s
    ARA
    DIH
    RES
    PIM
    SAN
    UNS
    1 50
    AB-
    NE0
    LIGI
    , 1
    MG/L
    IS E
                                                           NAME
                                                           ATR0LEI
                                                        DIMETHYLSULF0NE!
                                                        METH0XYBENZALDEHYDEI
                                                        MYRISTATEt
                                                        AR0MATIC  M V I68l
                                                        ANTEIS0 C-15 I
                                                        ACENAPHTHENEt
                                                        PENTAOECAN0ATEI
                                                        t
                                                        IS0PALMITATEI
                                                        PALMITATEl
                                                        PALM1TELAIDATEt
                                                        ME H0M0VANILLATEI
                                                        MARGARATE:
                                                        VERATRALDEHYDEl
                                                        VERATR0NES
                                                        STEARATE AND 0LEATEI
                                                        ME SYRINGALDEHYDEl
                                                        LIN0LEATEI
                                                        PHTHALATEt
                                                        <
                                                        3,4,5-TMAi
                                                        s
                                                        ARACHI DATEt
                                                        DIHEXYLPHTHALATEl
                                                        RESIN AND FATTY ACIDl
                                                        PIMERATEt
                                                        SAND-P AND 13-AB-18-:
                                                        UNSAT FATTY ACIDl
                                                        IS0PIMERATEI
                                                        AB- AND DEHYDR0AB-I
     PEAK
     II
     15
     18
     20
    
     23
     A
     86
    
     27
     28
     29
     32
     M
     33
     36
     97,38
     39
     40
    42
    
    43
    44
    46,49
    50
    51,53
    54
    55
    56,57
    59
    60
    IN '72
     YES
     YES
     YES
     YES
    
     YES
    
     YES
    
     YES
     YES
     YES
     YES
      N0
     YES
     YES
     YES
     YES
     YES
    YES
    
    YES
    YES
    YES
    YES
    YES
     N0
    YES
    YES
     N0
    YES
                                                                                 IS UN SATURATED.
    

    -------
                                               56,57
                            20
                                     30
                                              40
        B
                       15
    
                       I
     23
    18
    120
         ir
    
        27 29
                                33
         37,36
          \/
                                       49
                                         53
                                        51/
    26
                                          55
                                              56,57
                                               I
                    10
                                     30
    Figure  30   Gas  chromatogram of the  acid and phenol
                 extract of Mill  "A's"  (A}  raw effluent —
                 run  no.  1 and  (B)  treated  effluent
                               68
    

    -------
    Comparisons of the 1974 and the 1972 Samples
    Table 5 lists TOC, BOD  and total volatile components in the
    acid/phenol extracts from both mills in this study for both
    sampling times.
    
    Comparison of the collective pollution parameters indicates
    that BOD  removal is around 70-9OX in both mill wastewaters
    after treatment.  TOC reduction in the treated wastewaters
    of both mills probably varies between 60-90%.  Because of
    large amounts of suspended solids in the raw effluent of
    Mill "A", the 1972 TOC values may be erroneous.
    
    Reduction in total volatile acidic materials is about 65-BOX
    in both mills.  The decrease of only 24% in the 1972
    sampling of Mill "A" is probably not representative because
    of faulty sampling, as explained earlier.
    
    If treatment effectiveness is considered with respect to
    classes of compounds, the phenols appear to be the most
    susceptable to treatment.  Reduction in the volatile
    phenolic content of each mill was very consistent, ranging
    in Mill "A" wastewaters from a 7356 to a 77% reduction.
    Volatile phenols were reduced in the Interstate wastewaters
    by 94% to 95%.
    
    Resin acid reductions in the treated wastewaters ranged from
    about 50% to 90%.  The apparent increase in resin acid
    content of Mill "A" in 1972 is due to a non-representative
    grab sample in which the "slug" of effluent being sampled
    was apparently missed.
    
    Fatty acid content of the Interstate wastewaters was
    decreased by about 85% to 90%, but there were increases in
    overall fatty acid concentrations in both the 1972 and the
    1974 samples of Mill "A" treated wastewaters.  This is
    probably due to the production of fatty acids by the
    microbiota in the aerated lagoons.  An increase in number of
    branched and odd-carbon fatty acids was also noted.
    
    To maintain the proper perspective with respect to a mass
    balance, the total volatile acidic material as well as the
    three major classes of compounds comprising it is presented
    as a percentage of the TOC in Table 6.  The total of all the
    volatile acidic components in the wastewater extracts was
    less than 10% of the total organic carbon content of the
    wastewaters.  The neutral components, discussed in the next
    section, are usually less than 1% of the TOC.  The
                                    69
    

    -------
                                                        Table 5
                COLLECTIVE POLLUTION  PARAMETER MEASUREMENTS AND TOTAL CONCENTRATIONS OF THE VOLATILE
                                        COMPONENTS IN THE ACID-PHENOL EXTRACTS
                                                                    CONCENTRATIONS (mg/1)
    BOD5
    
    TOC
    Total GC Organics
    Total Phenols
    Total Fatty Acids
    Total Resin Acids
    Mill "A"
    1972
    Raw
    Outfall
    *
    Change
    1974
    Raw
    Outfall
    *
    Change
    Interstate Paper at Riceboro,
    1972
    Raw Outfall
    %
    Change
    Georgia
    
    1974
    Raw
    Outfall
    *
    Change
    323
    240
    9.38
    4.96
    1.01
    2.04
    88
    230
    7.12
    1.15
    1.46
    4.27
    -73
    - 4
    -24
    -77
    +45
    +109
    320
    350
    14.98
    2.31
    1.36
    10.77
    45
    350
    3.81
    0.62
    1.59
    1.39
    -86
    0
    -75
    -73
    +17
    -87
    438
    470
    21.69
    5.53
    1.40
    14.24
    70
    200
    7.24
    0.27
    0.14
    6.71
    -84
    -57
    -67
    -95
    -90
    -53
    440
    490
    30.77
    3.57
    1.34
    24.37
    52
    85
    6.91
    0.23
    0.19
    6.37
    -88
    -83
    -78
    -94
    -86
    -74
                         *Related to concentrations  of total gas chromatographable organic material.
    

    -------
                         Table 6
    VOLATILE ACIDIC COMPONENTS AS PERCENTAGES OF TOC
    PERCENTAGE OF TOC
    
    
    Total
    Total
    Total
    Total
    COMPONENT
    
    Acidic Volatiles
    Phenols
    Fatty Acids
    Resin Acids
    
    Mill A -
    Raw Effluent
    4.
    0.
    0.
    3.
    28
    66
    39
    08
    1974
    Outfall
    1.09
    0.18
    0.45
    0.40
    Interstate
    Raw Effluent
    6.28
    0.73
    0.27
    4.97
    - 1975 J
    Outfall
    8.13
    0.27
    0.22
    7.49
    

    -------
    sura of all the volatile components therefore is still less
    than 10% of the TOC.  Yet in this minority of the mass of
    dissolved organic material probably lies the bulk of problem-
    causing compounds—toxic compounds and those causing taste
    and odor.  The dark brown color of kraft pulp mill wastewaters
    is believed to be due to partially degraded lignin molecules.
    These high molecular weight non-volatile compounds form a
    significant portion of the balance of the TOC.  Other
    contributors to the TOC are the carbohydrates and, to a
    lesser extent, tannins and various other highly polar or
    non-volatile compounds.
    
    The increase in the proportion of the TOC represented by
    total volatiles and resin acids in the Interstate
    wastewaters is a reflection of the greater decrease in the
    non-volatile portion of the organic content as compared to
    the volatile and resin acid content.  Lime flocculation
    probably removed a large amount of the non-volatile organics.
    
    The major difference in the volatile organic content of
    wastewaters from the two mills was the fatty acid content.
    Whereas the fatty acids decreased significantly during the
    Interstate treatment, they increased during treatment in
    Mill "A".
    
    Reduction in BOD, TOC, total GC peak areas, and phenolic
    and resin acid content were similar in the wastewaters from
    the two mills.
                                   72
    

    -------
                             SECTION VI
    
                     IDENTIFICATION OF TERPENES
    The neutral volatile fraction of the paper mill wastewater
    extracts was not subjected to as complete a characterization
    as was the acidic and phenolic fraction.  There were several
    reasons for this decision:
    
         •  Dr. Bjorn Hrutfiord, University of Washington, has
            been conducting a similar study on an EPA grant for
            the past 2 years and has concentrated primarily on
            the terpene fraction and on a sugar fraction.42
    
         •  Our results indicated that the terpenes and other
            neutral volatiles are about one-tenth the
            concentration of the acids and phenols in the raw
            wastewaters.
    
         •  The terpenes appear to be generally susceptible to
            biological treatment and are minor constituents in
            the treated wastewaters being discharged.
    GC-MS ANALYSIS
    
    Chemical profiles of the neutral volatiles from the extracts
    of both mills are shown in Figures 31 and 32.  Table 7 lists
    the individual compounds corresponding to the peak numbers
    in Figures 31 and 32.  Since these samples were taken in
    1972, they may not be quantitatively representative of a
    slug of the effluent.  The concentrations of compounds in
    each sample are probably slightly low because extraction
    efficiencies are never 100%.  Several compounds were
    detected and identified even though their concentrations
    were less than 1 part per billion.
    
    Gas chromatograms from the 1974 sampling of the raw
    effluents and the treated effluents of both mills are shown
    in Figures 33 and 34.  No attempt was made to identify these
    compounds because of lack of time.  However, most of the GC
    peaks have similar relative retention time and areas as
    those from the 1972 neutral volatile extracts.
    GC-IR ANALYSIS
    
    Two of the 1972 neutral volatile extracts from Mill A were
    analyzed by a Digilab Fourier Transform infrared spectro-
                                    73
    

    -------
    Table  7.  NEUTRAL VOLATILES IDENTIFIED IN BOTH KRAFT PAPER MILL EFFLUENTS  WITH APPROXIMATE CONCENTRATIONS
    Approximate
    Cone, in mg/1
    Peak
    No.
    4
    62
    63
    64
    65
    66
    67
    68
    69
    70
    71
    72
    73
    9
    10
    11
    74
    75
    76
    77
    78
    79
    80
    81
    
    30
    82
    83
    
    84
    Total
    Compound Identified
    Methyl trisulfide
    Fenchone
    Hexachloroethane
    Sabinene
    Unidentified terpene ketone
    Camphor
    Unidentified terpene ketone
    Unidentified terpene ketone
    Fechyl alcohol
    Unidentified terpene ketone
    Terpene- 4 -ol
    2-Formy Ithiophene
    Methyl chavicol
    Borneol
    a-Terpineol
    Veratrole
    2 -Acety Ithiophene
    Myrtenol
    2 -Propiony Ithiophene
    Anethole
    Benzyl alcohol
    Methyl eugenol
    Unidentified terpene alcohol
    Unidentified aromatic similar
    to methyl isoeugenol (MW=178)
    Ethyl palmitate
    Unidentified monounsaturated
    CIQ fatty acid methyl ester
    Unidentified diunsaturated C19
    fatty acid methyl ester
    Unidentified phthalate diester
    
    Confirmed
    By
    
    MS.GC
    
    
    
    MS,GC,IR
    
    
    GC
    
    MS.GC
    
    MS,GC
    MS,GC,IR
    MS,GC
    MS,GC
    GC,IR
    
    GC,IR
    
    
    GC
    
    
    
    MS,GC
    
    
    
    
    
    
    0
    0
    
    
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    0
    
    0
    0
    0
    
    
    1
    1
    .003
    .007
    —
    —
    .055
    .045
    .045
    .020
    .065
    .025
    .050
    .010
    .045
    .275
    .645
    .020
    .025
    .010
    .025
    .007
    .013
    .002
    .006
    .006
    
    .006
    .038
    .016
    
    —
    .464
    Mill "A"
    Sample Points
    2 3
    0.004
    0.007
    —
    —
    0.050
    0.045
    0.040
    0.020
    0.065
    0.025
    0.045
    —
    0.040
    0.200
    0.700
    0.015
    0.025
    0.010
    0.025
    —
    0.012
    0.001
    0.007
    0.008
    
    —
    —
    _.
    
    —
    1.344
    0.008
    0.015
    —
    —
    0.055
    0.060
    0.050
    0.025
    0.035
    0.020
    0.040
    —
    0.030
    0.155
    0.625
    0.015
    0.030
    0.008
    0.025
    —
    0.008
    —
    0.010
    0.009
    
    —
    —
    ___
    
    —
    1.223
    4
    0.001
    0.015
    —
    —
    0.045
    0.090
    0.045
    0.020
    0.010
    0.004
    0.010
    —
    —
    0.090
    —
    0.008
    0.025
    —
    0.010
    —
    —
    —
    —
    —
    
    —
    —
    ._
    
    —
    0.711
    1
    	
    0.015
    —
    —
    0.040
    0.090
    0.045
    0.020
    0.105
    0.015
    0.030
    —
    0.030
    0.470
    0.490
    0.015
    0.012
    0.008
    0.020
    —
    0.025
    —
    0.030
    0.009
    
    —
    —
    __
    
    —
    1.469
    Approximate
    Cone, in mg/1
    Interstate
    Sample Points
    2 3
    	
    0.002
    —
    —
    0.010
    0.015
    0.006
    0.003
    0.040
    0.005
    0.010
    —
    0.010
    0.200
    0.215
    0.004
    0.002
    —
    0.005
    —
    0.004
    —
    0.015
    0.006
    
    —
    —
    __
    
    —
    0.552
    	
    0.001
    —
    —
    0.015
    0.020
    0.020
    0.008
    0.060
    0.009
    0.015
    —
    0.020
    0.260
    0.280
    0.008
    0.004
    —
    0.010
    —
    0.007
    —
    0.015
    0.008
    
    —
    —
    __
    
    —
    0.760
    4
    	
    <0.001
    <0.001
    0.003
    0.004
    0.035
    0.008
    0.002
    —
    —
    <0.001
    —
    —
    —
    0.080
    —
    <0.001
    —
    <0.001
    —
    —
    —
    0.008
    —
    
    —
    —
    __
    
    —
    0.145
    

    -------
                                                G-ln
    0   5   10    15   20   25   30   35  40   45   50   55   60   65
     Figure  31   Chemical profile of neutral volatiles from
                  Mill "A";  sample points 1-4
                                75
    

    -------
              I-In
                           '1'1
              I-2n
    \
               I-3n
              I-4n
    Figure 32    Chemical profile of neutral volatiles from
                 the  Interstate mill at Riceboro;  sample
                 points 1-4
                              76
    

    -------
                X 16
    Figure 33   Gas chromatogram of neutral volatile extract
                from Mill "A's" raw effluent  (A)  and  (B)
                treated effluent
                              77
    

    -------
           10
                    20
                            30
                                     40
                                              50
                                                       60
         B
    
       X 16
                                         A.
    A
           10
                    20
                            30
                                     40
                                              50
                                                       60
    Figure 34    Gas  chromatogram of neutral  volatile extract
                 from Interstate's raw effluent (A)  and  (B)
                 treated effluent
                               78
    

    -------
    photometer interfaced with a gas chromatograph (GC-IR).
    Spectra of the eluting compounds are obtained "on the fly"
    as they are with the GC-MS system.
    The gas chromatograms of the two samples analyzed by GC-IR
    are shown in Figure 35.  GKR-3 and GKR-4 correspond to G-3n
    and G-tn, respectively, in Figure 31.  A different peak
    notation system was used in Figures 35-45.  The peak numbers
    in these figures correspond to the identifications in Table
    6 in the following way:
      GC-IR
    Designation
        13
        14
        15
        16
        17
        18
        19
        20
        21
        22
        23
        24
         a
         b
         c
         d
         e
      Table 6
    Designation
        67
        68
      69-71
    
        73
       9,10
        74
        75
    
        76
    
        78
        65
        66
    
        67
        68
    Compound Name
    unidentified ketone
    unidentified ketone
    3 compounds
    
    methyl chavicol
    borneol and a-terpineol
    2-acetylth.iophene
    myrtenol
    
    2-propionylthiophene
    
    benzyl alcohol
    unidentified ketone
    camphor
    
    unidentified ketone
    unidentified ketone
                                    79
    

    -------
    Figure 35   Gas chromatograms of Mill "A" neutral volatile
                extracts analyzed by GC-IR; sample points 3-4
                                80
    

    -------
    The GC-IR spectra of the peaks in Figure 35 are shown in
    Figures 36-41.
    
    Although the exact structures of peaks 11,13, and 14 (a,d,
    and e in GKR-4)  were not identified from the GC-IR spectra
    (Figs.  38 and 41), they were all ketones.  Computer matching
    of the mass spectra of these same peaks had led to tentative
    identifications  of 1-cyclohexenyl methyl ketone, 4-nonyne,
    and 3-cyclohexen-1-yl methyl ketone, respectively.  The
    presence of ketone carbonyl absorption in the infrared
    spectra eliminates the possibility that one is 4-nonyne and
    confirms the methyl alkyl ketone structures of all three
    compounds.
    
    Four of the GC-IR identifications were confirmed by
    comparing the sample spectra with standards.  The spectra of
    camphor, borneol, 2-acetylthiophene, and 2-
    propionylthiophene are shown in Figures 42-45 respectively
    with the corresponding sample spectra.  The two terpenes had
    previously been  confirmed by GC-MS but the two thiophene
    isomers were confirmed only by GC-IR.
                                    81
    

    -------
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    -------
                               Cm ~'x 10 ~2
                                               I I
    Figure 41   GC-IR spectra of peaks a-e; sample point 4
                with inset of the corresponding portion of
                the gas chromatogram
                               87
    

    -------
    00
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                        3500       3000       2500
                                                  2000
    
                                                 Cm -I
                                                           1500       1000
        Figure 42    GC-IR spectrum of camphor  and corresponding GC-IR spectrum from
                     sample peak
    

    -------
    00
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                                 3000
                                         2500
                                                  2000
                                                  -I
         Figure 43    GC-IR spectrum of borneol  and corresponding  GC-IR spectrum from
                      sample peak
    

    -------
    
                                       2-ACETYLTHIOPHENE
                               _1_
                                          GKR-3
    
                                          PKN-19
                     3500       3000       2500       2000       1500       1000
    
                                               Dm -'
    Figure 44    GC-IR  spectrum of 2-acetylthiophene  and corresponding GC-IR
                  spectrum from  sample peak
    

    -------
                 '3500
                           3000
                                    2500
                                             2000
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    Figure 45
    GC-IR spectrum of 2-propionylthlophene and  corresponding GC-IR
    spectrum  from sample peak
    

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                             SECTION VII
    
                             REFERENCES
    1.   Keith, L. H.  Identification of Organic Contaminants
         Remaining in a Treated Kraft Paper Mill Effluent.
         Southeast Environmental Research Laboratory.
         )Presented at the 157th National Meeting of the
         American Chemical Society, Division of Water, Air, and
         Waste Chemistry.  April 14-18r 1969.)  6 p.
    
    2.   Keith, L. H., A. W. Garrison, M. M. Walker, A. L.
         Alford, and A. D. Thruston, Jr.  The Role of Nuclear
         Magnetic Resonance Spectroscopy and Mass Spectrometry
         in Water Pollution Analysis.  Southeast Environmental
         Research Laboratory.  (Presented at the 158th National
         Meeting of the American Chemical Society, Division of
         Water, Air, and Waste Chemistry.  New York.  September
         8-12, 1969.)  4 p.
    
    3.   Garrison, A. W., L. H. Keith, and M. M. Walker.  The
         Use of Mass Spectrometry in the Identification of
         Organic Contaminants in Water from the Kraft Paper Mill
         Industry.  Southeast Environmental Research Laboratory.
         (Presented at the 18th Annual Conference on Mass
         Spectrometry and Allied Topics.  San Francisco.  June
         14-19, 1970.)  9 p.
    
    4.   Keith, L. H. , arid S. H.  Hercules.  Environmental
         Applications of Advanced Instrumental Analyses:
         Assistance Projects, FY 69-71.  Environmental
         Protection Agency.  Washington, D.C.  Publication
         Number EPA-R2-73-155.  May 1974.  p. 50-63.
    
    5.   Alford, A. L.  Environmental Applications of Advanced
         Instrumental Analyses:  Assistance Projects, FY 72.
         Environmental Protection Agency.  Washington, D.C.
         Publication Number EPA-660/2-73-013.  September 1973.
         p. 27-31.
    
    6.   Adams, B. H., H. C. Vick, R. P- Lawless, T. B. Bennett,
         Jr., W. Hanks, and J. Shailer.  Supplement to Effects
         of Pollution on Water Quality, Perdido River and Bay,
         Alabama and Florida.  Environmental Protection Agency,
         Southeast Water Laboratory Technical Service Program,
         Athens, Georgia.   (1971).  p. 14-17.
    
    7.   Hill, J. S., and B. H. Adams.  Wastewater Survey St.
         Regis Paper Company, Cantonment, Florida.  Environmental
         Protection Agency,
    
    
                                 92
    

    -------
         Surveillance and Analysis Division, Athens, Georgia,
         (1972).  p. 29-30.
    
    8.   Private communication with Mr. Lawrence Wapensky, EPA,
         Denver Federal Center, Denver, Colorado (1973).
    
    9.   Webb,  R. G., A. W. Garrison, L. H. Keith, and J. M.
         McGuire.  Current Practice in GC-MS Analysis of
         Organics in Water.  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-R2-73-277.
         August 1973.  p. 48-54.
    
    10.  Davis, C. L.  Color Removal from Kraft Pulping Effluent
         by Lime Addition.  Environmental Protection Agency.
         Washington, D.C.  Publication Number 12040 ENC.
         December 1971.  p. iii.
    
    11.  Environmental Protection Agency Technology.  Color
         Removal from Kraft Pulping Effluent by Lime Addition.
         Technology Transfer Capsule Report 2.
    
    12.  Dostal, K. A., R. C. Peerson, D. G. Hager, and G. G.
         Robeck.  Carbon Bed Design Criteria Study at Nitro, W.
         Va.  J. Am. Water Works Assoc. 57;  663-674, 1965.
    
    13.  Bishop, D. F., L. S. Marshall, T. P. O'Farrell, R. B.
         Dean,  B. ©•Connor, R. A. Dobbs, S. H. Griggs, and R. V.
         Villiers.  Studies on Activated carbon Treatment.  J.
         Water Poll.  Contr. Fed.  39:  188-203, 1967.
    
    14.  Booth, R. L., J. N. English, and G. N. McDermott.
         Evaluation of Sampling conditions in the Carbon
         Adsorption Method.  J. Am. Water Works Assoc.  57:
         215-220, 1965.
    
    15.  Webb,  R. G., A. W. Garrison, L. H. Keith, and J. M.
         McGuire.  Current Practice in GC-MS Analysis of
         Organics in Water.  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-R2-73-277.
         August 1973.  p. 88.
    
    16.  Webb,  R. G., A. W. Garrison, L. H. Keith, and J. M.
         McGuire.  Current Practice in GC-MS Analysis of
         Organics in Water.  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-R2-73-277.
         August 1973. p. 90.
    
    17.  Bicho, J. G., E. Zavarin, and D. L. Brink.  Oxidative
         Degradation of Wood II.  TAPPI.  49:  218-226, 1966.
                                    93
    

    -------
    18.   Brink, D. L., Y. T. Wu, H. P. Noveau, J. G. Bicho, and
         M. M. Merriman.  Oxidative Degradation of Wood IV.
         TAPPI.  55:  719-721, 1972.
    
    19.   McGuire, J. M., A. L. Alford, and M. H. Carter.
         Organic Pollutant Identification Utilizing Mass
         Spectrometry-  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-R2-73-234.
         July 1973.  p. 10-13.
    20.  Hoyland, J. R., and M, B. Neher.  Implementation of a
         Computer-Based Information System for Mass Spectral
         Identification.  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-660/2-74-048.
         June 1974.  p. 5-33.
    
    21.  Ryhag, R., and E. Stenhagen.  Mass Spectrometry of
         Long-Chain Esters.  In: Mass Spectrometry of Organic
         Ions.  McLafferty, F. W.  (ed.).  New York, Academic
         Press, 1963.  Chapter 9, p. 399-443.
    
    22.  Hertz, H. S., R. A. Kites, and K. Biemann. Anal. Chem.
         43:  681, 1971.
    
    23.  Hoyland, J. R., and M. B. Neher.  Implementation of a
         Computer-Based Information System for Mass Spectral
         Identification.  Environmental Protection Agency.
         Washington, D.C.  Publication Number EPA-660/2-74-048.
         June 1974.  p. 1.
    
    24.  Mutton, D. B. Wood Resin.  In: Wood Extractives and
         Their Significance to the Pulp and Paper Industries.
         Hillis, W. E.  (ed.)  New York, Academic Press, 1962.
         Chapter 10.  p. 331-360.
    
    25.  Holmbom, B., and E. Avela.  Studies on Tall oil From
         Pine and Birch.  Acta Academiae Aboensis.  Ser. B. 31_;
         (13):  1-14, 1971.
    
    26.  McKee, J. E., and H. W. Wolfe.  Water Quality Criteria.
         California State Water Resources Control Board.
         Sacramento.  Publication Number 3-A.  Second Edition.
         1963.  p. 187.
    
    27.  Leach, J. M., and A. N. Thakore.  Identification of the
         constituents of Kraft Pulping Effluent That Are Toxic
         to Juvenil Coho Salmon.  J. Fish. Research Brd.
         Canada.  30:  479,  1973.
                                    94
    

    -------
    28.   Odham, G. , and E. Stenhagen.  Fatty Acids.  In:
         Biochemical Applications of Mass Spectrometry, Waller,
         G. (ed.).  New York, Wiley-Interscience,  1972.  Chapter
         8.  p. 211-228.
    
    29.   Rogers, I. H.  Secondary Treatment of Kraft Mill
         Effluents:  Isolation and Identification of Fish-Toxic
         Compounds and Their Sublethal Effects.  Pulp and Paper
         Magazine of Canada.  74:  T303-T308, 1973.
    
    30.   Van Horn, W. M., J. B. Anderson, and M. Katz.  The
         Effect of Kraft Paper Mill Waters on Fish Life.  Tappi.
         33:  209-212, 1950.
    
    31.   Maenpaa, R., P. Hynninen, and J. Tikka.  On the
         Occurrence of Abietic and Pimaric Acid Type Resin Acids
         in the Effluents of Sulphite and Sulphate Pulp Mills.
         Pap.  ja pun.  50:  143-150, 1968.
    
    32.   Hagman, N.  Resin Acids in Fish Mortality.  Finnish
         Paper and Timber J. .18:  32-34, 40-41, 1938.
    
    33.   Ebeling, G.  Recent Results of the Chemical
         Investigation of the Effect of Wastewaters from
         Cellulose Plants on Fish.  Vom Wasser.  5:  192-200,
         1931.  (C. A. 36:  2262).
    
    34.   Leach, J. M., and A. N. Thakore.  Identification of the
         Constituents of Kraft Pulping Effluent That Are Toxic
         to Juvenile Coho Salmon (Oncorkynchus kisutch).  J.
         Fisheries Res. Brd. Canada.  30:  479-484, 1973.
    
    35.   Zinkel, D. F., L. C. Zank, and M. F. Wesolowski.
         Diterpene Resin Acids.  U. S. Department of
         Agriculture.  Forest Service.  Madison, Wise. Forest
         Products Laboratory.  Washington, B.C.  1971.  p. C1-
         C32.
    
    36.   Chang, T., T. E. Mead, and D. F. Ziabel.  Mass Spectra
         of Diterpene Resin Acid Methyl Esters.  J. Am. Oil
         Chem.  Soc.  48:  455-461, 1971.
    
    37.   Chopin, J.  Phenolic Substances in Pulp Mill Effluents.
         J. Bull. Ass. Tech. Ind. Pap., No. 3; 147-155, 1959.
    
    38.   McKee, J. E., and H. W. Wolf.  Water Quality Criteria.
         California State Water Resources Control  Board.
         Sacramento.  Publication Number 3-A.  Second Edition.
         1963.  p. 238.
                                    95
    

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    39.  Shumway, D. L., and J. R. Palensky.  Impairment of the
         Flavor of Fish by Water Pollutants.  Environmental
         Protection Agency.  Washington, B.C.  Publication
         Number EPA-R3-73-010.  February 1973. p. 68-69.
    
    40.  Shumway, D. C.r and G. G. Chadwick.  Influence of Kraft
         Mill Effluent on the Flavor of Salmon Flesh.  Wat. Res.
         5:  997-1003, 1971.
    
    41.  Rogers, I. H., and L. H. Keith.  Organochlorine
         Compounds in Kraft Bleaching Wastes.  Identification of
         Two Chlorinated Guaiacols.  Environment Canada,
         Fisheries and Marine Service Technical Report Number
         465.  September 1974.  p. 8-17.
    
    42.  Hrutfiord, B. J.  Organic Compounds in Pulp Mill Lagoon
         Discharge.  Environmental Protection Agency
         Publication.  In Press.
                                    96
    

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                            SECTION VIII
    
    
    
                             APPENDICES
    
    
    
    
    
    
    
    
                                                          £§36
    
    
    
    
    A.   Procedure for diazomethane methylation            98
    
    
    
    
    B.   Procedure for dimethyl sulfate methylation        99
                                    97
    

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                             APPENDIX A
    
               Procedure for diazomethane methylation
    
    
    The apparatus is shown in Figure 6.
    
    1.   Evaporate the sample extract just to dryness with a
         stream of nitrogen in a centrifuge tube, the bottom
         tube of a Kuderna-Danish apparatus, or the sample
         storage vial.  A small amount of methylene chloride may
         be retained, but the presence of chloroform may produce
         artifacts.  Dissolve the extract in 0.5-1.0 ml
         distilled-in-glass ethyl ether.
    
    2.   Add about 5 ml of distilled-in-glass ether to the first
         tube of the apparatus to saturate the nitrogen carrier
         gas with ether.  Add 0.7 ml of carbitol [2-(2-
         ethoxyethoxy)ethanol], 1.0 ml of 31% aqueous KOH (not
         over 2 days old), and 0.1-0.2 g of N-methyl-N-nitroso-
         p-toluenesulfonamide ("Diazald," Aldrich Chemical Co.)
         to the second tube.  The base immediately begins to
         release diazomethane from the sulfonamide.
    
    3.   Immediately position the second test tube and adjust
         the nitrogen flow to about 10 ml per minute.   Caution;
         Diazomethane is an extremely toxic and explosive gas.
         A good fume hood and safety glasses are mandatory.   No
         chipped glassware should be used, as rough glass
         surfaces catalyze decomposition of diazomethane.
    
    4.   Position the third tube (a safety trap to prevent
         reagent carry-over) and the sample tube to bubble the
         nitrogen and diazomethane gas mixture through the
         sample.  Continue the reaction until the slight yellow
         color of diazomethane persists in the sample solution
         (from a few seconds to 30 minutes, depending upon the
         sample concentration).  In the case of dark colored
         extracts in which the diazomethane is not visible,  a
         reaction time of 30 minutes is recommended.
    
    5.   Allow the esterified sample to stand unstoppered in the
         hood for 15 to 30 minutes to allow excess diazomethane
         to escape from the ether solution.  Discard all waste
         from the reaction with care and rinse the apparatus
         with acetone.  Evaporate the sample to the volume
         necessary for gas chromatography.
                                    98
    

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                             APPENDIX B
    
             Procedure for dimethyl sulfate methylation
    
    
    The apparatus is shown in Figure  7.
    
    1.   Bring the original sample (300 ml)  to pH 11  with NaOH
         and extract with chloroform to remove neutral and basic
         compounds.
    
    2.   A 500-ml 3-neck (standard taper 24/40)  round bottom
         flask, equipped with a fourth neck for a thermometer,
         is fitted with two pressure-equalizing addition
         funnels, the probe of a single-probe pH meter, and a
         magnetic stirrer.
    
    3.   Nitrogen is introduced into the top of the first
         addition funnel and exits from the top of the second
         one.  Place forty ml of Eastman reagent grade dimethyl
         sulfate into the first addition funnel and a SOX
         solution of sodium hydroxide (80 ml)  into the second.
    
    4.   Pour the sample into the flask and flush the system
         with nitrogen.
    
    5.   After raising the temperature to 85° C, begin dropwise
         addition of both the dimethylsulfate and the sodium
         hydroxide solution.  Maintain temperature between 80
         and 90° C.   (Caution—exothermic reaction.  Have ice
         available to add to water bath.) and the pH between
         10.5 and 11.  Since dimethylsulfate is not readily
         soluble in water vigorous stirring must be used.  The
         addition time is about 1 hour.
    
    6.   After all the dimethylsulfate is added, maintain the
         reaction vessel at 85-90° C for an additional 15-20
         minutes and then cool to room temperature.
    
    7.   Add 5 ml concentrated ammonium hydroxide to destroy
         excess dimethylsulfate and re-extract the reaction
         mixture with chloroform to remove the methyl esters of
         acids and the methyl ethers of phenols.
    
    8.   Dry the chloroform extract and evaporate to the
         appropriate volume for GC analysis.
                                    99
    

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                                 TECHNICAL REPORT DATA    .
                           (Please read Instructions on the reverse before completing)
     REPORT NO.
      EPA-660/4-75-005
                                                      3. RECIPIENT'S ACCESSION-NO.
    4. TITLE AND SUBTITLE
     Analysis  of Organic Compounds in Two Kraft
     Mill Wastewaters
                                       B. REPORT DATE
                                        April,  1975
                                       6. PERFORMING ORGANIZATION CODE
    7. AUTHOR(S)
     Lawrence  H.  Keith
                                                      8. PERFORMING ORGANIZATION REPORT NO.
    9. PERFORMING ORG \NIZATION NAME AND ADDRESS
     Analytical Chemistry Branch
     Southeast  Environmental  Research Laboratory
     Athens, GA   30601
                                       10. PROGRAM ELEMENT NO.
                                         1BA027
                                       11. CONTRACT/GRANT NO.
    12. SPONSORING AGENCV NAME AND ADDRESS
     Environmental Protection  Agency
     Southeast  Environmental Research Laboratory
     College  Station Road
                                       13. TYPE OF REPORT AND PERIOD COVERED
                                         Final, FY67-74	
                                       14. SPONSORING AGENCY CODE
     Athens,  GA
    30601
    15. SUPPLEMENTARY NOTES
     Prepared  in fulfillment of  ROAP 07ABL-Tasks  02,  03
    16. ABSTRACT
     Wastewaters  from two kraft  paper mills in Georgia were sampled at
     various points in the waste treatment systems.   Gas chromatography of
     the organic  extracts and identification of many of the specific chemical
     components by gas chromatography-mass spectrometry provided  a  "chemical
     profile"  of  the effluents.   The mills, in different geographical
     locations, have very similar raw wastewater  compositions but different
     wastewater treatments.  In  spite of these differences, the treated
     effluents are qualitatively similar in composition although  the
     quantities of the various components differ.  After two years  the raw
     and treated  effluents of both mills were re-sampled.  Analyses showed
     that although concentrations of the organics  varied, the same  compounds
     are still present.  This report was submitted in ^fulfillment of ROAP
     07ABL, Tasks 02 and 03 by SERL, Athens, Georgia.  Work was completed as
     of April  1974.
    17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                   DESCRIPTORS
                                           b.lDENTIFIERS/OPEN ENDED TERMS
                                                   c. cos AT I Field/Group
     Pollutant identification*
     Mass spectrometry*
     Gas chromatography*
     Organic compounds*
     Water pollution sources*
                             paper mill  pollution
                             infrared  spectroscop
                             fatty acids
                             resin acids
                             phenols
    18. DISTRIBUTION STATEMENT
    
     Release Unlimited
                            19. SECURITY CLASS (ThisReport)'
    21. NO. OF PAGES
    
       109
                                           20. SECURITY CLASS (Thispage)
                                                                  22. PRICE
    EPA Form 2220-1 (9-73)
                             ft U. S. GOVERNMENT PRINTING OFFICE: 1975-699,183 /32 REGION 10
    

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