United States Office of Water Regulations EPA-440/1 -88-025 K
Environmental Protection anc| Standards TWH-552) March 1988
Agency Washington, DC 20460
U.S. EPA/Paper Industry
Cooperative Dioxin Screening
Study
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U. S. ENVIRONMENTAL PROTECTION AGENCY/PAPER INDUSTRY
COOPERATIVE DIOXIN SCREENING STUDY
MARCH 1938
U. S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF WATER
OFFICE OF WATER REGULATIONS AND STANDARDS
WASHINGTON, D.C. 20460
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12Ul Floor
Chicago. IL 60604^3590
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ACKNOWLEDGMENTS
Alexander C. McBride was USEPA's project director for this
study and Gary A. Amendola was USEPA's project manager. Russell 0.
Blosser, NCASI, was the project manager for the paper industry.
The principal authors of this report were Gary A. Amendola,
USEPA, and Raymond C. Whittemore, Ph.D., NCASI. Francis Thomas,
USEPA, and Lawrence E. LaFleur, NCASI, served as quality assurance
officers. Analysis of samples for 2,3,7,8-tetrachlorodibenzo-p-
dioxin and 2 , 3,7,8-tetrachlorodibenzofuran were conducted at the
Brehm Laboratory, Wright State University, Dayton, Ohio, under the
direction of Thomas 0. Tiernan, Ph.D. Analysis of samples for
selected chlorinated phenolics were conducted at the NCASI West
Coast Regional Center, Corvallis, Oregon, under the direction of
Lawrence E. LaFleur.
The authors acknowledge the contributions of the following
people who participated in the conduct of the field studies:
David R. Barna, Jonathan L. Barney, Danforth G. Bodien, Daniel S.
Granz, David A. Parrish, and Raymond E. Thompson, USEPA; Andre L.
Caron, James J. McKeown, and Steven Norton, NCASI; and the many
other people from participating paper companies, state pollution
control agencies, and USEPA, whose assistance was essential for
the successful completion of this project. The authors also
acknowledge the assistance of the Michigan Division of Dow Chemical
U.S.A. in conducting analyses of polychlorinated dibenzo-p-
dioxins and polychlorinated dibenzofurans for selected samples.
Ms. Carol Kopcak, USEPA, typed this report.
Finally, the authors acknowledge the efforts and contributions
of Russell 0. Blosser, senior vice president, NCASI, who provided
guidance and direction throughout the conduct of this study.
DISCLAIMER
This document has been reviewed in accordance with U.S.
Environmental Protection Agency policy and approved for publica-
tion. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
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EXECUTIVE SUMMARY
As a result of the National Dioxin Study findings of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (2378-TCDD) in native fish collected
downstream from a number of pulp and paper mills and subsequent
findings of 2378-TCDD in bleached kraft pulp and paper mill
wastewater sludges, the United States Environmental Protection
Agency (USEPA) planned a detailed process evaluation study at one
mill. Through subsequent discussions with the paper industry,
USEPA and the industry agreed in June 1986 to conduct a cooperative
screening study of five bleached kraft pulp and paper mills on a
shared resource basis. Three mills were selected on the basis of
known 2378-TCDD levels in sludges and two mills were volunteered
by their parent companies to attain the geographical diversity
desired for the study. The selection of the five mills, which
represent about 6 percent of the bleached kraft mills in the
United States, was not intended to characterize the entire
industry. The principal objectives of the study were:
1. Determine, if present, the source or sources of 2378-TCDD
and other polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs) at five bleached
kraft pulp and paper mills; and
2. Quantify the untreated wastewater discharge loadings, final
effluent discharge loadings, sludge concentrations, and
wastewater treatment system efficiency for 2378-TCDD and
other PCDDs and PCDFs.
Field work for the five-mill study was conducted during the
period June 1986-January 1987 through the combined efforts of four
USEPA regional offices, five state environmental control agencies,
the National Council of the Paper Industry for Air and Stream
Improvement, Inc. (NCASI), and the participating paper companies.
The analytical methods development program and analyses of samples
for selected PCDDs and PCDFs were conducted at the Brehm Laboratory,
Wright State University. Selected samples were analyzed for
certain chlorinated phenolics by NCASI.
This report is limited to presentation of the complete data
and the scientific and technical findings resulting from the
cooperative study. Consideration of public and occupational
health, environmental, consumer product, and regulatory issues
that may be associated with study findings is beyond the scope of
this report. Additional research is being planned and implemented
by both government and industry to deal with such issues.
111
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To accomplish the first study objective, it was necessary to
design a general comprehensive study plan of all major and minor
mill inputs, intermediates, and mill exports. The general plan
was modified as necessary to conform to the specific circumstances
of each mill. Because chlorine and chlorine derivatives are
first introduced in substantial quantities in the bleaching
process, emphasis was placed on detailed process sampling in
bleacheries .
The principal mill exports sampled were bleached pulps,
treated process wastewater effluents, and wastewater sludges
dewatered for disposal. Although bleached pulps are converted
into paper products at each mill, bleached pulps were considered
mill exports for purposes of this study. This eliminated the
need to sample and quantify mass outputs of numerous paper machines
which were not always related to bleachery operations during
field sampling.
The second objective was addressed by sampling combined
untreated wastewaters, intermediate and final wastewater sludges,
and treated process wastewater effluents. Evaluation of noncontact
cooling waters and possible atmospheric emissions were not included
in the study design.
Initially, the analytical program required, where possible, for
each sample, isomer-specific analyses of tetrachloro dibenzo-p-
dioxins (TCDDs) and tetrachlorodibenzofurans (TCDFs) and, where
possible, for selected samples,, isomer-speci f ic analyses of 2378-
substituted penta- through hepta- CDDs and CDFs, and OCDD and
OCDF. However, based upon anal/ses of a limited number of prelimi-
nary samples and a limited number of USEPA analyses of samples
from other mills, the scope of the analytical program was reduced.
The preliminary analyses indicate that 2378-TCDD and 2378-TCDF are
the principal PCDDs and PCDFs found in the pulp and paper mill
matrices, particularly when considered in light of USEPA's 2378-
TCDD toxicity equivalents approach. Accordingly, all samples
were analyzed for 2378-TCDD a nd 2378-TCDF, since the extensive
analytical methods development work required for isomer-specifie
analyses of the other compounds did not appear warranted.
Specific findings and observations from this study are
summarized in the sections thcit follow. They are grouped in a
manner similar to the organization of the report.
Data Quality and Data Limitations
1. The analytical protocol for 2378-TCDD and 2378-TCDF developed
for this study was found to be satisfactory for isomer-specific
determinations of 2378-TCDD and 2378-TCDF in selected pulp and
paper mill sample matrices. Intra-laboratory method validation
experiments for pulp, sludge, and wastewater effluent samples
IV
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indicate the performance of the analytical method with respect to
precision and spike recovery is demonstrably uniform. The method
performance does not appear to be sensitive to any specific
matrix or chemical effects which might be associated with the
manufacturing processes at a given mill. Limited inter-laboratory
comparisons incorporating different sample preparation, analytical
methods, and calibration standards confirmed the presence of
2378-TCDD and 2378-TCDF in selected samples. However, a consistent
bias was observed for quantitation of both 2378-TCDD and 2378-TCDF.
2. With few exceptions, the data quality assurance objectives
established for this study for 2378-TCDD and 2378-TCDF were
achieved.
(a) Laboratory precision expressed as relative percent differ-
ence between duplicate analyses for thirty-five 2378-TCDD
determinations was 15 percent mean (range 1-138 percent);
and for thirty-three 2378-TCDF determinations, 16 percent
mean (range 0-62 percent).
(b) Field precision for eight 2378-TCDD determinations was
14 percent mean (range 4-19 percent); and for nine 2378-
TCDF determinations, 22 percent mean (range 0-99 percent).
(c) For thirty-five 2378-TCDD determinations, accuracy ex-
pressed as percent spike recovery was 103 percent mean
(range 66-168 percent); and for thirty-five 2378-TCDF
determinations, 102 percent mean (range 58-153 percent).
(d) Including results from intra-laboratory method validation
experiments, 97 percent of the analyses met the quality
assurance objectives for laboratory precision and accu-
racy. Ninty-five percent of 133 determinations for
2378-TCDD and for 2378-TCDF resulted in analytical data
suitable for project objectives.
(e) Target analytical detection levels of 1 ppt for solid
samples were achieved for all but one sample for 2378-TCDD
and all but one sample for 2378-TCDF (different samples) .
Target analytical detection levels of 0.01 ppt for liquid
samples were achieved for all but three samples for 2378-
TCDD, and all but two samples for 2378-TCDF (different
samples) .
3. Mass flow calculations for 2378-TCDD and 2378-TCDF combine
analytical results with mass flow rates of solid materials (pulps,
sludges) and liquids (waters, wastewaters) . The mass flow rates
for pulps and final treated wastewater effluents are considered
to be accurate within less than ±10 percent while mass flow
rates for sludges, within less than ±10 percent to 15 percent.
Mass flow rates for internal plant wastewaters were generally based
upon best engineering estimates and are considered accurate to
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less than ±20 percent to 25 percent. The reliability of reported
bleach plant chemical application rates varied considerably from
mill to mill, and in two cases were best engineering estimates.
Non-detect analyses were treated as zero for mass balance calcula-
tions. The calculations and analyses presented in this report
should be viewed accordingly.
PCDDs and PCDFs Found in Pulp and Paper Mill Matrices
1. Analyses of polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs) from samples obtained at a
number of bleached kraft pulp and paper mills processing primarily
virgin fiber uniformly show that 2,3,7,8-tetrachlorodibenzo-p-
dioxin (2378-TCDD) and 2, 3,1,8-tetrachlorodibenzofuran (2378-TCDF)
are the principal PCDDs and PCDFs found. This is particularly
evident when the data are considered in light of USEPA's 2378-TCDD
toxic equivalents approach for dealing with mixtures of PCDDs and
PCDFs.
2. Data for the five mills included in this study show there is a
characteristic 2378-TCDF/2378-TCDD ratio associated with indi-
vidual bleach lines and individual mills, ranging from about 2 to
about 18. This observation suggests that once 2378-TCDD and
2378-TCDF are formed, they are not altered in further processing
or in wastewater treatment. Factors accounting for the differences
in 2378-TCDF/2378-TCDD ratios across bleach lines and across
mills have not been determined, nor has the possible process
significance been formulated.
Sources of 2378--TCDD and 2378-TCDF
1. 2378-TCDD and 2378-TCDF are formed during the bleaching of
kraft hardwood and softwood palps with chlorine and chlorine
derivatives at mills included in this study.
2. 2378-TCDD was not detected in seven unbleached kraft pulps
collected at the five mills at detection levels ranging from 0.3
ppt to 1.0 ppt. 2378-TCDF was? not detected in four of seven
unbleached pulps at detection levels less than 0.3 ppt, but was
found in three pulps collected at two mills at levels ranging from
1.1 to 2.3 ppt. The positive 2378-TCDF findings in unbleached
pulps may be attributed to reuse of contaminated paper machine
white waters for brownstock pulp washing or dilution.
3. 2378-TCDD was found in seven of nine bleached pulps collected
at the five mills at concentrations ranging from 3 to 51 ppt and
2378-TCDF was found in eight of nine bleached pulps at levels
ranging from 8 to 330 ppt. The median and mean concentrations
are presented below:
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2378-TCDD 2378-TCDF
Median 5 ppt 50 ppt
Mean 13 ppt 93 ppt
4. 2378-TCDD and 2378-TCDF were found in most untreated bleach
line filtrates sampled from the five mills. Wastewaters from
caustic extraction stages (E and E0) generally contained the
highest concentrations and mass discharges from the bleach lines
sampled.
5. The distributions of 2378-TCDD and 2378-TCDF in bleach line
exports (bleached pulp and bleach plant wastewaters) were found
to be highly variable from bleach line to bleach line. However,
2378-TCDD and 2378-TCDF were partitioned similarly to bleached
pulps and bleach plant wastewaters within each bleach line.
6. 2378-TCDD was found in paper machine wastewaters from three of
five mills and 2378-TCDF was found in paper machine wastewaters
from each mill. The levels of 2378-TCDD and 2378-TCDF found in
paper machine wastewaters were significantly less than found in
the respective bleach plant wastewaters at four of five mills.
7. 2378-TCDD was found in one of five sludge landfill leachate or
runoff samples at 0.025 ppt, while 2378-TCDF was found in four of
five samples at levels ranging from 0.01 to 0.11 ppt. 2378-TCDD
and 2378-TCDF were not detected in coal-fired power boiler ash
samples from two mills at detection levels less than 1.0 ppt.
8. 2378-TCDD and other TCDDs were found in a sample of blue dye
collected during preliminary sampling at one mill at levels of
3.4 and 53 ppt, respectively.
Formation of 2378-TCDD and 2378-TCDF
1. The rates of formation of 2378-TCDD and 2378-TCDF normalized
to Ibs/ton (kg/kkg) of air dried brownstock pulp are summarized
below:
10~8 Ibs/ton (kg/kkg) of Brownstock Pulp
Bleach Line Exports Total Mill Exports
2378-TCDD ^eight bleach lines) (five mills)
Range ND-20(10) 0.14(0.07)-11(5.5)
Median 4.1(2.0) 3.0(1.5)
Mean 8.0(4.0) 4.4(2.2)
2378-TCDF
Range 2.6(1.3)-360(180) 1.5 (0.75)-130(65)
Median 12.5(6.3) 19(9.5)
Mean 68 (34) 41(21)
VII
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The range computed from bleach line exports exceeds that
computed from total mill exports because of the integration of
results from mills with multiple bleach lines in the mill export
calculations. The extent to which these data are representative
of long-term operations at the five mills, or are representative
of the bleached kraft industry as a whole is not known.
2. Although the data from this study are limited, the results
suggest casual relationships between the formation of 2378-TCDD
and 2378-TCDF and (1) the degree of bleaching across bleach lines
as estimated by the chlorine and chlorine equivalents applied to
the unbleached pulp, and (2) the amount of lignin removed in the
pulp across chlorination and caustic extraction stages as estimated
by the difference in permanganate number (K) an,d CEK (permanganate
number after caustic extraction). Attempts were made to develop
statistical correlations with the limited data. However, the
results were generally poor.
3. Bleach lines processing exclusively softwood pulps had higher
rates of formation of 2378-TCDD and 2378-TCDF than bleach lines
processing exclusively hardwood pulps. However, bleaching condi-
tions on the softwood and hardwood bleach lines were different,
and thus, it is not possible to conclude that the general wood
species bleached is the determinant variable in formation of
2378-TCDD and 2378-TCDF.
Wastewater Treatment System Findings
1. 2378-TCDD was found in treated wastewater effluents from three
of five mills at levels ranging from 0.015 to 0.12 ppt and 2378-
TCDF was found in four of five effluents at levels from 0.011 to
2.2 ppt.
2. 2378-TCDD was found in wastwater treatment sludges collected
from each of the five mills at levels from 17 to 24 ppt (primary
sludges) , 11 to 710 ppt (secondary sludges) and 3.3 to 180 ppt
(combined sludges). 2378-TCDF was found at 32 to 380 ppt (primary
sludges), 75 to 10900 ppt (secondary sludges) and 34 to 760 ppt
(combined sludges).
3. Mass balance calculations around the wastewater treatment
systems for three mills showed that about 50 percent to 80 percent
of the 2378-TCDD and 40 percent to 60 percent of the 2378-TCDF
found in treatment system exports (treated effluent, wastewater
sludge) can be accounted for by treatment system inputs. For two
mills the treatment system input loadings exceeded the export
loadings by more than 200 percent. The poor mass balances are
attributed to uncertainties in sludge, influent, and effluent
flow rates, the sequencing of sampling at certain mills, and, to
some extent, analytical variability associated with trace level
analyses near method detection limits.
VI 1 1
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4. There is no evidence to suggest that 2378-TCDD and 2378-TCDF
are destroyed in wastewater treatment systems. Rather, they maybe
transferred, to varying degrees, to wastewater treatment sludges.
At two mills, about 10 percent to 15 percent of the 2378-TCDD and
2378-TCDF contained in untreated wastewater streams was transferred
to the sludges in the wastewater treatment systems, while at the
remaining three mills more than 80 percent transfer to sludges is
indicated. The precise distribution of these compounds in the
effluent between suspended solids and the liquid phase was not
determined in this study.
5. The distributions of 2378-TCDD and 2378-TCDF between wastewater
treatment exports (treated effluents and wastewater sludges) were
highly variable from mill to mill. However, the partitioning of
2378-TCDD and 2378-TCDF between treated effluents and wastewater
sludges was consistent within each mill. Mills with higher total
suspended solids in effluents had higher levels of 2378-TCDD and
2378-TCDF partitioned to the effluent rather than to the sludge.
Pulp and Paper Mill Exports
1. The distributions of 2378-TCDD and 2378-TCDF among pulp and
paper mill exports (bleached pulp, treated effluents, wastewater
sludges) were highly variable from mill to mill, but the parti-
tioning of 2378-TCDD and 2378-TCDF to the exports was consistent
within each mill.
2. Mass balance calculations indicate that bleach plant sources
accounted for about 90 percent to 140 percent of 2378-TCDD measured
in mill exports at three mills, and more than 300 percent at
another mill. 2378-TCDD was not detected in bleached pulp or
bleach plant wastewaters at one mill. For 2378-TCDF, bleach
plant sources were found to account for 70 to 130 percent of the
amount measured in mill exports at four mills, and more more than
300 percent in the last mill. The poor mass balance results at
some mills are attributed to uncertainties in mass flow rates of
wastewater, sludge, and pulp, and, to some extent, analytical
variability associated with trace level analyses near method
detection limits.
Chlorinated Phenolics
1. For this study, chlorina-ted phenolics include selected chlori-
nated phenols, chlorinated guaiacols, and chlorinated vanillins.
Chlorinated phenolics were formed in the bleaching process at
each of the five mills. These compounds were not detected in
treated intake process waters but were found in bleach plant
filtrates and wastewater treatment system influents and effluents.
Chlorinated phenolics were distributed differently at each mill.
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2. Wastewaters from caustic extraction stage (E and Eo) washers
accounted for most of the chlorinated phenolics. This finding is
similar to findings for 2378-TCDD and 2378-TCDF in bleach line
filtrates.
3. The amounts of chlorinated phenolics found in C-stage and
E-stage filtrates were normalized to Ibs/ton (kg/kkg) of air-
dried brownstock pulp and are summarized below:
10-3 Ibs/ton (kg/kkg) of Air-Dried Brownstock Pulp
Sum of C-Stage and
Sum of Chlorinated E-Stage Filtrates
Phenolics (eight bleach lines)
Range 9.3-54 (4.2-24)
Mean 35 (17)
Median 34 (17)
4. With the limited data available, correlations between the
presence of chlorinated phenolics and 2378-TCDD or 2378-TCDF in
wastewater treatment system influents or effluents were not
attempted. Because chlorinated phenolics were analyzed only for
the water matrix, an evaluation of total chlorinated phenolics
exports from bleach plants (i.,e., pulp and wastewaters) could
not be made. With the limited and incomplete wastewater data
available, mass balance calculations between internal bleach
plant filtrates and wastewater treatment system influents were
not attempted.
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USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
TABLE OF CONTENTS
EXECUTIVE SUMMARY ill
I. INTRODUCTION 1
II. STUDY DESIGN 3
III. THE FIVE BLEACHED KRAFT PULP AND PAPER MILLS 5
A. Mill A 5
B. Mill B 11
C. Mill C 15
D. Mill D 20
E. Mill E 25
IV. FIELD PROGRAM 30
A. Sampling Plan 30
B. Sample Collection, Sample Handling, and Sample Custody 32
C. Site-Specific Sampling 33
V. ANALYTICAL PROGRAM 35
A. PCDDs and PCDFs 35
1. Compounds Selected for Analysis 35
2. Preliminary Sanpling - March 1986 39
3. Analytical Methods for 2378-TCDD and 2378-TCDF 44
4. Identification and Quantitation of 2378-TCDD and 2378-TCDF 47
5. Intra-Laboratory Method Validation Experiments 48
6. Inter-Laboratory Method Comparison 54
B. Chlorinated Phenolics 55
C. Total Suspended Solids and Biochemical Oxygen Demand 55
VI. QUALITY ASSURANCE 56
A. 2378-TCDD and 2378-TCDF 56
1. Quality Assurance Objectives 56
2. Quality Assurance Results for 2378-TCDD and 2378-TCDF 58
B. Chlorinated Phenolics 62
XI
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TABLE OF CONTENTS (continued)
VII. RESULTS AND DISCUSSION
A. Observation on 2378-TCDF/2378-TCDD Ratio 65
B. Background Satiples 67
1. Treated Intake Process Water;; and Residuals 67
2. Kraft Pulping Process 70
C. Bleach Plant Findings 72
1. Bleach Plant Chemical Applications 72
2. Unbleached and Bleached Kraft Pulps -> 76
3. Bleach Plant Wastewaters 78
4. Distributions of 2378-TCDD and 2378-TCDF 87
5. Formation of 2378-TCDD and 2:!78-TCDF 89
D. Paper Machine Wastewaters, Utility Ashes, and Landfill Leachates 107
1. Paper Machine Wastewaters 107
2. Utility Ashes 107
3. Landfill Leachates 107
E. Wastewater Treatment System Findings 110
1. Influents to Wastewater Treatment 111
2. Wastewater Treatment Sludges 113
3. Treated Process Wastewater Effluents 113
4. Wastewater Treatment System Mass Balances 116
5. Distribution of 2378-TCDD and 2378-TCDF in Wastewater 119
Treatment System Effluents and Sludges
F. Pulp and Paper Mill Exports 120
G. Chlorinated Phenolics 127
H. Total Suspended Solids and Biochemical Oxygen Demand 131
VIII. FINDINGS AND CONCLUSIONS 134
A. Data Quality and Data Limitations 134
B. PCDDs and PCDFs Found in Pulp and Paper Mill Matrices 135
C. Sources of 2378-TCDD and 2378-TCDF 135
D. Formation of 2378-TCDD and 2378-TCDF 136
E. Wastewater Treatment System Findings 138
F. Pulp and Paper Mill Exports 139
G. Chlorinated Phenolics 139
REFERENCES 141
GLOSSARY 142
XII
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LIST OF ATTACHMENTS
A. USEPA/Paper Industry Cooperative Dioxin Screening Study;
June 1986, Amendment July 16, 1986.
B. USEPA/Paper Industry Cooperative Dioxin Screening Study;
Sampling Procedures, Sample Preservation, and Sample Handling.
C. Analytical Protocol for the Determination of 2,3,7,8-Tetra-
chlorodibenzo-P-Dioxin and 2,3,7,8-Tetrachlorodibenzofuran in
Paper Mill Process Samples (Woodchips and Paper Pulp) and
Paper Mill Effluents (Sludge, Ash, Mud, Treated and Untreated
Wastewater): Dioxin I Analyses; Wright State University,
Dayton, Ohio, June 1987.
D. NCASI Methods for the Analysis of Chlorinated Phenolics in Pulp
Industry Wastewaters; Technical Bulletin No. 498; July 1986;
Revised May 1987.
E. Analytical Results for 2378-TCDD and 2378-TCDF
(Master Sample Lists).
F. Mass Flow Rates of 2378-TCDD and 2378-TCDF.
G. Analytical Results for Chlorinated Phenolics, Total Suspended
Solids, and Biochemical Oxygen Demand.
Kill
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USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
I. INTRODUCTION
As a result of National Dioxin Study1 findings of 2,3,7,8-
tetrachlorodibenzo-p-dioxin (2378-TCDD) in native fish collected
downstream from a number of pulp and paper mills (levels from <5 to
85 parts per trillion (ppt)), and subsequent findings of 2378-TCDD
in bleached kraft pulp and paper mill wastewater sludges (levels
from <10 to 410 ppt), the United States Environmental Protection
Agency (USEPA) planned a detailed process evaluation study at one
mill. Through subsequent discussions with the paper industry,
USEPA and the industry agreed in June 1986 to conduct a cooperative
screening study of five bleached kraft pulp and paper mills on a
shared resource basis (Attachment A). Three mills were selected
on the basis of known 2378-TCDD levels in sludges and two mills
were volunteered by their parent companies to attain the geo-
graphical diversity desired for the study. The selection of the
five mills, which represent about 6 percent of the bleached kraft
mills in the United States, was not intended to characterize the
entire industry. The principal objectives of the study were:
1. Determine, if present, the source or sources of 2378-TCDD
and other polychlorinated dibenzo-p-dioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs) at five bleached
kraft pulp and paper mills; and
2. Quantify the untreated wastewater discharge loadings, final
effluent discharge loadings, sludge concentrations, and
wastewater treatment system efficiency for 2378-TCDD and
other PCDDs and PCDFs.
Field work for the five-mill study was conducted during the
period June 1986-January 1987 through the combined efforts of
four USEPA regional offices, five state environmental control
agencies, the National Council of the Paper Industry for Air and
Stream Improvement, Inc. (NCASI), and the participating paper
companies. The analytical methods development program and analyses
of samples for selected PCDDs and PCDFs were conducted at the
Brehm Laboratory, Wright State University. Selected samples were
analyzed for certain chlorinated phenolics by NCASI. Conventional
pollutants (total suspended solids (TSS) and five-day biochemical
oxygen demand (6005)) were determined for selected samples by mill
laboratories for three mills, by a USEPA laboratory for one mill,
and by a local water authority for the remaining mill.
-1-
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-2-
This report is limited to presentation of the complete data
and the scientific and technical findings resulting from the
cooperative study. Consideration of public and occupational
health, environmental, consumer product, and regulatory issues
that may be associated with study findings is beyond the scope of
this report. At this writing, additional research is being
planned and implemented by both government and industry to deal
with such issues.
-------
-3-
II. STUDY DESIGN
To accomplish the first study objective, it was necessary to
design a general comprehensive study plan of all major and minor
mill inputs, intermediates, and mill exports. The general plan
was modified as necessary to conform to the specific circumstances
of each mill. Because chlorine and chlorine derivatives are
first introduced in substantial quantities in the bleaching
process, emphasis was placed on detailed process sampling in
bleachecies. Mill inputs include wood chips, treated river
waters used for processing, and numerous process additives
including pulping chemicals, bleaching chemicals and paper mill
additives (clays, alums, dyes, slimicides, etc.). Intermediates
include river and well water supply treatment residuals, chemical
recovery muds, brown pulps, untreated process wastewaters, and
certain wastewater sludges. The principal mill exports include
bleached pulps, treated process wastewater effluents, and waste-
water sludges dewatered for disposal. Although bleached pulps
are converted into paper products at each mill studied, bleached
pulps were considered mill exports for purposes of this study.
This eliminated the need to sample and quantify mass outputs of
numerous paper machines which were not always related to bleachery
operations during field sampling. At some mills wastewater
sludge landfill leachates are also mill exports. They were
sampled but assumed to be minor sources compared to bleached
pulps, effluents, and sludges.
The second objective was addressed by sampling combined
untreated wastewaters, intermediate and final wastewater sludges,
and treated process wastewater effluents. Evaluation of noncontact
cooling waters and possible atmospheric emissions were not included
in the study design.
Initially, the analytical program required, where possible, for
each sample, isomer-specific analyses of tetrachloro dibenzo-p-
dioxins (TCDDs) and tetrachloro dibenzofurans (TCDFs) and, where
possible, for selected samples, isomer-specific analyses of 2378-
substituted penta- through hepta- CDDs and CDFs, and OCDD and
OCDF. However, based upon analysis of a limited number of
preliminary samples and a limited number of USEPA analyses of
samples from other mills, the scope of the analytical program was
reduced. The preliminary analyses indicate that 2378-TCDD and
2378-TCDF are the principal PCDDs and PCDFs found in the pulp and
paper mill matrices, particularly when considered in light of
USEPA's 2378-TCDD toxicity equivalents approach.2 Accordingly,
all samples were analyzed for 2378-TCDD and 2378-TCDF, since the
extensive analytical methods development work required for isotner-
specific analysis of the other compounds did not appear warranted.
-------
-4 -
A considerable effort was expended to develop the analytical
protocol used in this study for isomer-specific 2378-TCDD and
2378-TCDF determinations. The results from field, laboratory and
native spike duplicate, and native spike recovery experiments are
presented herein. Sample analyses were conducted on a priority
basis to minimize the total analytical burden. Limited experiments
were conducted to develop analytical methods for isomer-specific
determinations of 2378-substituted penta- through hepta- CDDs
and CDFs, and OCDD and OCDF., Limited inter-laboratory method
comparisons were conducted for four samples.
Selected samples were analyzed for chlorinated phenolics, total
suspended solids (TSS), and biochemical oxygen demand (8005).
The chlorinated phenolics analyses were conducted to determine
whether there is any relationship between the presence of those
compounds and the presence of PCDDs and PCDFs. The TSS and BOD5
analyses were conducted principally to determine whether there
were any abnormal wastewater treatment system operations during
the surveys.
-------
-5-
III. THE FIVE BLEACHED KRAFT PULP AND PAPER MILLS
A. Mill A
Mill A is an integrated bleached kraft mill with a capacity
of 580 tons per day of fine papers. Products include bond,
business forms, coating base, envelope, ledger, reprographic, and
tablet papers. Four batch digestors are used to pulp 400 tons
per day of hardwood and softwood chips with a typical mix of 70%
hardwood and 30% softwood. Pulping capacity exists for 365 tons
per day bleached kraft (400 tons per day unbleached kraft) .
The hardwood and softwood pulps are bleached separately in
three lines. The softwood line consists of a CEOH sequence while
the hardwood line is split following common C and Eo stages. One
hardwood line has a single H stage while the other consists of two
H stages followed by a peroxide (P) stage. All three bleaching
lines are schematically shown in Figures III-l and III-2. Sample
identification codes and flow rates at the time of sampling are
noted next to each sampling location. Nominal operating conditions
and chemical usages are listed in Table III-l. It is significant
to note that chlorine use at this mill was estimated from monthly
inventory reports.
(DE020901)
180 Tons/day
Air Dried
Eo
H
(DE020902)
160 Tons/Day
Air Dried
(DE020906)
1.73 mgd
a) Possible Over Flow to S1 Seal Box
b) Possible Over Flow to S2 Seal Box
(DE020907)
1.44 mgd
(DE020908)
0.68 mgd
FIGURE III-l. Mill A Softwood Bleaching Line Schematic
-------
-6-
(OE020803)
386 Ton«/d«y
Air Dried
C
( \
K6
(DE020904)
176 Ton«/d«y
Air Drl»d
(•) Poulbl* Ov*r Flow to K2 Seal Box
(b) PoHltal* Ov«r Flow to K4 3««l Bo«
(c) Po««lbl« Over Flow to K1 3<>l Box
(DE020909)
1.68 mgd
T
Ki
•v. 1
>
I
' •
h
\
*-
*
K
3
(OE0209I2)
0.34 y
Air Drl.d
FIGURE III-2. Mill A Hardwood Bleaching Line Schematic
The power boiler burns gas and approximately 350 tons per
day of bark to produce 650,000 Ibs of steam per hour. Fly ash from
the boiler is collected by electrostatic precipitation, combined
with the wastewater treatment plant sludge and disposed of in a
landfill. There is no contact of the boiler ash with the general
mill sewer.
Raw water to the mill is pumped from a nearby river, treated
with caustic, chlorine, alum, and mixed media filtration prior to
use in the mill. Residues from this treatment are sewered.
Approximately 20 MGD of treated process water are used. In
addition, another 5.0 MGD is used for noncontact cooling water on
the turbine condensers. A general schematic of the mill sewer
system is shown in 'Figure III-3. This figure provides identifi-
cation codes and flow rates associated with each sample location.
The measurements or estimates were the best available at the time
of sampling.
-------
-7-
TABLE III-l
MILL A BLEACH PLANT
Parameter
Softwood
Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
°2
NaOCl
Residual C12 (%C12)
Wet Brightness
Permanganate No.
Hardwood 1
*Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
02
NaOCl
Residual C12 (%C12)
Wet Brightness
Permanganate No.
Hardwood 2
*Throughput (BDT/day)
Residence Time (hours)
pH
Temperature (°F)
Chemical Usage (Ib/ton)
C12
NaOH
02
NaOCl
H202
Residual C12 (%C12)
Wet Brightness
Permanganate No.
OPERATING
C
w «
1
1.9
99
80
—
—
—
0.24
38.3
20.2
C
_ M
0.6
2.4
104
60
—
—
—
0.23
34
11.4
C
__
0.6
2.4
104
60
—
—
—
--
—
34
11.4
CONDITIONS
Bleachi
EO
— —
1.3
10.5
145
30
10-12
30
AND CHEMICAL USAGES
ng Stage
H H
184
1 1
9.0 8.4
95 95
*
— —
— —
110
1.1 0.85
55.5 77. 5-79. 5 79.0-81.0
2.5-3.0
EO
303
0.8
10.5
148
—
25.3
8
—
--
54
2.9
E0
303
0.8
10.5
148
—
25.3
8
—
__
—
54
2.9
_ — _ •_
H H
151.5
1.2 1.2
8.9
104
— __
— —
— —
70
1.1 0
79 79.5-80.5
_ — _ _
H H P
151.5
1.5 1.5 1.5
9.0 8.4 9.8
100 96 150
— — —
3.8
— — —
70
10
0.53 0.14 0.35(H202)
75.7 — 78.5-79.5
— — _ _ _ „
*303 BDT through Eo Stage, then split into two equal flows.
-------
-8-
River Water
Treated
Water
(T>E020801)
20 mgd
(DE020915)
Bleach Plant
7.6 mj|d
(DE020802)
(DE020803)
Raw Water Treatment
1.6 - 2 mgd
Evaporator
drain
0.5 mgd
To Waste Treatment
(DE020921)
20.1 mgd
(DE020806)
Pulping
3.6-4 mgd
(DE020807)
Recovery
0.17 mgd
Powerhouse
(DE0208J8)
0.6 mgd
(DE020811)
Paper machines
4.3 mgd
FIGURE III-3. Mill A Sewer System Schematic
The wastewater treatment (system consists of primary clarifi-
cation and oxygen activated sludge (UNOX) with 8.4 hours aeration
time. All mill wastewaters go to the primary clarifier with no
bypass. Combined primary and secondary sludge are dewatered with
belt filter presses prior to landfill disposal. The noncontact
cooling water mixes with the secondary effluent prior to river
discharge. The wastewater treatment plant schematic is shown in
Figure III-4. Identification codes and flow rates at the time of
sampling are noted next to each sampling location. Typical
operating conditions and performance are shown in Tables III-2
and III-3. These data reflect, average operating conditions for
both winter and summer months.
-------
-9-
Primary
Clarlfler
r.
(D
<
A ,
J-
r^
Primary
Sludge
E020920)
66 T/D
i
UNOX
Activated
Sludge
4 '
Secondary
Clarlfler
V-
Cooling water
16.2 mgd
) (DE020922) River
/ 23.2 mgd
Secondary Sludge
(DE020820) 7.2 T/day
. Fly ash
(DE020919) *0ven drled
20 T/D
Combined Sludge
(DE020920) -82.2 T/D
FIGURE III-4. Mill A Wastewater Treatment Plant Schematic
TABLE III-2
MILL A WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
Parameter
Flow (MGD)
Residence Time (days) .
Mixed Liquor Suspended Solids (mg/L)
Return Sludge Recycle (%)
Aeration Horsepower (HP/million gallons)
Value
21-25
0.5
3200
73
33
-------
-10-
TABL1S 111-3
MILL A WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter Winter Summer
BOD5 Loading (Ibs/day) 20,000 18,800
BOD5 Removal (%) 94 83
Suspended Solids Loading (Ibs/day) 18,800 20,700
Suspended Solids Removal (%) 68 58
Primary Sludge Production (tons/day) 55*
Consistency (%) unknown
Waste Activated Sludge Production (tons/day) 7.2*
Consistency (%) 1.6
Combined Dewatered
Sludge Production (dry tons/day) 59 65
Consistency (%) 37 39
*0ven dried basis
-------
-11-
B. Mill B
Mill B is an integrated bleached kraft mill with a capacity
for 875 tons per day of miscellaneous papers plus 150 tons per
day of market pulp. Major paper products include bond, facial
tissue, toilet tissue, napkin tissue, freezer paper, toweling, and
newsprint. Two continuous digestors (Kamyr , Bauer) are used to
pulp both hardwoods and softwoods with a typical mix of 20% hardwood
and 80% softwood. The bleached/semi-bleached kraft pulp capacity
is 775 tons per day with an additional 300 tons per day of pulp
generated by refiner mechanical groundwood. The latter is used
primarily for the newsprint production.
The bleach plant consists of a
sequence; however, during the survey,
CDEHHD sequence. The bleach plant
single line with a CEHED
the line was operated in a
The bleach plant is shown schematically in
Figure III-5. Sample identification codes and flow rates of both
pulp and washer filtrates are listed next to each sampling location.
Nominal operating conditions and chemical usages are listed in
Table III-4.
(86374611)
860 T/day
Air Dried
C
^
1 '
L E
>
*-!
<
\
^
(86374613)
6.06 mgd
^
1
i
»
- H
' (86374616) \
4
r
•
N
0.24
1
i
(86374616)
2.20 mgd
mgd
i
»
•
t
E
i
i
1
i
D
<86374617) i
1.36 mgd
r
i
>
(86374614
1.67 mgd
(86374612)
770 T/day
Air Dried
FIGURE III-5. Mill B Bleaching Line Schematic
-------
-12-
TABL:*: in-4
MILL B BLEACH PLANT OPERATING CONDITIONS AND CHEMICAL USAGES
Bleaching Stage
Parameter C E
H
Throughput (ADT/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
Cl2
NaOH
NaOCl (as available Cl2)
C102
Residual Cl2 (Ibs/ton)
Permanganate No.
Br ightness
100
3.5
19.8
58
4.5
34
Trace
59
D
34.5
0.23
—
102
34.5
0.70
10.2
150
34.5
0.15
9.1
150
34.5
0.08
--
150
34.5
2.80
2.1
150
61
10
Trace
83
The power boiler at the mill uses both gas and oil to produce
200,000 Ibs/hour of steam. There is no significant contact of
residues from this operation with the mill general sewer.
Raw water to the mill is taken from a nearby river, treated
with filtration, and chlorinated prior to use in the mill.
Approximately 40 MGD of treated water are used in the process.
Filter plant backwash from this process is returned to the river.
The general mill sewer is shown schematically in Figure III-6.
This figure provides identification codes and flow rates associated
with each sample location. These flow values represent measure-
ments or estimates where flow is not routinely monitored.
The wastewater treatment system consists of primary clarifi-
cation and a holding pond with 8 hours detention time. The pond
is followed by an activated sludge system with an additional
8 hours aeration time. The acid sewer from the bleach plant
bypasses primary treatment and is put directly into the holding
pond. Primary sludge is dewatered on a coil filter, while the
waste activated secondary -sludge is dewatered with a Winkle
press. Polymer is used as an aid in dewatering this sludge.
Primary sludge is landfilled on site while secondary sludge is
disposed off site. The wastewater treatment plant is shown
schematically in Figure III-7., Identification codes and flow
rates at the time of sampling are noted next to each sample
location. Typical operating conditions and performance during
both winter and summer months are shown in Tables III-5 and III-6.
-------
-13-
TABLE III-5
MILL B WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
Parameter Value
Flow (MGD) 40.8
Residence Time (days) 0.8-0.9
Mixed Liquor Suspended Solids (mg/L) 3100
Return Sludge Recycle (%) 97
Aeration Horsepower (HP/million gallons) 208
TABLE III-6
MILL B WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter Winter Summer
BOD5 Loading (Ibs/day) 55,000 55,000
BOD5 Removal (%) 93 94
Suspended Solids Loading (Ibs/day) 98,000 98,000
Suspended Solids Removal (%) 88 88
Primary Sludge Production (tons/day) 40 40
Consistency (%) 17 17
Secondary Sludge Production (tons/day) 3 15
Consistency (%) 13 13
-------
-14-
Backwash
(86374602)
1.3 mgd
i
*Proc
To P
River Water
1
/" N Treated V/ater
• / * — *-
L
>
To River
ess Sewer
rlmary Treati
• Artificial Sample of
untreated wastewater made
by combining this sewer
with Acid Sewer (C Stage
Effluent 86374613). New
sample number Is 86374644
C Stage effluent bypasses
primary.
J (86374601) "
37.1 mjjd
i
nent
\
A
Pulp
Dryer
<
E Stage
filtrate
(86374615)
2.2 mgd
Corrosive Sewer
Recaust
Evaporators
Refiner
(86374607)
3.1 mgd
r
k
^#1, #2 Paper machine
(86374621)
6.9 mgd
,(86374609)
21.3 mgd
^ 0
(2.2 mgd)
^#3, #4 Paper machine
* (4.7 mgd)
Brown Stock Effluent
(86374606)
10.8 mgd
FIGURE III-6. Mill B Sewer System Schematic
Primary
Clarlfler
Acid Sewer
(86374613)
6.05 mgd
31.3 mgd
Holding
Pond
AantlOfi
Pond
< Primary Sludge
(86374641)
36 T/day
Bone Dried
*(86374643 with polymer)
t
Effluent
-• >•
(86374646)
36.6 mgd
Secondary
Clarlflers
Secondary Sludge
(86374642)*
17 T/day
Bone Dried
(86374646)
Landfill Leachate
not added to
waste treatment
FIGURE III-7. Mill B Wastetwater Treatment Plant Schematic
-------
-15-
C. Mill C
Mill C is an integrated bleached kraft mill with a capacity
for 1170 tons per day of printing and writing papers. Products
include business form paper, carbonless copy paper, cover paper,
and tablet grade paper. Eight batch digesters are used to pulp
2200 tons per day of hardwood chips. Pulping capacity exists for
1000 tons per day of bleached kraft, although current production
is 800 tons per day.
The brownstock pulp is bleached with a single C/DEOD sequence.
The bleach plant is shown schematically in Figure III-8. Sample
identification codes and flow rates are noted next to each sampling
location. Nominal operating conditions and chemical usages are
listed in Table III-7.
(DE026002)
1004 Air Dried
Tone/day
C/D
Eo
(DE026003)
768 Air Dried
Tons/day
D
(DE026004)
2.96 mgd
T
(DE026006)
4.9 mgd*
(DE026006)
6.03 mgd*
Normally no discharge
FIGURE III-8. Mill C Bleaching Line Schematic
-------
-16-
TABLE III-7
MILL C BLEACH PLANT NOMINAL OPERATING CONDITIONS AND CHEMICAL USAGES
Bleaching Stage
Parameter C/D Eo D
Throughput (ADT/day) 1000
Residence Time (hours) 0.3 0.62 4.5
PH 1.7 11.5 4.0
Temperature (°F) 130 170 170
Chemical Usage (Ibs/ton)
C12 60
C102 5 -- 18
02 -- 12.5
NaOH — 20
Other (S02) -- -- 50
Residual C12 Trace
Brightness — 47 >88
Four power boilers are used to produce 1.3 million Ibs of
steam/hour. Three burn coal while the fourth burns wood wastes
(800 tons per day). Fly ash from the three coal boilers is
collected by electrostatic precipitators while ash from the wood
waste boiler is collected by a wet scrubber. All ash including
bottom ash is landfilled. Wastewater is used to convey some of
these ashes and is then sewered.
Raw water to the mill is supplied from two sources including
river water "and wells. Portions of the total (30 MGD) receive
treatment with either sand filtration or lime softening prior to
use in specific parts of the mill. Residues from both processes
are sewered. The general mill sewer system is shown schematically
in Figure III-9. Identification codes and flow rates for each
sample location are provided.
-------
-17-
I
o ^* ^ *••
s|lll
Scomza
*
1
— .
"S
E
T-
s
A
•o
i»:
c
„ Z
ts
*•— o
*R z
ov= 3 i- •
CM en o j • ^
CM . -r,-O CO 0
00 0 0 = «-5
•""sSw jo
U-.
I
c
«
*u
*
j>
'
U
cc
c
I1
"*]
t
V
r . ^
' i!
•^ ^ Q ^
o
o
•3L
a.
6
Z
r <
w>
CO
i
Z
CM
6
z
d
Ecx
*^
(4.0 mgd)
— 5 ~
o S ^>
co J E
0 | S
u a —
o 9
-.T" ' ' e>
** i, E
O
J f c~
« o 6 • —
I* I °*l
» 1 > 285
25 S s I S
So m co o u.
• 9
°!~
ta W
•g o E
r = 6
o2-
0 = 0
Z c E
°I2
CM 4. o>
all
— c o
to'o a'"
ills
Not. 21,22,23,24 PM
O
•f-i
JJ
m
s
a;
u
CO
tu
-P
w
Q)
S
a>
CO
u
OS
D
CM
-------
-18-
The wastewater treatment system consists of primary clarifi-
cation followed by a 10-acre aerated stabilization basin (ASB) and
a 7-acre activated sludge (AST) system. Excess solids from the
two secondary clarifiers are returned to both the primary clarifier
and the sludge thickener. Thickened secondary sludge and primary
sludge are combined prior to dewatering. Dewatered solids are
utilized commercially and/or sent to a landfill. Nearly 2 MGD of
the secondary effluent is recycled back into the mill and used in
the woodwaste boiler scrubber. The remaining portion is discharged
to a river.
The wastewater treatment plant is shown schematically in
Figure 111-10. Identification codes and flow rates at the time
of sampling are noted next to each sample location. Typical
operating conditions and performance are shown in Tables III-8
and III-9. These data reflect average operating conditions for
both winter and summer months.
2 mgd
Recycle
Secondary
Clarlflers
Primary
Clarifier
Final
Effluent
(DE026013
(28 mgd)
(DE026011)
Combined Dewatered
Sludge (800 Tons/day * 27% Solids)
FIGURE 111-10. Mill C Wastewater Treatment Plant Schematic
-------
-19-
TABLE III-8
MILL C WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
Parameter Value
Flow (MGD) 28
Residence Time (days) 1.5
Mixed Liquor Suspended Solids (mg/L) 2400
Return Sludge Recycle (%) 50
Aeration Horsepower (HP/million gallons) 38
No
TABLE III-9
MILL C WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter
BOD5 Loading (Ibs/day) 100,000-150,000
8005 Removal (%) 97
Suspended Solids Loading (Ibs/day) 409,000
Suspended Solids Removal (%) 96
Primary Sludge Production (wet tons/day) 2500
Consistency (%) 8
Waste Activated Sludge Production (tons/day) 5800
Consistency (%) 0.6
Combined Dewatered Sludge
Production (wet tons/day) 800
Consistency (%) 27%
significant differences between winter and summer operations,
-------
-20-
D. Mill D
Mill 0 is an integrated bleached kraft mill with a capacity
for 1105 tons per day of paper products. Major products are
newsprint and telephone directory paper. Six batch digestors are
used to pulp softwood chips. Pulping capacity exists for 460
tons per day bleached kraft (425 tons per day unbleached kraft).
In additional there is capacity for 830 tons per day groundwood
production.
The bleach plant consists of two lines, each utilizing a CEH
sequence. The bleach plant is shown schematically in Figure
III-ll. Sample identification codes and flow rates of both pulp
and washer filtrates are listed next to each sampling location.
Mominal operating conditions and chemical usages are listed in
Table 111-10. The relatively high hypochlorite use in the 3 bleach
line hypochlorite stage is related to high caustic carryover from
an undersized E-stage washer. Chlorine use on the B bleach line
was computed from tank car inventories.
A Side
•(DF024409)
• A »
250 Tons/day
(DF24410)
|(DF0244I2)
1 1.42 mgd
T-(DF024413)
(DF024414)
1.42 mgd
B Side
(DF024411)
120 Tons/day
(DF24409)
-------
-21-
TABLE 111-10
MILL D BLEACH PLANT OPERATING CONDITIONS AND CHEMICAL USAGES
SOFTWOOD LINE A
_ Parameter _
Throughput (dry tons/hour)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
Bleaching Stage
NaOH
NaOCl
Monoethanolamine
Residual Cl2
Semi-bleached Brightness
c
13.3
0.91
2.3
67.1
0
0
0.25
2.0
—
E
13.3
0.30
10.5
0
46
0
0
—
—
H
13.3
1.16
8.5
0
0
90
0.14
14.9
69
SOFTWOOD LINE B
_ Parameter _
Throughput (dry tons/hour)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
Bleaching Stage
NaOH
NaOCl
Monoethanolamine
Residual Cl2
Semi-bleached Brightness
C
5.8
2.0
76. 5
0
0
—
4.0
—
E
5.8
0.5
0
53
0
0
—
—
H
5.8
2.5
0
0
227
0.39
9.9
69
NOTE: Brownstock pulp permanganate number for
both bleach lines is typically 24.5.
-------
-2.2-
Power boilers at the mill burn gas and approximately 600 tons
per day of bark to produce 550,000 Ibs per hour of steam. Black
liquor is burned in a recovery boiler. Fly ash from the bark
boiler is collected with a 'nechanical dust collector and a wet
scrubber. Both fly ash and bottom ash are landfilled. The
scrubber water is sewered.
Raw water to the mill is takan from a nearby lake and from
wells. Water from both sources is chlorinated prior to use in
the mill. Approximately 22 MGD are used in the process. The
general mill sewer is shown in Figure 111-12. This figure provides
identification codes and flow rates associated with each sample
location. These flow values represent measurements or estimates
where flow is not routinely monitored.
(DF024401)
No. Entry
few Water
10.2 mgd
(DF024402)
10.2 mgd
"(DF024403)
11.7 mgd
So. Entry
Raw Water
11.7 mgd
3)
<
1
(DF024601)
Qroundwood
'aper Machines
9.60 mgd
i
' i
B
Pulp Mill
^Brownstock 2.8 mgd
Dregs, Old Caust
*(DF024406) 0.7 mgd
r \
t
i
Lime Kiln
Sewer
0.06 mgd
'(DF024406)
Evap. Sewer
" O.il mgd
Recovery
Boiler Sewer
0.1 mgd
leach Plant H Stage
1 (DF024414)
A Side Acid ^ 1.42 mgd
(DF024412) 1.42 mgd
IH Stage
(DF024418)
0.92 mgd
TrJF024416) 0.96 mgd
Caustic Sewer
(DF024413) 2.722 ms
i
{
i t
i
(DF024616)
0.06 mgd
Boiler Sewer
d
' To Wast<
(DF0246
Woodyard
0.6 mgd
FIGURE 111-12. Mill D General Mill Sewer Schematic
-------
-23-
The wastewater treatment system consists of primary clarifi-
cation followed by activated sludge with 2 to 3 hours detention
time. A dissolved air flotation system is used to control
suspended solids prior to the secondary clarifiers. Waste solids
are returned to the lagoon. Waste activated sludge is returned
to the primary clarifier. The combined sludge is dewatered and
sent to landfill for disposal. Chlorine (1000 Ibs/day) is
regularly used to control secondary sludge bulking. The waste
treatment plant is shown schematically in Figure 111-13. Identi-
fication codes and flow rates at the time of sampling are noted
next to each sample location. Typical operating conditions and
performance during both winter and summer months are shown in
Tables III-ll and 111-12.
Primary
Clarifiers
Sludge Recycle
10 mgd • 0.6% Solids
(DF024611)
18.85 mgd
r
^
Activated
Sludge
Solids Recycle
Dissolved
Air Flotation
*r\.
\
j
\
' ht
(
Wasted Sludge
Primary Sludge
(DF024614)
0.46 mgd
* 3%
Dewatered
Sludge
*(DF024613)
Secondary
Clarifiers
(DF024616)
0.4 mgd
• 0.5%
(DF024519)
after Chlorlnatlon
(DF024512)
18.49 mgd
FIGURE 111-13. Mill D Wastewater Treatment Plant Schematic
-------
-24-
TABLE III-ll
MILL D WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
Parameter Value
Flow (MGD) 20
Residence Time (days) 0.75
Mixed Liquor Suspended Solids (mg/L) 1200-1500
Sludge Age 2-2.5 days
Return Sludge Recycle (%) 50
Aeration Horsepower (HP/million gallons) 30
Primary Sludge Production (gal/day) 600,000
Consistency (%) 2-2.5
Waste Activated Sludge Production (gal/day) 400,000
Consistency (%) 0.50
TABLE 111-12
MILL D WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter Winter Summer
BOD5 Loading (Ibs/day) 15,000-30,000 15,000-30,000
BODs Removal (%) 85-90 90-93
Suspended Solids Loading (Ibs/day) 100,000-200,000 100,000-200,000
Suspended Solids Removal (%) 90-98 95-99
Combined Dewatered
Dry Sludge Production (tons/day) 50-100 50-100
Consistency (%) 15-18 15-18
-------
-25-
E. Mill E
»
Mill E is an integrated bleached kraft mill with a capacity
for 1330 tons per day of miscellaneous papers. Major products
include bond, business form paper, carbonizing, envelope, ledger,
offset paper, coated publication paper, and tablet. Two continuous
Kamyr digestors are used to pulp both hardwood and softwood chips
with a typical mix of 30% hardwood and 70% softwood. The kraft
pulp capacity is 1200 tons per day with an additional 130 tons
per day groundwood production.
The bleach plant consists of two lines both with a CDEOH/D
sequence. One of the lines alternately bleaches hardwood and
softwood pulp. The bleach plant is shown schematically in Figure
111-14. Sample identification codes and flow rates of both pulp and
washer filtrates are listed next to each sampling location.
Nominal operating conditions and chemical usages are listed in
Table 111-13.
A Side
(RQ186364)
CD
*
7 ^
i
t
\
4(RQ186369)
* 3 mgd
E0
'
k
1
Y ^
^
i
>
t(R0186370)
T 1.8 mgd
1
H/D
4
L
*T ^
^ •
— • — w
(R0186366)
600 Dry Tons/Day
J[R0186371)
* 1.0 mgd
B Side
+£5:
(RQ186366)
D
H/D
(RQ186367)
600 Dry Ton8/Day
f(RQ186372)
1.1 mgd
(R0186373)
X 1.6 mgd
WRQ186374)
^ 0.76 mgd
FIGURE 111-14. Mill E Bleaching Line Schematics
-------
-26-
TABLE 111-13
Parameter
LINE A - SOFTWOOD
Throughput (tons/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
Cl2
C102
NaOH
02
NaOCl
Residual Cl2 (gm/L)
Brightness
LINE B - HARDWOOD
Throughput (tons/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
C102
NaOH
02
NaOCl
Residual C12 (gm/L)
Brightness
LINE B - SOFTWOOD
Throughput (tons/hours)
Residence Time (hours)
PH
Temperature (°F)
Chemical Usage (Ibs/ton)
C12
C102
NaOH
02
NaOCl
Residual Cl2 (gm/L)
Brightness
AT ING CONDITIONS AND CHEMICAL USAGE:
Bleaching Stage
/-i
25
0.67
1.8
110
120
3.3
—
—
—
0.019
—
CD
25
0.33
1.80
130
80.4
2.03
—
—
—
0.022
—
CD
21
0.33
1.80
130
80.4
2.03
—
—
—
0.022
— —
E0
25
1.7
10.7
160
_ _
81
7.85
2.97
—
—
Eo
25
1.50
11.2
155
_ _
—
116.5
4.7
—
—
—
E0
21
1.50
11.2
155
_ _ .
116.5
4.7
— —
— —
— —
H
25
0.20
9.4
185
— —
2.65
—
17.2
0.0
66.3
H
25
0.20
10.1
185
~ _
—
0.35
—
24.6
0.0
64.5
H
21
0.20
10.1
185
-_ -_
0.35
—
24.6
0.0
66.1
D
25
1.5-2.0
6.7
180
— _
11.17
2.71
—
—
0.06
84.2
D
25
1.5-2.0
7.0
180
_• «
14.9
4.05
—
—
0.0
85.8
D
21
1.5-2.0
7.0
180
— —
14.9
4.05
—
— —
0.09
84.8
-------
The power
bone dry tons
steam per hour
-27-
boiler at the mill burns oil and approximately 250
per day of bark to produce 1.1 million pounds of
Both bottom and fly ash are sewered directly.
Raw water to the mill is taken from a nearby river/ treated
with alum flocculation, sand filtration, and chlorination prior to
use in the mill. Residues from the alum flocculation are sewered.
Approximately 38 MGD of treated water are used in the process.
The general mill sewer is shown schematically in Figure 111-15.
This figure also provides identification codes and flow rates
associated with each sample location. These flow values represent
measurements or estimates when flow is not routinely monitored.
River
Water
(RQ1-86366)
38 mgd
Treated Water
• fr{RG1-8635$)
34.6 mgd
Water
Treatment
Purge
0.9 mgd *
A-B Side
General
Sewer
(RQ1-86361)
4.2 mgd
Combined
Paper Machines
(RQ1-86379)
A-B Side Recaust.
Evap, Power
(RQ1-86362)
2.6 mgd
Otis Mill
(RQ1-86380)
2.6 mgd
A Side Eo (RQ1-86370)
B Side Eo (RQ1-86373)
A Side D (RQ1-86371)
B Side 0 (RQ1-86374)
* To WTP
(RQ1-86386)
37 mgd
FIGURE 111-15. Mill E Sewer System Schematic
-------
-28-
The wastewater treatment system consists of primary clarifi-
cation followed by an activated sludge system with 1.1 day
aeration time. The acid sewer bypasses primary treatment and is
put directly into the aeration lagoon. Secondary sludge is
gravity thickened prior to dewatering with the primary sludge on
sludge presses. Overflow from the gravity thickener is recycled
to the primary clarifier.
The wastewater treatment plant is shown schematically in Figure
111-16. Identification codes and flow rates at the time of sampling
are noted next to each sample location. Typical operating condi-
tions and performance during both winter and summer months are
shown in Tables 111-14 and 111-15.
TABLE 111-14
MILL E WASTEWATER TREATMENT PLANT OPERATING PARAMETERS
Parameter Value
Flow (MGD) 40
Residence Time (days) 1.2
Mixed Liquor Suspended Solids (mg/L) 1300-1400
Return Sludge Recycle (%) 53
Aeration Horsepower (HP/million gallons) 44
TABLE 111-15
MILL E WASTEWATER TREATMENT PLANT PERFORMANCE DATA
Parameter
BODs Loading (Ibs/day) 80,000-120,000
BODs Removal (%) 93-94
Suspended Solids Loading (Ibs/day) 430,000
Suspended Solids Removal (%) 93-95
Secondary Sludge Production (dry tons/day) 35
Combined Sludge Production (dry tons/day) 200
-------
-29-
Comblned
Acid Sewer
(RQ1-86368)
4.03 mgd
Influent
(RQ1-86386)
37 mgd
Effluent
To River
(RQ1-86388)
41 mgd
(RQ1-86397)
0.43 mgd
(RQ1-86387)
90 Dry Tons/Day
FIGURE 111-16. Mill E Wastewater Treatment Plant Schematic
-------
-30-
IV. FIELD PROGRAM
The field program for this study was conducted according to
the schedule shown below:
Mill A June 24-25, 1986
Mill B September 8-10, 1986
Mill C October 15-18, 1986
Mill D December 2-3, 1986
Mill E January 13-15, 1987
In addition, preliminary grab samples were collected from Mill A
in March 1986 for analytical methods development and prescreening
of selected samples including wood chips, unbleached and bleached
pulps, selected untreated wastewaters, paper machine additives,
wastewater sludges, and treated process wastewater effluents.
A. Sampling Plan
The study design called for sampling all mill inputs thought
to be significant; intermediate process materials and untreated
process wastewaters; and mill exports including bleached pulps,
wastewater sludges, and treated process wastewater effluents.
Table IV-1 presents the detailed sampling plan for Mill A. Similar
plans were developed for each mill after site reconnaissance
visits to review process water treatment systems, process opera-
tions, sewerage systems, and wastewater treatment systems.
Based upon the results of the reconnaissance visits, specific
sampling locations were selected to determine mass flow rates of
process waters, wastewaters, and process materials. The sampling
plans were reviewed in detail by USEPA, NCASI, and mill personnel
prior to implementation. Arrangements were made to acquire pulp
mill, bleach plant, and wastewater treatment system operating
logs during each sampling survey. Note that primary flow moni-
toring devices have not been installed on most internal plant
process wastewater streams. Accordingly, crude measurements or
best engineering estimates of flow were developed for these
streams. This is particularly common for the individual bleach
plant pulp washing stages between chemical applications. Mass
flow rates of pulps and final treated process wastewater effluents
were generally determined with primary monitoring devices and are
considered to be more accurate. Also, the determination of
chemical applications in the bleach plants from the operating
logs was found to be difficult due to differences in reporting,
solution strength measurement methods, and mill-specific data
recording procedures.
-------
-31-
TABLE IV-1
MILL A - DETAILED SAMPLING PLAN
SAMPLE
NUMBER
DE020801
DE020802
DE020803
DE020804
DE020805
SAMPLE DESCRIPTION
A. Background Samples
Treated River Water
Water Treatment Precip. Sludge
Water Treatment Sandfilter Sludge
Softwood Chips
Hardwood Chips
B. Pulping Process
DE020806 Combined Pulping & Recaust WWs
C. Chemical Recovery Plant
DE020807 Combined Process Wastewater
DE020808 Lime Mud
D. Bleach Plant
DE020901 Unbleached Softwood Pulp
DE020902 Bleached Softwood Pulp
DE020903 Unbleached Hardwood Pulp
DE020904 Hypo Hardwood Pulp
DE020905 Peroxide Hardwood Pulp
Softwood Bleach Line
DE020906 S-l Washer, C Stage
DE020907 S-2 Washer, Eo Stage
DE020908 S-3 Washer, H Stage
Hardwood Bleach Lines
DE020909 K-6 Washer, C Stage
DE020910 K-4 Washer, EQ Stage (Hypo line)
DE020911 K-5 Washer, H Stage (Hypo line)
DE020912 K-2 Washer, Eo Stage (Per line)
DE020913 K-3 Washer, H Stage (Per Line)
DE020914 K-l Washer, H Stage (Per Line)
DE020915 Combined Process Wastewater
DE020809 Hypo Solution
DE020810 Caustic Solution
SAMPLE
NUMBER SAMPLE DESCRIPTION
E. Paper Machines
DE020811 Combined Process WW Process Additives
DE020812 Alum
DE020813 Clay-1
DE020814 Clay-2
DE020916 Dye-1
DE020917 Dye-2
DE020815 Resin Size Emulsion
DE020816 High Brightness Filter
DE020817 Slimicide
DE020822 Soda Ash
DE020823 Sodium Thiosulfate
DE021001 White Water - Clean
DE021002 White Water - Dirty
F. Utilities, Wastewater Treatment
DE020818 Powerhouse Wastewater
DE020918 Bottom Ash
DE020919 Fly Ash
DE020819 WWTP Primary Sludge
DE020820 WWTP Secondary Sludge
DE020920 WWTP Composite Sludge
DE020921 Combined Untreated Wastewater
DE020922 Final Wastewater Effluent
DE020821 Landfill Leachate
G. Other
DE020923 Sludge - not from Mill A
DE020824 Thiosulfate & H2S04 Reagent Blank
-------
-32-
The sampling plan for each mill called for 24-hour composite
sampling of mill inputs, intermediates, and exports, except for
paper machine additives (alum, clays, dyes, slimicides) and, for
some mills, power boiler ashes and landfill leachates. Discrete
grab samples of those materials were collected during or imme-
diately after the 24-hour sampling period. At most mills where
multiple dyes are used, samples were collected of at least two
dyes used at the time of the survey and of one or two dyes most
heavily used throughout the prior year. For four of the mills,
final process wastewater effluent sampling was delayed to account
for the estimated time-of-travel or residence time of the
wastewater through the respective wastewater treatment systems.
Mill-specific field sampling is described in Section IV.C.
B. Sample Collection, Sample Handling, and Sample Custody
Attachment B presents the field protocols followed for the
five-mill study. Precleaned sample collection devices and sample
containers (one gallon or one quart glass bottles) were used
throughout the study. The cleaning procedures are outlined in
Attachment B. For liquid samples (treated process water, untreated
and treated wastewaters, liquid or slurry sludges, and dilute
process additive solutions) one gallon samples were collected.
For solids and semi-solids (wood chips, clays, dewatered sludges,
ashes, and pulps) and concentrated liquid additives (slimicides,
dyes, and certain paper machine additives) one quart samples were
collected. The pulp samples were partially dewatered in the
field at the time of collection by manually squeezing individual
grab samples used to make up the 24-hour composite samples. The
analytical data for solid and semi-solid samples including liquid
sludges were determined on a dry weight basis. All other samples
were analyzed on a wet weight basis. At most mills, individual
or combined paper machine wastewaters were sampled at convenient
sewer locations and combined on a flow-proportioned basis with
other paper machine wastewaters to form one composite paper
machine wastewater sample from the mill.
The 24-hour composite samples were manually collected and
comprised of eight discrete grab samples obtained at approximate
three-hour intervals.
All samples were iced during the collection period and secured
in locked ice chests or in ice chests secured with custody seals
or tape. With few exceptions, individual or multiple ice chests
were specifically assigned to a sampling location to minimize
chances of sampling errors. Wastewater samples suspected of
containing chlorine were checked for total residual chlorine at
the time of collection. Total residual chlorine was neutralized
-------
-33-
with a slight excess of sodium thiosulfate in solution or in
crystalline form at the time of collection. Also, samples
collected for chlorinated phenolics were adjusted to pH <2 with
6M sulfuric acid upon collection for sample preservation.
C. Site Specific Sampling
The sampling at each mill was conducted according to the
sampling plans and protocols described above and in Attachment B.
Unique sampling and deviations from the sampling protocols at
each mill are described below:
1. Mill A
Sample Number DE020818 - Due to minimal wastewater flows, the
powerhouse wastewater was grab sampled.
Sample Number DE020821 - The landfill leachate and runoff
sample was a grab sample vs. a 24-hour composite sample since the
leachate and runoff collected in a pond with long retention time.
The wastewaters are discharged on an intermittent basis to the
wastewater treatment facilities.
Sample Number DE020922 - The final effluent 24-hour composite
sample was collected concurrently with samples from the mill.
Hence, the estimated residence time in the wastewater treatment
system was not taken into account in the sampling program as was the
case for the other four mills included in the study.
2. Mill B
Sample Number 86374621 - The first aliquots for the individual
24-hour field composite samples from the newsprint machine #3
(station E-2A) and forms bond machine (station E-2B) were not
taken due to sampling error.
Sample Number 86374646 - The landfill leachate sample was a
short term composite sample vs. a 24-hour composite sample since
the discharge flow rate was minimal and the discharge was direct
rather than to the wastewater treatment system.
3. Mill C
Sample Number DE026006 - Only one aliquot of D-stage filtrate
was collected during the first 12 hours of the survey due to a
plugged sample port. Sampling resumed as normal for the balance
of the survey. The D-stage filtrate was not sewered during the
survey.
-------
-34-
Sample Number DE026011 - Due to minimal wastewater volume and
remote location, the wastewater sludge landfill leachate was grab
sampled.
Sample Numbers DE026013 and DE026206 - 24-Hour composite
samples of secondary wastewater effluent were collected during
the 24-hour sampling period for the mill (0-24 hours) and on a
delayed basis (36-72 hours) to account for residence time in
the wastewater treatment facilities. The 0-24-hour sample was
collected to characterize about 2 MGD of treated effluent returned
to the .mill during the survey period.
4. Mill D
No significant changes from the sampling protocols.
5. Mill E
Sample Number RG1-86357 - A two gallon concentrated sample of
river intake water filter backwash was obtained by decanting one
gallon samples from six separate filter backwashes.
Sample Numbers RG1-86367, 72, 73, and 74 - Due to production
scheduling at the mill, the B bleach line was sampled for a 4-hour
period after the 24-hour sampling period for the mill and after a
change from softwood to hardwood production. Precautions were
taken in the field to insure hardwood pulp was being sampled on
this line. However, based upon a review of process operating
logs, the short-term bleached pulp composite sample obtained was
comprised of undetermined amounts of both softwood and hardwood
pulps.
Sample Numbers RG1-86380/92 - An untreated paper machine
wastewater from a nonintegrated paper mill located near Mill E was
sampled as it entered the Mill E wastewater treatment system.
-------
-35-
V. ANALYTICAL PROGRAM
A. Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated
Dibenzofurans (PCDFs)
1. Compounds Selected for Analyses
Analyses of preliminary samples from two mills indicated that
2378-TCDD and 2378-TCDF are the principal PCDDs and PCDFs found
in various pulp and paper mill matrices. Samples from other pulp
and paper mills analyzed by USEPA reveal similar patterns.3
Tables V-l to V-3 present data for six mills for isomer specific
determinations of 2378-TCDD, data for the determination of 2378-
TCDF plus possible co-eluting isomers, and data for higher chlori-
nated PCDDs and PCDFs. Each of these mills process primarily
virgin fiber. Mills A and E (Tables V-l and V-2) are among the
five mills included in the cooperative study. Mill 1 (Table V-l)
and Mills 2, 3, and 4 (Table V-3) are other bleached kraft mills
not included in this study. Data for Mill E were developed using
procedures previously demonstrated to be isomer specific for
2378-TCDF. Also summarized are the 2378-TCDD toxic equivalents
computed to the extent possible for all detected PCDDs and PCDFs.
Very few of the higher congener measurements were made using
procedures which have been demonstrated to be isomer specific for
the 2378-substituted isomer. Accordingly/ the results must be
qualified as possibly reflecting the presence of co-eluting
isomers. Nevertheless, conservative calculations of the toxic
equivalents (TEQs) were made assuming the concentrations reported
for the 2378-substituted isomers were all the most toxic isomer.
Note that the analyses were completed by three laboratories
(Dow Chemical (Table V-l); Wright State University (Table V-2);
and USEPA-ERL Duluth (Table V-3)) using different sample cleanup,
extraction, and analytical protocols. Accordingly, the results
may not be fully comparable. Nonetheless, the data are consistent
in the relative absence of the higher chlorinated PCDDs and PCDFs.
The 2378-TCDF concentrations measured as part of a full
congener analysis for Mill A and Mill 1 (Table V-l) were shown to
be substantially correct based upon split sample analyses using
procedures which were isomer specific for this compound. It
should also be noted that only the 2378-substituted isomers were
quantitated in the Mill A and Mill I analyses. However, the
comparatively low relative toxicity equivalency factors for the
higher congener non-2378-substituted isomers indicate that this
data limitation does not substantially alter the conclusion that
virtually all the TEQs are associated with 2378-TCDD and 2378-TCDF.
-------
-36-
TA3LE V-l
PCDDs and PCDFs IN BLEACHED KRAFT PAPER MILL MATRICES
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
DOW CHEMICAL ANALYSES
PCDDS
2378-TCDD
12378-PeCDD
123789-HxCDD
123678-HxCDD
123478-HxCDD
1234678-HpCDD
OCDD
Mill A
Bleachery
Wastewaters9
150 ppq
6 (6)
ND (20)c
ND (15)
ND (15)
45 (10)
220 (40)
Mill A
Final
Effluent9
73 ppq
ND (7)
ND (20)
ND (15)
ND (15)
30 (15)
220 (30)
Mill A
Wastewater
Sludgeb
17 ppt
ND (1)
ND (7)
ND (7)
ND (7)
ND (6)
59 (9)
Mill 1
Combined
Wastewater
Sludgeb
240 ppt
25
6 (3)
} 9 (5)
150
1400
Notes
PCDFs
2378-TCDF
23478-PeCDF
12378-PeCDF
234678-HxCDF
123789-HxCDF
123678-HxCDF }
123478-HxCDF
1234789-HpCDF
1234678-HpCDF
OCDF
SAMPLE TEQf
% TEQ from
2378-TCDD &
2378-TCDF
2500 ppq
23 (3)
27 (3)
ND (5)
ND (7)
9 (2)
ND (10)
10 (5)
30 (15)
410 ppq
98%
1000 ppq
16 (3)
16 (2)
ND (5)
ND (5)
5 (3)
ND (10)
7 (7)
20 (10)
180 ppq
98%
300 ppt
3 (1)
3 (1)
2 (2)
ND (2)
1 (1)
ND (3)
2 (2)
5 (5)
48 ppt
99%
2300 ppt
53
140
3 (1)
<4
20
5
11
43
(2)
500 ppt
94%
d
d
d
d
d,e
d
NOTES; (a) Concentrations in liquid samples determined on the basis of the
total weight of the samples.
(b) Concentrations in sludge samples determined on dry weight basis.
(c) ND - Not detected at stated detection level; detection level is
reported in parentheses ( ). Detection level reported in
parentheses ( ) when analytical result is less than 10 times
detection level.
(d) Data may reflect presence of co-eluting isomers.
(e) Maximum possible concentration.
(f) Sample TEQ computed assuming isomer-specific analyses for listed
compounds. Sample TEC computed by USEPA (see Reference 2).
-------
-37-
TABLE V-2
PCDDs and PCDFs IN BLEACHED KRAFT PAPER MILL MATRICES
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
WRIGHT STATE UNIVBRSITY ANALYSES
PCDDS
2378-TCDD
12378-PeCDD
123789-HxCDD
123678-HxCDD
123478-HxCDD
1234678-HpCDD
OCDD
Mill E
Bleachery
Wastewaters
970
ND
ND
ND
ND
130
1800
ppq
(70)
(70)
(30)
(30)
Mill E
Final
Effluent
80
ND
ND
ND
ND
80
990
ppq
(12)
(100)
(50)
(120)
Mill E
Combined
Wastewater
Sludge
190
12
ND
ND
ND
26
298
ppt
(13)
(23)
(1.9)
PCDFs
2378-TCDF
23478-PeCDF
12378-PeCDF
234678-HxCDF
123789-HxCDF
123678-HxCDF
123478-HxCDF
1234789-HpCDF
1234678-HpCDF
OCDF
SAMPLE TEQ
% TEQ from
2378-TCDD &
2378-TCDF
4600 ppq
ND (20)
ND (90)
ND (870)
ND (130)
ND (150)
ND (70)
ND (40)
ND (10)
70
360 ppq
ND (15)
ND (5)
ND (410)
ND (450)
ND (340)
ND (130)
ND (90)
ND (20)
86
1400 ppq
(1500)C
>99%
(96%)C
120 ppq
(150)C
>99%
(78%)C
760
ND
ND
ND
ND
ND
ND
ND
ND
ND
PPt
(12)
(19)
(68)
(29)
(19)
(11)
(4)
(2)
(9)
270 ppt
(280)c
98%
(96%)C
NOTES: (a)
(b)
(c)
ND - Not.detected at stated detection
level; detection level is reported in
parenthesis ( ) .
Data for 2378-TCDD, 2378-TCDF, OCDD, OCDF
are isomer specific. Data for other com-
pounds may reflect the presence of co-eluting
isoraers.
Sample TEQ and percentage attributable to
2378-TCDD and 2378-TCDF shown in ( ) were
computed assuming all compounds present at
stated analytical detection levels.
-------
-38-
TABLE V-3
PCDDs and PCDFs; IN BLEACHED KRAFT
PAPER MILL WASTEWATER SLUDGES
USEPA-ERL DULUTH ANALYSES
2378-TCDD
TCDD-Other
12378-PeCDD
PeCDD-Other
123678-HxCDD
HxCDD-Other
1234678-HpCDD
1234679-HpCDD
OCDD
2378-TCDF
TCDF-Other
12378-PeCDF
PeCDF-Other
123678-HxCDF
HxCDF-Other
HpCDF-Total
OCDF
SAMPLE TEQ
% TEQ from
2378-TCDD &
2378-TCDF
Mill 2
Combined
Wastewater
Sludge
Mill 3
Combined
Wastewater
Sludge
ppt
(10!
(5)
(5)
150
ND
ND
ND
17
62
110
82
1860
880 ppt
640
29
140
5
30
5
53
260 ppt
93%
37
ND
ND
ND
2
21
1380
1240
14000
200
310
2
15
31
240
360
310
PPt
(5)
(5)
(5)
ppt
Mill 4
Combined
Wastewater
Sludge
61 ppt
94%
53
ND
ND
ND
2
10
33
29
710
280
220
ND
ND
ND
ND
22
ND
PPt
(1)
(5)
(5)
(2)
ppt
(5)
(5)
(5)
(5)
(20)
81 ppt
>99%
NOTES: (a) ND - Not detected at stated detection level;
detection level is reported in parentheses
(b) Data for 2378-TCDD, OCDD, and OCDF are
isomer specific. Data for other 2378-
substituted compounds may reflect the
presence of co-eluting isomers.
(c) Mills 2, 3, and 4 were not among the
five mills included in this study.
-------
-39-
Note that for Mill E (Table V-2) , TEQs were computed in two
ways: (1) assuming that compounds not detected were present at the
stated analytical detection level; and (2) that compounds not
detected were not present, i.e., concentration of zero. This was
done because of the relatively high analytical detection levels
observed for several higher chlorinated 2378-substituted PCDDs
and PCDFs in the bleachery wastewater and final effluent samples.
For the bleachery wastewater there is no significant difference
in the proportion of the TEQ associated with 2378-TCDD and 2378-TCDF
with either of the methods described above. For the final effluent
only 78% of the TEQ would be associated wath 2378-TCDD and
2378-TCDF, if it were assumed that all of the higher chlorinated
compounds not detected were present at the stated analytical
detection levels. However, this is unlikely given the findings
in wastewater sludge from that mill. The conservative calculations
have the tendency to overstate the TEQs associated with the higher
congeners. Despite this bias, the 2378-TCDD and 2378-TCDF concen-
trations for the remaining mills clearly represent the major
portion of the total PCDD/PCDF toxic equivalents (TEQ). Based
upon these data, the principal focus of the analytical program
for this study was directed at isomer-specific analyses for
2378-TCDD and 2378-TCDF.
Each of the mills listed in Tables V-l to V-3 and each of the
five mills included in this study are reported to produce virgin
hardwood or softwood pulps. Extraneous sources of fiber that
might include wood treated with chemical preservatives are not
used at these mills. Hence, the introduction of higher chlorinated
dioxins and furans associated with pentachlorophenol is not likely.
2. Preliminary Sampling - March 1986
As part of the analytical methods development for this study
preliminary grab samples of selected matrices were collected from
Mill A in March 1986. The analytical results for the process
samples are presented in Table V-4, while the results for wastewater
and sludge samples and process additives are presented in Tables
V-5 and V-6, respectively. The sample preparation, sample extract
processing, and GC/MS analytical methods used for analyses of
these samples were not the final methods selected for the five-mill
study. The data for 2378-TCDF were not isomer-specific and only
total homologue data were developed for penta-octa CDDs and CDFs.
In some cases, the analytical detection levels attained were not
consistent with the study objectives. Finally, since the samples
were grab samples, the representativeness of the results with
respect to mass- flow rates is questionable. Nonetheless, the
results provide some insight to the formation of PCDDs and PCDFs
in this bleached kraft pulp and paper mill and to the relative
distribution of 2378-TCDD and 2378-TCDF versus other PCDDs and
PCDFs.
-------
-40-
In Table V-4, 2378-TCDD and 2378-TCDF were not found in
softwood chips, weak liquor, or recovery system mud, all samples
obtained prior to pulp bleaching; neither were TCDDs, PeCDDs,
HxCDDs, or TCDFs, PeCDFs, HxCDFs, HpCDFs, or OCDF at detection
levels in the 0.5 to 12 ppt range. Total HpCDDs and OCDD were
found in the softwood chips (37 and 154 ppt, respectively) and in
the recovery mud (3.3 and 10.7 opt, respectively). The brownstock
pulp contained only OCDD at 1.2 ppt while the bleached pulp
contained 2378-TCDD and 2378-TCDF plus possible co-eluting isomers
at 8 and 70 ppt, respectively. Other TCDDs and TCDFs were not
found at significantly higher levels in the bleached pulp, and
penta-hepta CDDs and CDFs and OCDF were not found at detection
levels of less than 1 ppt. OCDD was found in the bleached pulp
at nearly 1 ppt. These data indicate that 2378-TCDD and 2378-TCDF
plus possible co-eluting isomecs are formed in the bleaching of
softwood pulp and these compounds are preferentially formed over
higher chlorinated PCDDs and PCDFs.
The wastewater and sludge results presented in Table V-5
show similar trends. Wastewater samples obtained prior to pulp
bleaching show no detectable PCDDs and PCDFs at detection levels
in the 0.01 to 0.02 ppt range, except for OCDD at 0.04 ppt. The
combined untreated bleach plant wastewaters contained 1.1 ppt of
2378-TCDD and 3.9 ppt of 2378-TCDF plus possible co-eluting
isomers. While no other TCDDs were found, about 3 ppt of TCDFs
other than 2378-TCDF were found. Considerably lower levels of
2378-TCDD (0.09 ppt) and 2378-TCDF plus possible co-eluting isomers
(0.45 ppt) were detected in the paper machine wastewaters.
Penta-octa CDDs and CDFs were not analyzed in the bleach plant
and paper machine wastewaters. The treated final process waste-
water effluent contained both 2378-TCDD (0.25 ppt) and 2378-TCDF
plus possible co-eluting isomers (1.0 ppt). Higher chlorinated
PCDDs and PCDFs were not found in the treated effluent in the
0.01 to 0.05 ppt range. The combined wastewater treatment sludge
sample contained about 65 ppt of 2378-TCDD (average of two analyses)
and 280 ppt of 2378-TCDF plus possible co-eluting isomers. Except
for OCDD, higher chlorinated PCDDs and PCDFs were not detected in
the sludge.
TCDDs and TCDFs were not detected in samples of slimicide,
alum, clays, and a yellow dye at detection levels of less than 1 ppt
(Table V-6). However 2378-TCDD and other TCDDs were found in a
sample of blue dye at 3.4 ppt and 53 ppt, respectively. TCDFs
were not found in the blue dye.
The distribution of PCDDs arid PCDFs in these samples were also
considered in the decision to focus the analytical program on
2378-TrCDD and 2378-TCDF.
-------
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-------
-44-
3. Analytical Methods for 2378--TCDD and 2378-TCDF
As noted above, in the initial phase of the assessment of paper
mill process samples and waste products, attention was focused on
accurate quantitative measurement of 2,3,7,8-tetrachlorodibenzo-p-
dioxin (2378-TCDD) and 2, 3 , 7 ,- 8-tetrachlorodibenzof uran (2378-
TCDF). Target detection limits of 1-2 parts per trillion (ppt)
for these isomers in solid media were established, while the target
limits for these isomers in aqueous media were set at 0.001 to
0.010 ppt (1-10 parts per quadrillion (ppq) ) . Analyses of the
preliminary samples at Wright State University indicated that
achieving these detection levels was not practical using the
traditionally applied sample extraction and cleanup techniques.
Moreover, an extensive evaluation of the separation capabilities
of the several capillary gas chromatography columns which are
usually employed in such analyses (DB-5, SP-2330, SP-2340), using
all 38 TCDF isomers, revealed that 2378-TCDF co-elutes with one
or more of the other TCDF isomers on all of these columns.
Therefore, 2378-TCDF could not be uniquely determined by using
any of these columns. Accordingly, Wright State, in consultation
with USEPA and NCASI, undertook the development and validation of
sample extract cleanup procedures which utilized a multiple silica,
alumina, and carbon column 1iquid-chromatographic cleanup sequence
which has the capacity to remove larger quantities of matrix
constituents and other chemical residues. These methods also
utilize modified alumina column elution procedures, in which the
strength of the eluting solvent mixtures is more critically
adjusted in order to optimize separation of 2378-TCDD and 2378-TCDF
from other extraneous chemicals in the sample extract. Finally,
gas chromatographic studies were accomplished which led to the
development of a hybrid phase DB-225/DB-5 capillary GC column,
which was demonstrated to completely resolve 2378-TCDF (<10% to
<25% valley) from the other 37 TCDF isomers. This column was
applied routinely for definitive 2378-TCDF analyses. A brief
summary of the overall analytical procedures applied to determine
2378-TCDD and 2378-TCDF in the samples characterized in this
study follows. The final analytical protocol is presented as
Attachment C.
a. Sample preparation
Sludge samples were mixed thoroughly to achieve uniformity
and two aliquots were withdrawn. One aliquot was subjected to
oven drying at 105°C until the sample attained constant weight.
This aliquot was then discarded. The percent solids determined
on this basis was used for determining the concentration of the
analytes in the second aliquot, which was the portion of the
sample actually analyzed for 2378-TCDD and 2378-TCDF. The second
-------
-45-
sample aliquot was dried on a stainlass steel screen which was
supported within a desiccator. The dried sample was homogenized
in a laboratory blender and an aliquot was removed for analysis.
Wood chip samples were reduced to a particle size of 1 cm
diameter or less using a laboratory mill. The pulverized wood was
then dried, homogenized, and subsampled in the same .manner as the
sludge samples just described.
Ash samples were prepared in the same manner as sludge samples,
except that that they were dried in a shallow flat dish placed in
a desiccator.
Pulp samples were manually compressed to removed the bulk of
water contained therein and the sample was broken up to small
pieces (2 cm or less in diameter) which were then dried,
homogenized, and subsampled in the same manner as the sludge
samples.
Slurries (secondary sludge and similar materials) were stirred
to suspend particulate matter and an aliquot was removed for total
suspended solids determination (Standard Methods for the Exami-
nation of Water and Wastewater, 17th Edition, APHA, AWWA, WPCF,
1986, Method 209C) . The remainder of the sample was allowed to
settle, under refrigeration, and the supernatant was removed and
filtered through a tared Gelman Type A/E filter. The solids thus
recovered were dried, homogenized and subsampled, in the same
manner as described for sludge samples.
Water and wastewater samples were agitated in the original
sample vessel to resuspend solids contained therein, and the
sample was split into four portions, each portion being placed in
a new sample bottle. One of the split samples was spiked with
isotopically labelled C-, 2-2378-TCDD and TCDF internal standards
in an acetone solution and the sample was stirred vigorously for
15 minutes to disperse the spiking standards. The aqueous sample
was then filtered through a Whatman 42 filter and the filtrate
was retained for analysis. The filter and solids recovered were
dried in a desiccator to constant weight and the solids were
retained for analysis.
Exceptional samples which were too wet to dry efficiently in
a desiccator but could not be filtered were first air dried
at ambient temperature, then desiccated.
-------
-46-
b. Extraction of 2378-TCDD and 2378-TCDF from the sample matrices
Methylene chloride was added to internal-standard spiked
aqueous filtrates (1 liter, typically) and the sample was stirred
for 16 hours. The aqueous and organic phases were allowed to
separate and the organic phas;e was removed and retained for
analysis. The aqueous sample was reextracted sequentially with
two additional portions of methylene chloride and those were
pooled with the original extract. This extract solution was
concentrated and combined with the benzeneracetone solvent in the
Soxhlet apparatus used to extract the solid portion of each
filtered aqueous sample, as described below.
Portions (typically 7-10 grams) of the solid samples (dried
sludges, ash, wood chips, pulp, solids from water and wastewater)
were placed in a Soxhlet apparatus, spiked with 13c-j2-2378-TCDD
and TCDF internal standards, and extracted with a 50:50 solution
of benzene:acetone for a period of 16 hours. Extracts were
concentrated to a volume of about 15 mL using a Snyder column.
These extracts were cleaned up as described below.
c. Preliminary fractionation of sample extracts to separate
2378-TCDD and 2378-TCDF from other extract constituents
Organic extracts prepared as described above were subjected
to a series of sequential washes with 20% aqueous potassium
hydroxide, concentrated sulfuric acid and double-distilled water,
discarding the aqueous portions and retaining the organic phase
in each case.
Each washed organic extract was subjected to a sequence of
liquid chromatographic column separations, including, (a) passage
through a composite column of silica gel, base-modified and acid-
modified silica gel, eluting tVie column with hexane and retaining
the eluate; (b) passage through a Woelm basic alumina column,
eluting sequentially with 3% methylene chloride-in-hexane, 20%
methylene chloride-in-hexane and 50% methylene chloride-in-hexane,
retaining only the last eluate fraction; (c) passage through a
second basic alumina column, as just described; (d) passage
through a carbon/celite column, eluting with hexane, 50% methylene
chloride/50% cyclohexane, then with 50% benzene/50% ethyl acetate,
and finally reverse eluting with toluene, retaining only the last
eluate fraction; and (e) passage through a third basic alumina
column, just as described earlier. The final eluate fraction
collected was concentrated just to dryness, and was reconstituted
with 10 micro liters of tridecane containing other appropriate
standards, prior to GC/MS analysis.
-------
-47-
d. Gas chroraatographic-mass
sample extracts
spectrometric (GC/MS) analyses of
Sample extracts prepared by the procedures described in the
foregoing were analyzed by GC/MS utilizing an appropriate capillary
GC column (temperature-programmed) while the MS is operated in
the selected ion monitoring (SIM) mode, monitoring simultaneously
the ion masses appropriate for detection of 2378-TCDD, 2378-TCDF,
and the 13C12-labelled internal standards of these. Typically,
1 to 5 uL portions of the extract are injected into the GC. Sample
extracts were initially analyzed using a 60 meter DB-5 capillary
GC column at a typical mass spectral resolution of 1:600 to obtain
data on the concentration of 2378-TCDD and to determine if 2378-TCDF
or other isomers which co-elute with 2378-TCDF are present. If
the latter were detected in this analysis, then another aliquot
of the sample extract was analyzed in a separate run, using a
newly developed hybrid column which consists of a 10 meter section
of a 0.25 mm I.D. fused silica open tubular DB-5 capillary column
coupled with a 30 meter section of a 0.25 mm I.D. DB-225 column.
Again, the mass spectrometer was operated at low resolution
(typically 1:600) in the first analysis with this column. The
hybrid column uniquely separates 2378-TCDF from the other 37 TCDF
isomers and therefore yields definite data on the concentration
of 2378-TCDF in the extract which is analyzed. However, in some
instances compounds are present in the sample exract which give
rise to ion masses which, at low mass resolution (1:600) , interfere
with the quantitation of 2378-TCDF. In these instances the
analysis of the sample extract was repeated, using the DB-5/DB-225
hybrid column, but this time at a mass spectral resolution of
1:6,500 or higher.
The analytical
in Attachment C.
procedures summarized here are fully described
4. Identification and Quantitation of 2378-TCDD and 2378-TCDF
The following criteria were established for positive identi-
fication and quantitation of the target analytes:
(1) Mass spectral responses must be observed for the following
ions monitored, i.e;:
13,
•12
13
TCDD:
-TCDD:
TCDF:
c12~TCDF:
320, 322, and 257
332 and 334
304, 306, and 241
314 and 316
(2)
The signal to noise ratio of the molecular ions (2378-TCDD
-- 320 and 322; 2378-TCDF -- 304 and 306) must be greater
than 2.5:1 for the ions to be considered detectable.
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(3) The molecular ions for a given analyte should co-maximize
within no more than plus or minus one scan of each other.
(4) The ratio of the [M]+ to [M + 2]+ intensities must be at
or within ±15% of the theoretically expected ratio of
0.77; i.e., 0.65 to 0.,89 for 2378-TCDD and 2378-TCDF.
(5) The chromatographic retention time of the unlabelled 2378-
TCDD or 2378-TCDF must be within five seconds of the
corresponding l^C-labelled internal standard.
(6) The GC column resolution must be demonstrated to provide
a 25% valley or less between 2378-TCDD and its closest
eluting isomers on the DB-5 column or between 2378-TCDF
and its closest eluting isomers on the DB-5/DB-225 column.
(7) If responses are detected for the molecular ions of 2378-
TCDF on the DB-5 column, the sample extract must be re-
injected and reanalyzed on the DB-5/DB-225 column to
ensure isomer specific quantitation.
(8) No response must be seen at M/Z = 374, the [M]+ ion for
hexachlorodiphenyl ether, at the same retention time as
2378-TCDF. This ether would give fragment ions identical
to 2378-TCDF, and hence cause false positives.
(9) The target percent recoveries of the 13c_;i.abeiecl analogs
for 2378-TCDD and 2378-TCDF were set at 40%-120%.
5. Intra-Laboratory Method Validation Experiments
This study was one of the first large-scale attempts at
quantifying 2378-TCDD and 2378--TCDF on an isomer-speci f ic basis,
at ppt and ppq levels, in pulp and paper mill matrices. These
matrices were expected to provide considerable difficulties in
cleanup and isolation of the target analytes due to the high
levels of particulate matter, dissolved organics and other chemi-
cals. It was also felt that the var iabil ity of feedstock, in-plant
processes, chemical application rates, etc., could cause problems
that were specific to samples from particular mills. Therefore,
method validation experiments were carried out on selected
matrices. These analyses were to characterize any inherent
deficiencies in the analytical methodology that would result in
inter-mill data comparability problems. Since virtually all of
the samples were to.be analyzed by a single laboratory for 2378-TCDD
and 2378-TCDF, the primary goal was to validate the method
internally within the scope of the study.
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Method validation studies were carried out on three distinctly
different matrices that are the primary exports from pulp and
paper mills. The three matrices were bleached pulp, wastewater
treatment sludge, and treated process wastewater effluent. The
cleanup and the last would be demanding because of the relatively
low target detection limit of 0.010 ppt. A restricted study was
carried out on a fourth matrix, namely an artificial composite
caustic extraction stage effluent made up of equal volumes of
caustic extraction stage effluents from the five mills. Samples
for each matrix from four of the five mills surveyed in this
screening study were analyzed in duplicate. . Additional sample
aliquots were spiked with 2378-TCDD and 2378-TCDF at concentration
levels two to three times the native concentrations. In general,
16 determinations each were made for 2378-TCDD and 2378-TCDF in
these selected matrices. An exception was the caustic extraction
stage wastewater where a composite sample made up of equal volumes
from all five mills was used for the method validation experiment.
A single sample spike and spike duplicate analytical sequence was
carried out for this composite sample.
The analytical results obtained, i.e., concentrations, native
spike recoveries, and relative percent differences in the detected
levels are presented in Tables V-7 to V-10. Examination of these
results indicate that with the exception of one treated process
wastewater, that gave an elevated recovery, these experiments
were an unqualified success. These data indicate that the
analytical method is relatively insensitive to the variations in
sample composition or chemical loading that exist from mill to
mill due to variations in manufacturing processes. While not
every sample matrix has undergone this type of method validation
study, these data provide experimental documentation of the
overall method performance for the matrices tested.
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TABLE V-7
METHOD VALIDATION EXPERIMENT
BLEACHED KRAFT PULPS
Pulp 1 (DE020902)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 2 (86374612)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 3 (DF024411)
Duplicate
Matrix Spike
Spike Duplicate
Pulp 4 (RG1-86367)
Duplicate
Matrix Spike
Spike Duplicate
Concentration
(ppt.pg/gm)
15.2
16.3
47.5
51.7
10.2
11.0
37.5
38.0
3.89
3.99
15.9
15.8
55.7
46.7
161
171
2378-TCDD
% Spike
RPD Recovery
7
105
9 118
8
99
1 102
3
110
1 109
18
92
6 100
Concentration
(ppt.pg/gm)
333
1064
912
54.3
64.4
211
203
7.68
7.9
21.5
21.6
181
183
575
559
2378-TCDF
% Spike
RPD Recovery
121
15 96
17
112
4 107
3
84
0 84
1
92
3 87
NOTE: (1) RPD - Relative Percent Difference.
(2) Each analysis (original, duplicate, matrix spike, and matrix spike
duplicate) was conducted on a separate aliquot of unprocessed sample.
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TABLE V-8
METHOD VALIDATION EXPERIMENT
WASTEWATER TREATMENT SLUDGES
Sludge 1 (DE026011)
Duplicate
Matrix Spike
Spike Duplicate
Sludge 2 (R61-86387)
Duplicate
Matrix Spike
Spike Dupl icate
Sludge 3 (DF024606)
Duplicate
Matrix Spike
Spike Duplicate
Sludge 4 (DE020920)
Duplicate
Matrix Spike
Spike Duplicate
Concentration
(ppt,pg/gm)
3.37
3.27
13.0
11.8
193
168
552
576
19.2
17.4
71.2
64.0
37.4
35.8
119
127
2378-TCDD
% Spike
RPD Recovery
3
97
10 86
14
88
4 95
10
106
11 91
4
104
7 115
Concentration
(ppt.pg/gm)
42.6
34.5
142
148
879
670
2641
3023
35.7
31.9
129
125
624
732
2023
1883
2378-TCDF
% Spike
RPD Recovery
21
104
4 111
27
99
13 119
11
95
3 91
16
113
7 101
NOTES: (1) RPD - Relative Percent Difference.
(2) Each analysis (original, duplicate, matrix spike, and matrix spike
duplicate) was conducted on a separate aliquot of unprocessed sample.
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TABLE V-9
METHOD VALIDATION EXPERIMENT
TREATED PROCESS WASTEWATER
Effluent 1 (86374645)
Dupl icate
Matrix Spike
Spike Duplicate
Effluent 2 (DE026006)
Dupl icate
Matrix Spike
Spike Duplicate
Effluent 3 (DF024512)
Dupl icate
Matrix Spike
Spike Dupl icate
Effluent 4 (RG1-86388)
Dupl icate
Matrix Spike
Spike Duplicate
2378-TCDD
Concentration % Spike
(ppt,pg/gm) RPD Recovery
0.0157
0.0145 8
0.0550 95
(2)
ND(0.0034)
ND(0.0042)
0.0156 158
0.0125 22 125
ND(0.0075)
ND(0.0072)
0.0203 115
0.0178 13 101
0.0881
0.0953 8
0.538 112
(2)
2378-TCDF
Concentration % Spike
(ppt,pg/gm) RPD Recovery
0.133
0.110 19
0.376 97
(2)
0.0085
0.0140 49
0.0279 84
0.0365 27 126
ND(0.0069)
ND(0.0066)
0.0187 106
0.0253 30 143
0.447
0.441 1
2.140 85
(2)
NOTES: (1) RPD - Relative Percent Difference.
(2) Not analyzed due to insufficient sample volume.
(3) Each analysis (original, duplicate, matrix spike, and matrix spike
duplicate) was conducted on a separate aliquot of unprocessed sample.
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TABLE V-10
METHOD VALIDATION EXPERIMENT
COMPOSITE CAUSTIC EXTRACTION STAGE WASTEWATER SAMPLE
Sample
Matrix Spike
Spike Duplicate
Concentration
(ppt,pg/gm)
961
2774
3010
2378-TCDD
RPD
8
% Spike
Recovery
87
94
2378-TCDF
Concentration
(ppt.p'g/gm)
7080
20,312
23,301
RPD
14
% Spike
Recovery
85
99
NOTE: (1) RPD - Relative Percent Difference.
(2) Sample consisted of a composite of equal volumes
of the caustic extraction stage samples collected
at each of the five mills. Sample was not run in
duplicate.
(3) Each analysis (original, matrix spike, and matrix
spike duplicate) was conducted on a separate
aliquot of the composite sample.
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6. Inter-Laboratory Method Comparison
A limited inter-laboratory method comparison study was at-
tempted involving Dow Chemical and Brehm Laboratory, Wright State
University (WSU). At the outset of the study, two wastewater and
two sludge samples were analyzed by both laboratories. The data
and the relative percent difference (RPD) are presented below:
Sample
Number
DE020915
Wastewater
2378-TCDD
2378-TCDF
Concentrations (ppt)
Dow*
0.150
2.50
WSU
Range
Mean
0.296
NA**
RPD
65
DE020922
Wastewater
DE020920
Sludge
DE020923
Sludge
2378-TCDD 0.073 (0.111-0.150) 0.124 52
2378-TCDF 1.00 ~ 2.18 74
2378-TCDD 17.0 (35.8-37.4) 36.6 73
2378-TCDF 300 (624-732) 678 77
2378-TCDD 240 (317-470) 394 49
2378-TCDF 2300 (3270-4190) 3730 47
* The Dow Chemical analytical results for 2378-TCDF
may reflect the presence of co-eluting isomers.
** NA - Sample consumed in analytical method development
experiments.
The Dow Chemical results confirm the presence of 2378-TCDD
and 2378-TCDF in these samples. However, the mean RPD of 62%
indicates notable differences in reported concentrations when
compared to the high degree of precision achieved for intra-
laboratory and field duplicate samples. The bias observed in
the data is consistent in both direction and magnitude. These
differences can be attributed to variations in extraction and
cleanup procedures and to the fact that different calibration
standards were used. Additional inter-laboratory method com-
parisons have not been conducted as part of this study. The
above data clearly indicate the need for further inter-laboratory
studies involving these atypical sample matrices.
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B. Chlorinated Phenolics
Selected water and wastewater samples were analyzed for the
following chlorinated phenolics using NCASI GC/MS analytical
methods (Technical Bulletin No. 498, July 1986):
Chloroguaiacols
4,5-Dichloroguaiacol
3,4,5-Trichloroguaiacol
4,5,6-Trichloroguaiacol
Tetrachloroguaiacol
Chlorovanillins
5-Chiorovan ill in
6-Chlorovanillin
5,6-Dichlorovanillin
Chlorophenols
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
1,4/2,5-Dichlorophenol
3,4-Dichlorophenol
2,5-Dichlorophenol
2,3-Dichlorophenol
2,4,5-Tr ichlorophenol
Pentachlorophenol
A revised quantitation procedure (May 1987) incorporating
stable isotope internal standards was used in the analysis of
samples from Mills C, D, and E. All analyses were completed by
NCASI at its West Coast Regional Center located at Corvallis,
Oregon. The NCASI methods are fully described in Attachment D.
C. Total Suspended Solids and Biochemical Oxygen Demand
Selected water and wastewater samples were analyzed for total
suspended solids and five-day biochemical oxygen demand by mill
laboratories for four mills and by a local water authority for
one mill. The analytical methods used were those contained in
Standard Methods for the Examination of Water and Wastewater,
15th Edition, 1980
Analysis of Water
(APHA, AWWA, WPCF)
and Wastes, EPA
USEPA, EMSL-Cincinnati, Ohio,
; or, Methods for Chemical
600/4-79-020, March 1979,
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VI. QUALITY ASSURANCE
A. 2378-TCDD and 2378-TCDF
1. Quality Assurance Objectives
Prior to undertaking the five-mill screening study, data
quality objectives for precision, accuracy, and completeness were
established. The primary goal was to provide reliable measure-
ments of the concentrations of 2378-TCDD and 2378-TCDF at low ppt
levels in solids and low ppq levels in liquids. The approach
included the isotope dilution analytical methodology used in the
National Dioxin Study. An isotopically labelled analogue (l^c
labelled) for each of the target compounds was added as early as
possible in the sample preparation process. This labelled compound
would then be present throughout the entire extraction, cleanup,
and instrumental analysis. Any losses of the unlabelled naturally
occurring TCDD or TCDF would be; mimicked by the labelled TCDD or
TCDF. Therefore, operational problems would be compensated for
and final recoveries of the labelled analogues would serve as
indicators of overall method efficiencies.
In this discussion, 2378-TCDD and 2378-TCDF results are
evaluated as two separate analyses on the same sample even though
the sample extraction, multi-column cleanup, and concentration
steps were common to both compounds. The only divergence in
analytical methodology occurs at the gas chromatographic stage
where capillary columns of different polarities were utilized to
ensure isomer specificity for both 2378-TCDD and 2378-TCDF.
a. Laboratory precision
As noted in the analytical methods section, a considerable
amount of sample processing, i.e., drying, blending, filtering,
splitting, etc., takes place before the extraction and cleanup
stages. Therefore, documenting laboratory precision was of
paramount importance. This was done by carrying out replicate
analyses of sample aliquots and calculating the relative percent
difference (RPD). In cases where multiple determinations were
made, the percent relative standard deviation (% RSD) was cal-
culated. Duplicate aliquots of samples were also spiked with
2378-TCDD and 2378-TCDF and the precision evaluated by comparison
of these concentrations. A QA objective of precision £50% RPD
was established for this study.
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b. Field precision
Field precision targets were not established prior to initia-
ting this screening study due to the wide range of matrix types,
variability of solids content, and the collection of both grab
and multi-hour composite samples. However, a selected number of
field duplicate samples for each type of sample matrix were
collected and analyzed to provide an indication of field sampling
precision.
c. Accuracy
The accuracy of the analytical process was evaluated by
analyzing samples spiked with known amounts of 2378-TCDD and 2378-
TCDF. Subsequently, percent recoveries of the spiked compounds
were calculated. This was done in addition to calculating the
percent recoveries of the labelled dioxin and furan to provide an
estimate of the accuracy of the analytical system. Since valid
measurements of accuracy require reasonable spike levels, samples
were analyzed once, to determine the native concentration, and
then reextracted and reanalyzed after spiking at a level of 2 to
3 times the native concentrations.
d. Completeness
A target of 80%-100% completeness was established at the
beginning of the study. This was the percentage of sample analyses
that met all other QA objectives. Since a substantially larger
number of samples, particularly background and chemical additives,
were collected than were essential to characterize mill operations,
completeness is a measure of the percentage of the samples analyzed
deemed critical by the project manager that were subjected to
analysis.
e. Internal standard recovery
One of the quality assurance targets established at the
beginning of the screening study was that the recoveries of the
isotopically labeled internal standards should be in the range of
40%-120%. As mentioned in the analytical protocol, the internal
standards 13C-, 2-2378-TCDD, 13C12-2378-TCDF, and 37C14~1278-TCDF
are added to the samples before sample processing, carried through
the entire extraction and cleanup process, and finally quantified
against 13C12~1234~TCDD and C14-1278-TCDF added prior to in-
jection on the GC/MS.
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2. Quality Assurance Results for 2378-TCDD and 2378-TCDF
Table VI-1 provides a tabulated summary of how well the QA
objectives were .met in the course of the study. As indicated in
the previous section concerning the methods validation experiments
(V.A.5), three matrices believed to be the most environmentally
significant were selected for extensive laboratory duplicate,
spike and spike duplicate analyses. In addition, a similar group
of analyses were carried out on a five-mill caustic extraction
stage composite sample. These results are presented in detail in
Tables V-7 to V-10.
In the course of carrying out the analytical portion of the
study, it was noted that certain samples had internal standard
recoveries of less than 40%, primarily for the 2378-TCDF internal
standard. For the majority of these instances, the recoveries
were in the 30%-40% range and gave acceptable signal to noise
(S/N) ratios. In addition, the samples in which 2378-TCDD or
2378-TCDF were not detected, had detection limits that were judged
acceptable for the purposes of the study.
In order to better assess any possible impact that internal
standard recoveries less than 40% may have on data quality or
usability, leading chemists in the field of dioxin/furan analyses,
in both the public and private sectors, were polled. These
reviewers were in general agreement that internal standard re-
coveries of less than 40% could produce usable data. Several
commented that the analytical system would have to meet criteria
regarding adequate S/N, correct isotope ratios, and correct mass
measurements. The possible impact of decreased S/N would be
questionable extraction or cleanup efficiency, elevated detection
limits, and decreasing precision.
Careful examination of the analytical data acquired in this
study showed 11 samples that had pairs of positive results
with internal standard recoveries bracketing the 40% criterion.
Calculation of the relative percent difference (RPD) between the
two concentrations for each sample resulted in RPDs less than 50%
for 10 of the 11 samples. The one outlier had an RPD of 62%.
The mean RPD for the 11 samples was 20%. These data clearly
suggest that internal standard recoveries of between 10% and 40%
do not significantly impact quantisation of the target analytes in
this study. Accordingly, for purposes of the mass balance
calculations, the mean of the duplicate results, including results
with low internal standard recoveries, was used to characterize
the sample, provided all other QA criteria were met.
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TABLE VI-1
QUALITY ASSURANCE SUMiMARY
Laboratory Precision as RPD
Quality Assurance Objectives
Number of Determinations^
Range (mean)
Percent Meeting QA Objectives
2378-TCDD
< 50
35
1-138 (15)
97
2378-TCDF
< 50
33
0-62 (16)
97
Field Precision as RPD
Quality Assurance Objectives
Number of Determinations
Range (mean)
NA
8
4-19 (14)
NA
9
0-99 (22)
Accuracy as % Spike Recovery
Quality Assurance Objectives
Number of Determinations^
Range (mean)
Percent Meeting QA Objectives
50-150%
35
66-160 (103)
97
50-150%
35
58-153 (102)
97
Completeness
Quality Assurance Objectives 80-100%
Number of Determinations 133
Percent Meeting QA Objectives 95%
80-100%
133
95%
NOTE: (1) The number of determinations for laboratory precision
and accuracy include those from intralaboratory method
validation experiments (Section V.A.5). Thus, the
percents meeting QA objectives are weighted toward
the mill exports (bleached pulp, treated wastewater
effluent, and wastewater sludge). Refer to the text
for discussion of other sample matrices.
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Analysis of the field duplicates indicated excellent field
sampling reproducibility in the great majority of the cases. Two
dioxin field duplicate pairs ancl one furan pair gave inconclusive
results as one analysis gave a positive result and the other a
nondetect. An evaluation of these results and their use within
the scope of this study are presented Section VII.
QA results on a matrix-specific basis are presented below for
the main matrices of interest.
a. Bleached and unbleached pulps
Bleached pulp was one of the matrices selected for intra-
laboratory method validation experiments. Bleached pulp samples
from four of the five mills were analyzed in duplicate before and
after spiking with 2378-TCDD and 2378-TCDF (see Table V-7).
Fifteen of the sixteen determinations gave RPDs less than 18,
with one analysis being rejected due to a high peak ratio for
m/m+2 for 2378-TCDF in the unspiked sample. This indicates
excellent precision in laboratory operations as these samples
were dried, blended, homogenized,, and subsampled prior to analysis.
All spike recoveries ranged between 84% and 121% indicating
acceptable accuracy. Spike recoveries were comparable (81%-108%)
with those for unbleached pulp. When field duplicates were
analyzed for both the bleached and unbleached pulps, the RPDs
ranged from 0 to 33. Clearly, the pulp matrix is one that can be
accommodated by the field and laboratory protocols and the data
generated are of high quality.
b. Bleach plant wastewaters
Since caustic extraction stage filtrates were determined to be
critical process samples, with high levels of organic materials
and high pH, a composite sample was prepared by blending equal
amounts of the E-stage samples from all five mills. This sample
was analyzed in duplicate after spiking with twice the estimated
concentrations of 2378-TCDD and 2378-TCDF. The results presented
in Table V-10 indicate good precision and accuracy. One additional
laboratory duplicate and two field duplicate determinations for
actual field samples had RPDs of 0 to 5. Note that many of the
initial analyses for caustic extraction stage filtrates had very
low internal standard recoveries and/or high detection limits.
Reanalyses using medium or high resolution were conducted on a
number of these samples to confirm the initial results or improve
detection limits.
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The chlorination stage samples had considerable variation in
both spike recoveries and RPDs. Four sample spikes gave recoveries
ranging from 94% to 160%. The one sample spike recovery of 160%
is out of the QA range of 50-150%. It is probable that this
high recovery is due to sample inhomogeneity rather than method
inaccuracies as the same sample also gave a high RPD of 138. The
five laboratory duplicates covered an RPD range of 3 to 138. The
two field duplicate pairs also gave anomalous results with 2378-
TCDF RPDs covering a range from 13 to 99 and 2378-TCDD giving one
positive result and one nondetect in each case. These samples
were not subjected to additional cleanup and analysis with a view
to lowering the levels of interferring compounds and possibly
confirming the presence of 2378-TCDD. While these analytical data
point to problems in field and laboratory precision for chlori-
nation stage wastewaters, they were judged not so significant as to
render the data unusable.
In contrast, analyses of D-stage and H-stage wastewaters gave
good QC results, with one elevated recovery of 153% for a matrix
spike of 2378-TCDF as the only outlier. The other three matrix
spike results ranged from 99% to 124% recovery. The same sample
that was used for matrix spikes was also analyzed as a field
duplicate, gave acceptable results for 2378-TCDD, and a positive at
0.0272 ppt and an ND at 0.0056 ppt for 2378-TCDF. This is no
clear reason for the discrepancy in the 2378-TCDF results. One
additional laboratory duplicate gave an RPD of 12 for 2378-TCDF.
c. Wastewater treatment sludges
Composite sludges from four of the five mills were analyzed
as part of the method validation experiments and gave excellent
results for all sixteen precision and accuracy determinations.
These results are presented in detail in Table V-8. One composite
sludge was analyzed in quadruplicate using both the routine
protocol and a modified procedure being developed for isomer-
specific determinations of all 2378-substituted PCDDs and PCDFs.
The results gave a 9% RSD for 2378-TCDD and a 12% RSD for 2378-TCDF.
These results demonstrate good sample homogenization and a high
degree of analytical precision. One additional matrix spike
experiment on a primary sludge gave a 90% recovery for 2378-TCDD
and 95% recovery for 2378-TCDF.
d. Treated wastewaters
Since these wastewaters are discharged into streams and rivers,
they are of particular environmental significance. Every attempt
was made to achieve the lowest possible detection limits. A
method validation study was undertaken to determine if any mill-
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specific processing could affect the analytical method performance.
Laboratory duplicates and matrix spike analyses were carried out
on samples from four mills. Matrix spike duplicate results could
only be obtained on samples from two mills due to the lack of
sufficient sample volume from tne other two mills. These results
are presented in detail in Table V-9 and indicate good precision
and accuracy with one outlier, i.e., a recovery of 158% for a
2378-TCDD matrix spike, slightly above the upper bound of the
acceptable range of 50% to 150%. The duplicate analyses for this
sample (DE026006) resulted in no detectable 2378-TCDD at detection
levels of 0.003 and 0.004 ppt, respectively; and the spike level
was about 0.010 ppt. Given that 2378-TCDD might be present in
this sample at less than detectable levels, the computation of
percent spike recovery may be influenced by trace levels of
native 2378-TCDD present. In retrospect, slightly higher spike
levels (e.g., 0.015 or 0.020 ppt) should have been chosen.
Samples from three mills were run in triplicate with results
ranging from 0 to 18% RSD. One sample run in triplicate for
2378-TCDF gave an RSD of 12?. Overall this indicates good
laboratory precision in splitting the effluent samples into
multiple aliquots and in carrying out the analyses.
B. Chlorinated Phenolics
Since chlorinated phenols are known to be produced in the
bleaching process, it was thought that chlorination in the
bleaching stage could be followed by cyclization forming chlori-
nated dibenzodioxin and dibenzofuran products. In order to
determine the amounts and species of chlorinated phenols produced,
selected background, bleach plant, and wastewater samples from
all five mills were analyzed for chlorinated phenols, vanillins,
and guaiacols.
The analytical methodology underwent slight alterations in the
course of this survey in order to utilize procedures more comparable
with the isotope dilution quarititation used for 2378-TCDD and
2378-TCDF. The samples from Mill A were acetytlated, extracted,
and quantitated against 3,4,5--tr ichlorophenol as the internal
standard. Two stable labelled internal standards, namely ^3-2,4-
dichlorophenol and Cg-pentacnlorophenol, were added to the
samples from Mill B prior to derivatization. The samples from the
last three mills were treated in a similar fashion except for
he inclusion of two additional deuterium labelled compounds,
H4-chlorophenol and 2H2-2,4,5-trichlorophenol.
Table VI-2 provides a summary of the results obtained for
duplicate and spike samples analyzed from each of the five mills.
Overall, the data obtained met established quality assurance
objectives.
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-63-
TABLE VI-2
QUALITY ASSURANCE SUMMARY FOR CHLORINATED PHENOLICS
Mill: A B C D
Precision as RPD
QA Objectives £40 £40 £40 £40 £40
No. of determinations 24 8 18 22 1
Range 0-70 2-53 1-93 3-40 5.4
Mean 13 16 18 16 5
% meeting QA objectives 96 88 94 100 100
Accuracy as % Recovery
QA Objectives 60-140 60-140 60-140 60-140 60-140
No. of determinations 65 28 42 42 14
Range 52-149 82-127 71-122 63-125 66-98
Mean 93 108 99 99 85
% meeting QA objectives 95 100 100 100 100
Completeness
QA Objectives 80-100 80-100 80-100 80-100 80-100
No. of determinations 98 126 112 112 154
% meeting QA objectives 96 99 99 100 100
NOTE: (1) For Mill A, the quality assurance summary includes one
sample analyzed by GC/EC. The data for Mill A do not
include spike recoveries for spike levels less than twice
the background.
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-64-
VII. RESULTS AND DISCUSSION
Attachment E contains the master sample lists for the field
surveys conducted at each of the five mills. All samples collected
at each mill are identified by a unique sample number and a brief
description. For those samples analyzed, the following information
is displayed: 2378-TCDD and 2378-TCDF concentrations in ppt;
ratio of monitored molecular ion clusters for identification of
2378-TCDD and 2378-TCDF; percent recoveries of the internal
standards used to quantitate 2378-TCDD and 2378-TCDF; and, for
those samples where both 2378-TCDD and 2378-TCDF were found, the
2378-TCDF/2378-TCDD ratio. Where detectable quantities of 2378-
TCDD or 2378-TCDF were not found, the analytical detection level
is presented with the percent recovery of the respective internal
standard. Positive findings are reported for only those samples
where criteria established for identification of 2378-TCDD and
2378-TCDF were achieved (i.e., 2378-TCDD, 320/322 ratio (0.65 to
0.89); 2378-TCDF, 304/306 ratio (0.65-0.89)). For reference
purposes, the date of the laboratory report for each analysis is
also presented.
The following protocols were followed to establish the
2378-TCDD and 2378-TCDF concentrations used in this report for
mass balance calculations:
1. For samples with no detectable levels of 2378-TCDD or
2378-TCDF, concentrations of zero were assigned.
2. For samples with multiple analyses (blind or known field
duplicates and laboratory duplicates), the mean values of
the multiple analyses were used to characterize the
samples, with nondetects counted as zero.
There were three field duplicate sample pairs where duplicate
2378-TCDD analyses yielded a nondetect and a positive finding.
For one of those pairs (Mill D, sample numbers DF024511/604) the
positive finding was used in the mass balance calculations based
upon consideration of findings in tributary streams and the
2378-TCDF/2378-TCDD ratio characteristic of that mill (see Sec-
tion VILA) . There was reasonably good agreement between 2378-TCDF
analyses for this sample pair. For the second sample pair (Mill B,
sample numbers 86374613/73), the average of the 2378-TCDD results
was used based upon consideration of the 2378-TCDF/2378-TCDD
ratio characteristic of that mill. The 2378-TCDF analyses were
in good agreement. For the third sample pair (Mill D, sample
numbers DF024412/605), agreements between the field duplicate
analyses and the laboratory duplicate analyses for sample DF024605
were poor, as was agreement for the corresponding 2378-TCDF
analyses. Lacking any suitable criteria to evaluate these data,
-------
-65-
all results were averaged to characterize this stream. The
resulting 2378-TCDF/2378-TCDD ratio fell in the mid-range of
other samples from Mill D. Finally, there was one field duplicate
sample pair (Mill C sample numbers DE026003/013) where analyses
for 2378-TCDF yield a nondetect and a positive finding. The
average value of these analyses was assigned to this sample.
This had no impact on mass balance calculations since there was
no discharge of wastewater to the mill wastewater treatment
system from this source during the survey. Aside from these four
sample pairs, agreement between analyses of field duplicate
samples and agreement between laboratory duplicate analyses for
the remaining 28 sample pairs was considered good (generally within
±15%). The impact on mass balance calculations would not be
significant had either of the duplicate analytical results been
used for the remaining samples.
The data contained in Attachment E are presented as received
from the laboratory with no editing of significant figures. These
data were used with the mass flow rates of pulps, untreated and
treated wastewaters, and sludges and ashes to compute the mass
flow rates of 2378-TCDD and 2378-TCDF for each mill. The concen-
tration data, mass flow data, and mass flow rates of 2378-TCDD
and 2378-TCDF are presented by mill for each sample in Attachment F.
The mass flows of process waters, treated and untreated waste-
waters, pulps, and sludges and ashes were obtained for the survey
periods from primary measurement devices or from best engineering
estimates by mill personnel. As noted earlier, the mass flow
rates of treated process water, treated effluents, pulps and, to a
lesser extent, sludges are considered to be fairly accurate.
However, in most cases, the mass flow rates of untreated wastewater
streams, particularly bleach plant filtrates, can only be char-
acterized as reasonable estimates. The mass flow data were not
edited as to significant figures for the calculation of mass flow
rates of 2378-TCDD and 2378-TCDF. For purposes of reporting in
this section, the computed mass flow rates of 2378-TCDD and
2378-TCDF were generally rounded to two significant figures.
A. Observation on 2378-TCDF/2378-TCDD Ratio
In the course of obtaining and reviewing analytical results
from the laboratory over a period of several months, certain
trends in the data began to emerge. Among these was the observation
that the ratio of the concentration of 2378-TCDF to that of 2378-
TCDD for samples where both were detected appeared to be somewhat
uniform within mills or within bleach lines. The data for
individual bleach lines for all five mills are presented in Table
VII-1. These data demonstrate considerable variations in the
mean 2378-TCDF/2378-TCDD ratio across the seven bleach lines.
However, for the softwood bleach lines at Mills A, B, D, and E, and
-------
-66-
TABLE VII-1
2378-TCDF/2378-TCDD RATIO
BLEACH LINE SUMMARY
MILL:
Softwood Lines
Bleached Pulp
Filtrates
B
Range
Mean
MILL:
Hardwood Lines
Bleached Pulp
Filtrates
Range
Mean
c
Eo
H}
H
16
21.1
16.0
17.9
16.9
.0-21.1
18.0
Hypochlor
9.7
C 14.4
E0 ND
H ND
9.7-14.
—
5.4
CD 2.9 C
E 4.7 E
H 4.4 H
H 6.9
D 4.5
2.9-6.9
4.8
A
ite Peroxide
16.8
C 14.4
E0 7.0
H 4.2
H 7.0
P — —
4 4.2-16.8
9.9
A B
ND 2.0 5.4
1.8 C 3.3 C/D 3.9
1.8 E 1.8 E 4. 5
1.6 H 1.8 D 5.2
1.6-3.3 3.9-5.4
2.0 4.8
C E
ND 3.6
C/D ND C/D 4.9
E0 ND E0 3.9
D ND D 4.8
3.6-4.9
4.3
NOTES; (1) ND - 2378-TCDD not detected.
(2) Mill D - A and B softwood bleach lines with combined
E-stage filtrates.
(3) Mill A - Hardwood bleach lines - common C and
E0-stages; separate E0-stage washers and filtrates.
-------
-67-
for the hardwood bleach line at Mill E, the ratios were remarkably
uniform. The ranges of ratios computed for the hardwood bleach
lines at Mill A and the softwood bleach line at Mill B were
somewhat larger. The 2378-TCDF/2378-TCDD ratio could not be
computed for Mill C because 2378-TCDD was not detected in the
bleached hardwood pulp or bleach plant filtrates from that mill.
Table VII-2 presents 2378-TCDF/2378-TCDD ratios for paper
machine wastewaters, combined untreated wastewaters, final efflu-
ents, wastewater sludges, and landfill leachates for the five
mills. The characteristic high ratio for the softwood bleach
line at Mill A was in evidence for all other samples at Mill A
except for the landfill leachate. In similar manner, the bleach
line ratios observed at Mills D and E were also observed in other
samples from those mills with little variation. For Mill B, the
final effluent and secondary wastewater treatment sludge exhibited
somewhat higher ratios than the bleach plant samples, while the
ratio for the primary wastewater treatment sludge was more in
line with the bleach plant ratio. This possibly suggests prefer-
ential partitioning of 2378-TCDF in biological solids at Mill B.
The limited data preclude a more definitive statement.
Factors accounting for the differences in 2378-TCDF/2378-TCDD
ratios across bleach lines and across mills have not been deter-
mined nor has the possible process significance been formulated.
Controlled laboratory or bench scale research studies would be
necessary to provide insight into the mechanisms of formation of
2378-TCDD and 2378-TCDF.
B. Background Samples
1. Treated Intake Process Waters and Residuals
Table VII-3 presents analytical results for the treated
intake process waters at the five mills. Intake process waters are
obtained from surface waters at three mills and from a combination
of surface water and ground water at two mills. In each case, the
untreated intake process waters are treated by coagulation and
sedimentation or filtration followed by chlorination (residual
chlorine about 1 mg/L) prior to use in the pulp and papermaking
processes. The samples obtained were after chlorination but
prior to any uses. The data indicate no 2378-TCDD or 2378-TCDF
contamination of treated intake process waters at or below the
desired analytical detection level of 0.01 ppt.
For Mill E, a concentrated sample of river water filter
backwash was obtained and analyzed. The solids in this sample
are comprised principally of river sediment and coagulants used
-------
-68-
TABLE VII-2
2378-TCDbV2378-TCDD RATIO
MILL SUMMARY
Bleached Pulp
MILL:
B
D
Softwood Line
Hardwood Line
16.0-17.9 2.9-6.9
4.2-14.4
ND
E
Softwood
Hardwood
Bleach Plant Filtrates
21.1 5.4
9.7, 15.8
— ND, 2.0 5.4
ND — 3.6
1.6-3.3 3.9-5.2
3.9-4.9
Paper Machine Wastewaters
9.3
ND
18.6
ND 3.3, 3.5
Combined Untreated Wastewaters
14.1
ND
ND
2.1
4.7
Final Effluents
17.6
8.1
ND
ND
4.7
Wastewater Sludges
Pr imary
Secondary
Combined
1(5.3 5.3
15.4 9.1
18.5
6.7
11.6
1.8
2.2
1.9
4.3
4.2
Landfill Leachates
4.4
ND
ND
ND
ND
Number
Range
Mean
Std. Dev.
17 9
4.2-21.1 2.9-9.1
13.3 5.7
5.3 2.0
3 11 14
6.7-18.6 1.6-3.3 3.3-5.4
12.3 2.0 4.4
0.5 0.6
NOTE: ND - 2378-TCDD not detected.
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-69-
TABLE VII-3
MILL INPUTS
TREATED INTAKE PROCESS WATERS
[Concentrations in parts per trillion (ppt) or pg/gm.]
2378-TCDD 2378-TCDF
MILL A ND (0.005) NO (0.011)
MILL B ND (0.007) ND (0.010)
MILL C ND (0.005) ND (0.007)
MILL D ND (0.005) ND (0.005)
MILL E ND (0.006) ND (0.007)
NOTE: ND - Not detected; analytical detection level in
parentheses ( ).
-------
-70-
for water treatment prior to chlorination. There are two bleached
kraft pulp and paper mills located upstream from Mill E. 2378-TCDD
was not found in the solids fraction of the Mill E filter backwash
at a detection level of 1.8 ppt. 2378-TCDF was found at about
8 ppt. However, due to low recovery of the internal standard
for the 2378-TCDF analysis (13%), quantitation at that level is
questionable. A second analysis of a much smaller mass of remaining
solid filter residue confirmed the presence of 2378-TCDF; however,
quantitation is again questionable because of the low mass of
sample analyzed. Nonetheless, these data indicate 2378-TCDF is
present in the river system upstream of Mill E. The source or
sources cannot be identified from this information, nor can the
amount removed in the Mill E water treatment process or the mass
amount contributed to the Mill E wastewater treatment system.
Based upon the results obtained for major wastewater flows at
Mill E, the amount of 2378-TCDF contributed to the wastewater
treatment system from the river water filter backwash system is
believed to be a relatively small fraction of the untreated
process wastewater loading.
2. Kraft Pulping Process
Seven unbleached kraft (brownstock) pulps from the five mills
were analyzed for 2378-TCDD and 2378-TCDF. The data are displayed
in Table VII-4. 2378-TCDD was not detected in any of the unbleached
pulps at detection levels ranging from 0.3 to about 1.0 ppt.
2378-TCDF was not found in the unbleached pulps from Mills A, C,
and D at detection levels less than 0.3 ppt.
2378-TCDF was found in the unbleached softwood pulp at Mill B
at 1.5 ppt and in the unbleached softwood and hardwood pulps at
Mill E at 1.1 and 2.3 ppt, respectively. These findings may be
accounted for by reuse of paper machine white waters for brownstock
pulp washing or dilution at both mills. As shown later (Section
VII.D.I, Table VII-16), paper machine white waters contain 0.11 ppt
and 0.17 ppt of 2378-TCDF at Mills B and E, respectively. It is
theorized that the 2378-TCDF is transferred to the brownstock
pulp during pulp washing and dilution. The mass amounts of
2378-TCDF found in the brownstock pulps at Mills B and E are
substantially less than the masis amounts contained in the respec-
tive paper machine white waters discharged to the wastewater
treatment systems. This suggesits that the 2378-TCDF found in the
brownstock pulps may be accounted for by the volume of paper machine
white waters reused at these mills. Representatives from Mills C
and D report no reuse or recycle of paper machine white waters to
the respective pulping processes, while reuse of paper machine
white waters for brownstock pulp dilution is practiced at Mill A.
More detailed mass balance studies would be necessary to determine
-------
-71-
TABLE VII-4
UNBLEACHED KRAFT PULPS
[Concentrations in parts per trillion (ppt) or pg/gm.]
2378-TCDD 2378-TCDF
MILL A
Softwood ND (0.74) ND (0.27)
Hardwood ND (0.31) ND (0.23)
MILL B
Softwood ND (0.95) 1.5
MILL C
Hardwood ND (0.56) ND (0.16)
MILL D
Softwood ND (0.70) ND (0.20)
MILL E
Softwood ND (0.44) 1.1
Hardwood ND (0.98) 2.3
NOTE: ND - Not detected; analytical detection level in
parentheses ( ).
-------
-72-
the extent to which the brownstock pulp findings can be attributed
to this practice. The 2378-TCDF data and the 2378-TCDF/2378-TCDD
ratio for other mill streams also suggest that the brownstock
pulps at Mills B and E may contain 2378-TCDD at less than detectable
levels.
Based upon the negative 237&-TCDD findings and the intermittent
and relatively low level contamination of unbleached pulps with
2378-TCDF, analyses of pulping process and chemical recovery system
wastewaters and lime muds were not conducted in order to conserve
analytical resources. Analyses of preliminary samples from Mill A
(Section V.A.2) indicate no detectable levels of 2378-TCDD or
2378-TCDF in pulping process wastewaters or lime rnud at that mill.
C. Bleach Plant Findings
1. Bleach Plant Chemical Applications
As noted earlier, bleach plant process operating logs were
obtained from the respective mills during the weeks of the field
surveys. The data for the 24-hour sampling periods were reduced
and are presented in Table VII-5 for each bleach line. A
significant finding from this e;xercise is that interpretation of
the process operating logs from different mills is not straight-
forward. Mill personnel sometimes record data entries on log
sheets that are different than called for by the headings on the
logs (e.g., % valve opening vs. gpm of chemical solution); NaOCl
solution strength and flow may not be monitored routinely; and mass
flow rates of chlorine may not be monitored with a reasonable
degree of accuracy. In many ccises, these practices have evolved
over a number of years. They are the reported process control
information most useful for bleach plant operators. However,
these practices created considerable difficulty in determining
reasonably accurate chemical application rates for the sampling
periods for this study. Accordingly, it is strongly recommended
that further mill scale research or monitoring efforts be proceeded
by a thorough review of existing bleach plant process operating
monitoring systems and data reporting procedures.
Notwithstanding, the data reported on Table VII-5 are believed
to be fair representations of chemical applications during the
survey periods for most of the fi^e mills. Data for Mill D are rough
engineering estimates of typical chemical usages determined from
inventories over a monthly period encompassing the field program
for that mill. Deficiencies in monitoring equipment in the
bleach plant precluded collection of more reliable chemical
application rate data for the survey period. Data for the other
mills were developed in large measure directly from the bleach
plant operating logs with adjustments suggested by mill personnel
-------
-73-
TABLE VII-5
BLEACH PLANT CHEMICAL APPLICATIONS
(Ibs/ton of Air Dried Unbleached Pulp)
Mill A - Softwood Bleach Line (June 24-25, 1986)
C12
NaOH
02
NaOCl
PH
PN:
Mill A -
C12
NaOH
02
NaOCl
H202
PH
PN:
Mill B -
Unbleached
Pulp
19.0/19.6/20.
Hardwood Bleach
Unbleached
Pulp
11.6/11.8/12.
Softwood Bleach
Unbleached
Pulp
C
64/75/89
1.8/1.9
3 CEK:
Line (June
C
55/66/73
2.5/2.8
2 CEK:
E0 H H
25/29/32
91.4 76.9
10.3/10.8 8.6/8.8 8.3/8.6
2.9/3.0/3.2
24-25, 1986)
E_ _i N 14 J. N LI HP
22/23/24
61.3 69.5
NA
9.7/10.7 8.2/9.4 8.3/9.3 7.7/8.7
2.7/2.9/3.0
Line (September 8-9, 1986)
Cn
E H H D
C12 50/82/117
C102
NaOH
NaOCl
pH
PN:
NOTES:
11.1/19.6/26.
0/0.6/1.
NA
4 CEK:
(1) Mi nimun/ Average/Maximum
5 8.6/11/12
38/54/72
19/33/52 0/2.7/4.4
10.2/10.7 8.5/8.9 NA 1.9/2.6
2.2/4.6/5.9
( Ibs/ton) .
(2) pH - Minimum/Maximum standard units.
(3) PN - Permanganate number or K number for unbleached
kraft pulp - minimum/average/maximum.
(4) NA - Data not available.
(5) NM - Not measured.
(6) CEK - Caustic extraction stage pulp permanganate
number or K number - minimum/average/maximum.
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-74-
TABLE VII-5 (continued)
BLEACH PLANT CHEMICAL APPLICATIONS
(Ibs/ton of Air Dried Unbleached Pulp)
Mill C - Hardwood Bleach Line (October 15-16, 1985)
Unbleached
Pulp Cn En D
C12 42/50/65
C102 3.7/4.3/5.0 14/15/17
NaOH 15/19/22
02 12/12/14
pH 1.5/1.9 10.5/11.6 MA
PN: 12.9A3.7/14.4 CEK: 2.1/2.3/2.5
Mill D - Softwood Bleach Line - A (December 2-3, 1986)
Unbleached
Pulp C E H
C12 69
NaOH 46
NaOCl 89
pH 2.3 9.5A0.6 7.8/9.1
Pf-J: 22.0/24.3/26.9 CEK: NM
Mill D - Softwood Bleach Line - B (December 2-3, 1986)
Unbleached
Pulp C E H
C12 73
NaOH 53
NaOCl 226
pH 2.3/2.4 9.7A0.6 7.5/8.8
PN: 22.0/24.3/26.9 CEK: NM
Mill E - Softwood Bleach Line (January 13-14, 1987)
Unbleached
Pulp CD EQ H
C12 120/147/191"
C102 3.4 12/13/13
NaOH 108/139/187 2.4 2.4
02 7.1
NaOCl 12A9/28
pH 1.8 10.5/11.3 8.2/9.9 3.9/9.0
PN: 10.1/18.8/24.5 CEK: 2.5/3.0/3.3
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-75-
TABLE VII-5 (continued)
BLEACH PLANT CHEMICAL APPLICATIONS
(Ibs/ton of Air Dried Unbleached Pulp)
Mill E - Hardwood Bleach Line (January 14, 1987)
Unbleached
Pulp
C12
C102
NaOH
02
NaOCl
PH
Cn
76/93/107
1.8/1.9/2.2
1.8
Eo
90/93/97
4.2
11.4/11.5
H
14/23/38
9.9/10.7
D
13 A 5/16
6.5/7.3
PN:
11/16.7/22.4
CEK: 2.1/2.8/3.7
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-76-
in certain cases. The permanganate numbers for the unbleached
kraft pulps fed to the chlorination stages and the minumum and
maximum pH values recorded at each stage of bleaching are also
presented in Table VI1-5.
The bleaching practices at the five mills cover a fairly
broad spectrum of bleaching sequences and chemical application
rates. However, these plants do not represent the full range of
bleaching sequences, bleaching tower configurations, or chemical
application rates in United States bleached kraft pulp and paper
mills. For the five mills, first stage chlorination rates range
from 50 to 108 Ibs Cl2/ton of air dried brownstock pulp, or 2.5%
to 5.4%. Chlorine dioxide is added in the chlorination stage at
four of eight bleach lines at rates of 0.6 to 4.3 Ibs/ton.
Sodium hydroxide is applied from 19 to 139 Ibs/ton in caustic
extraction stages. Oxygen is added in five of eight caustic
extraction stages. Sodium hypochlorite is also applied in two of
eight caustic extraction stages, both with oxygen. For the four
mills with hypochlorite stages, the range of sodium hypochlorite
application rates is 19 to 227 Ibs/ton. These data are used and
discussed in subsequent sections.
2. Unbleached and Bleached Kraft Pulps
The unbleached pulp 2378-TCDD and 2378-TCDF data from Table
VII-4 are presented in Table VI1-6 with the corresponding bleached
pulp data for the five mills. Nine samples of bleached pulp were
collected vs. seven samples of unbleached pulp. At Mill A, the
unbleached hardwood pulp is bleached using CEOHH and CEOHHP
bleaching sequences. At Mill D, the unbleached softwood pulp is
bleached in parallel CEH sequences.
These data clearly show the1 effect of bleaching kraft pulps
on the formation of 2378-TCDD arid 2378-TCDF. 2378-TCDD was found
in seven of nine bleached pulps at concentrations ranging from 3 to
51 ppt and 2378-TCDF was found in eight of nine pulps at levels
ranging from 8 to 330 ppt. The median and mean concentrations
are presented below with nondetects counted as zero:
2378-TCDD 2378-TCDF
Median 5 ppt 50 ppt
Mean 13 ppt 93 ppt
There does not appear to be a clear relationship between the
type of wood pulp processed and the concentrations of 2378-TCDD
or 2378-TCDF found in the fully bleached pulps. At the outset of
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-77-
TABLE VI1-6
UNBLEACHED AND BLEACHED KRAFT PULPS
[Concentrations in parts per trillion (ppt) or pg/gm.]
2378-TCDD
MILL A
Softwood
Hardwood
MILL B
Softwood
MILL C
Hardwood
MILL D
Softwood A
Softwood B
MILL E
Softwood
Hardwood
Unbleached Pulp Bleached Pul]
ND (0.74)
NO (0.31)
ND (0.95)
ND (0.56)
ND (0.70)
ND (0.70)
ND (0.44)
ND (0.98)
16
(4.9(H)
3.0(P)
11
ND (0.62)
ND(1.0)
3.9
26
51
2378-TCDF
Unbleached Pulp Bleached Pulp
ND (0.27)
ND (0.23)
1.5
ND (0.16)
ND (0.20)
ND (0.20)
1.1
2.3
330
(47(H)
50(P)
61
15
ND(1.2)
7.8
140
180
NOTES: (1) ND - Not detected; analytical detection level
in parentheses ( ).
(2) Mill A - H = Bleached pulp from CEOHH sequence.
P = Bleached pulp from CEOHHP sequence.
Unbleached kraft hardwood pulp is
processed in common C and Eo stages.
(3) Mill D - A common unbleached kraft pulp is supplied
to both bleach lines at Mill D.
(4) Mill E - The hardwood line bleached pulp sample con-
tained an unknown amount of softwood pulp.
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-78-
this study, it was hypothesized that bleaching of softwood pulps
may result in higher levels of 2378-TCDD and 2378-TCDF based upon
the higher lignin content typically found in softwoods. However,
the data displayed in Table VII--6 do not support that hypothesis.
Note that although precautions were taken in the field to insure
that hardwood pulp was sampled on the B bleach line at Mill E
after a change over from softwood pulp bleaching, a review of
process operating logs indicates the pulp sample designated as
hardwood contains undetermined amounts of both hardwood and
softwood pulp. The relatively high concentrations of 2378-TCDD
and 2378-TCDF in that sample and the uncertainty surrounding its
actual composition confuses this analysis. Variables other than
the general wood type furnished to the bleach plant would appear
to have more influence on the formation of 2378-TCDD and 2378-TCDF.
It should be noted that the results presented in Table VII-6 may
not account for either sampling or process variability and it
would be inappropriate to generalize further on the effect of
wood species with this limited data base. This question is
examined further in Section VII.C. 5. in the context: of the relative
amounts of lignin removed during bleaching.
The pulp samples were squeezed during collection to remove
any loose water in the pulp mat and the pulps were analyzed on
dry weight basis. Hence, the 2378-TCDD and 2378-TCDF concentra-
tions reflect findings on the bleached pulp carried over to the
paper machine areas. The next section presents the findings for
bleach plant filtrates (wastewaters).
3 . Bleach Plant Wastewaters
The bleach plant sampling plan for each mill was focused on
the collection of wastewater sstmples as close to the individual
bleaching stages as possible. In every mill, seal tank overflows
or seal tank contents were sampled following each stage in the
respective bleaching sequence. While sampling in this manner
yielded analytical results for 2378-TCDD and 2378-TCDF close to
process, the computation of mass discharges was confounded by the
overall lack of primary flow measuring devices on these streams.
In some cases, these flows were not continuous. For every bleach
line, best engineering estimates by mill personnel served as the
basis for the wastewater flow rates from each pulp washing stage.
For Mill A, the estimates ,were refined after the field survey by
mill personnel through supplemental field testing. Although the
accuracy of the flow estimates could not easily be verified at
most mills, they are considered reasonable for computing the mass
discharges of 2378-TCDD and 2378-TCDF in these streams. Often
the mills relied upon prior special study situations in which
water balances were estimated for the bleach plant and other
process areas.
-------
-79-
The computation of mass flow rates of 2378-TCDD and 2378-TCDF
from the bleacheries is also affected by the reliability of the
analytical results. As described in Section VI, the analytical
results are considered to be highly reliable with few exceptions.
Analyses of field duplicate samples and duplicate laboratory
analyses for bleach plant samples yielded agreement within ±15%
and recovery of labeled spiked compounds were within acceptable
ranges. Data for two C-stage samples with duplicate field or
laboratory analyses (Mill B - 86374613/73; Mill D - DF024412/605)
did not yield good agreement as discussed above. These data
suggest the possibility of field sampling problems (e.g., collec-
tion of nonrepresentative duplicate samples) or laboratory-related
issues (e.g., nonhomogeneity of sample aliquots analyzed) . Analy-
tical difficulties peculiar to C-stage filtrates may be possible.
As described earlier, the analytical results for 2378-TCDD
and 2378-TCDF presented in Attachment E were combined with the
wastewater flow estimates and pulp production rates to compute
the mass flow rates of 2378-TCDD and 2378-TCDF presented in
Attachment F. While the data contained in Attachment F were
generated with a computer program to more than two significant
figures, the resultant mass flow rates are considered accurate at
most to only two significant figures.
Table VII-7 presents a summary of the bleach line wastewater
data for 2378-TCDD and 2378-TCDF. 2378-TCDD was detected in
bleach line wastewaters from four of five mills, Mill C being the
exception. 2378-TCDF was found in every bleach line wastewater
sampled. Although 2378-TCDD was not found in the bleached pulp
or in bleach line wastewaters from Mill C, it is probably present
at less than analytical detection levels since it was found in
combined paper machine wastewaters and wastewater sludges from
that mill. (Another possible source of 2378-TCDD in the wastewater
sludge at Mill C is purchased bleached softwood pulp from outside
sources.) Generally the highest concentrations and mass discharges
of 2378-TCDD and 2378-TCDF were found in caustic extraction stage
(E or Eo) wastewaters with lesser amounts in hypochlorite (H, H/D)
and chlorination stage wastewaters (C, CD, and C/D) .
Individual bleach line summaries are presented in Tables VII-8
to VI1-12. The summaries include concentrations and estimated
mass loadings of 2378-TCDD and 2378-TCDF in unbleached and bleached
kraft pulps and individual bleach line wastewaters. The estimated
total daily bleach line generation rates of 2378-TCDD and 2378-TCDF
were determined as the sum of the mass flow rates in bleached
kraft pulps and bleach line wastewaters (bleaching stage fil-
trates) . The relatively minor amounts of 2378-TCDF found in
unbleached kraft pulps at Mills B and E were not discounted from
the bleached pulp results for purposes of estimating the amount
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of 2378-TCDF produced in bleach lines at those mills. Also,
recycle of paper machine white waters practiced at some mills was
not taken into account in these calculations owing to the relatively
low-level contamination found in paper machine wastewaters (see
Section D below). The practice of recirculating white waters may
be intermittent depending upon the availability of warm process
water for pulp transport or dilution.
The wastewater data for the softwood bleach line at Mill A
(Table VII-8), the softwood and hardwood lines at Mill E (Table
VII-12), and, to a lesser extent, the softwood lines at Mills B
and D (Tables VII-9 and VII-11) show similar patterns in that the
greatest amounts of 2378-TCDD and 2378-TCDF were found in caustic
extraction stage effluents. That trend is not evident in the
hardwood bleach line at Mill A. At Mill C 2378-TCDD was not
detected in bleach line wastewaters. The 2378-TCDF data at Mill C
show an even distribution in Co-stage and Eo-stage wastewaters.
As noted above, the C-stage and H-stage wastewaters generally
contain significantly less 2378-TCDD and 2378-TCDF than the E-stage
wastewaters.
The bleach plant wastewater data do not clearly distinguish the
point or points of dioxin formation in the bleacheries. However,
these data indicate formation in the C stages and possibly in the
E stages. It is not possible with these data to determine whether
2378-TCDD and 2378-TCDF are formed in the highly acidic C stage
and extracted from the pulp in the E stage, or, whether there is
additional formation in the highly alkaline environment of the E
stage. The data also suggest formation of 2378-TCDD and 2378-TCDF
in subsequent bleaching stages. This point is particularly
evident from the Mill D data which show that 2378-TCDD and 2378-TCDF
can be found in the final hypochlorite bleaching stage. Rigorous
mass balance studies around each bleaching stage in several
bleach lines are necessary to fully investigate this question.
Recent data from other researchers where inter-stage pulp samples
were collected in bleach lines suggests that 2378-TCDD and
2378-TCDF formation is concentrated in the chlorine stage.4'5
4. Distributions of 2378-TCDD and 2378-TCDF
Total bleach line exports of 2378-TCDD and 2378-TCDF are
presented in Table VII-13 with the distribution between pulp and
wastewater from each line. Within each bleach line the distribu-
tions of 2378-TCDD and 2378-TCDF agree within 4%, which is
substantially less than the sampling and analytical error and
uncertainty in wastewater flow measurements expected in this
study. These data indicate the partitioning of 2378-TCDD and
2378-TCDF between bleached pulp and wastewaters within bleach
lines is essentially the same. There is considerable variability
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-89-
in the distributions between pulp and wastewaters across the
eight bleach lines. There is no obvious pattern associated with
the type of pulp bleached or the degree of application of bleaching
chemicals. Factors accounting for these differences are not
known, but may be related to the efficiency of chemical mixing
within the bleaching reactors, bleach tower pH or temperature,
the efficiency of pulp washing between bleaching stages, or some
mechanism associated with the chemical or physical characteristics
of the partially bleached pulps.
5. Formation of 2378-TCDD and 2378-TCDF
The rates of formation of 2378-TCDD and 2378-TCDF for the five
mills are presented in Table VII-14 computed as follows:
1. From individual bleach line exports - the sum of the
bleached pulp and bleach line wastewater loadings was
divided by the respective brownstock pulp inputs to the
respective bleach lines; and
2. From total mill exports - the sum of the bleached pulp,
treated wastewater effluent, and wastewater sludge load-
ings was divided by the sum of brownstock pulp inputs to the
bleach lines.
This method of presenting the data was initially selected
because it was hypothesized that the major source of 2378-TCDD
and 2378-TCDF was the bleaching process. Thus, reducing the data
based upon the brownstock pulp entering the bleach plant was
considered logical.
For Mills A, B, and C the rates of formation computed from
the total mill exports fall within the range or are close to the
rates computed from the individual bleach line exports. The rates
of formation computed from the total mill exports at Mills D and
E are less than those computed from the individual bleach line
exports. Agreement between the rates of formation computed from
bleach line and total mill exports is considered reasonably good.
The extent to which formation of 2378-TCDD and 2378-TCDF determined
for the bleach lines at the five mills and from the total mill
exports is representative of long-term average conditions at these
mills is not known. The extent to which the data from these mills
are representative of the industry is also not known.
Although the scope of this study was limited to screening for
sources of dioxins at five bleached kraft pulp and paper mills,
there were several hypotheses that developed during the course of
the study regarding the formation of 2378-TCDD and 2378-TCDF. At
the outset, the principal hypothesis was that bleaching of kraft
-------
-90-
TABLE VII-14
FORMATION OF 2378-TCDD AND 2378-TCDF
[10-8 Ibs/ton (kg/kkg) of brownstock pulp bleached]
MILL
A - Softwood
A - Hardwood
From Bleach Line Exports
2378-TCDD 2378-TCDF
20
0.9
360
11
From Total Mill Exports
2378-TCDD 2378-TCDF
7.2
130
B - Softwood
2.6
13
3.0
19
C - Hardwood
ND
3.2
0.14
4.7
D
D
E
E
- Softwood A
- Softwood B
- Softwood
- Hardwood
1.4
5.7
13
20
2.6
12
63
76
0.76
11
1.5
51
MEDIAN!
MEAN
4.1(2.0)
8.0(4.0)
12.5(6.3)
68 (34)
3.0(1.5)
4.4(2.2)
19(9.5)
41(21)
NOTES: (1) ND - 2378-TCDD not detected.
(2) Bleach line exports include bleached pulp and
bleach line wastewater streams discharged from
the process at each bleach line.
(3) Paper mill exports include bleached pulp from
all bleach lines, treated wastewater effluent,
and combined wastewater sludge. The formation
of 2378-TCDD and 2378-TCDF was computed on a
production weighted basis for mills with
multiple bleach lines.
(4) The Mill E hardwood line bleached pulp sample
contained an unknown amount of softwood pulp.
-------
-91-
pulps with chlorine and chlorine derivatives would, in some manner,
give rise to formation of 2378-TCDD and 2378-TCDF. This was
clearly indicated by the results from preliminary sampling at
Mill A (Section V) and was confirmed by the data from full-scale
sampling at the five mills. With that hypothesis confirmed,
attention was directed at using the available data and recorded
process information to explore other relevant hypotheses beyond
the principal one noted above. The data obtained from this limited
study are clearly not sufficient to establish any of the following
hypotheses. However, some useful insights can be gained from the
analyses presented below:
a. Bleaching softwood vs. hardwood kraft pulps
As noted earlier, it was theorized that bleaching softwood
kraft pulps might result in higher rates of formation of 2378-TCDD
and 2378-TCDF than bleaching of hardwood kraft pulps due to the
higher lignin content of softwoods. The data presented in Table
VII-14 do not indicate a clear trend with respect to wood types.
While the formation rates for 2378-TCDD for all of the softwood
bleach lines are higher than those for the hardwood bleach lines
at Mills A and C, the hardwood bleach line at Mill E generated
2378-TCDD at a rate equivalent to the highest softwood bleach
line (Mill A) . (Note the bleached pulp sampled at the Mill E
hardwood bleach line on a short-term basis was a combination of
hardwood and softwood pulps resulting from a process change.)
For 2378-TCDF, the softwood bleach line at Mill A generated more
2378-TCDF per ton of brownstock pulp bleached than did any other
bleach line. (The 2378-TCDF/2378-TCDD ratio for this bleach line
was the highest among all bleach lines sampled). The softwood
and hardwood bleach lines at Mill E also generated considerably
more 2378-TCDF, as well as 2378-TCDD than all other bleach lines
except the softwood line at Mill A. Analysis of particular wood
species beyond the general hardwood/softwood classifications has
not been attempted here but may prove to be worthwhile.
To investigate bleaching of hardwood pulps vs. softwood pulps
further, estimates of lignin removal in the chlorination and
caustic extraction stages in each bleach line were made. The
average CEK number (permanganate number of the partially bleached
pulp after caustic extraction) was subtracted from the average
K-number (permanganate number) of the brownstock pulp for each
bleach line. K-CEK for Mill D was not determined since CEK is
not monitored at the bleach lines at Mill D. The K-CEK values
are uniformly higher for partially bleached softwood pulps.
-------
-92-
Figures VII-1 and VII-2 are plots of 2378-TCDD and 2378-TCDF
formation for each bleach line vs. the difference in permanganate
number from brownstock pulp to partially bleached pulp after the
caustic extraction stages (K-CEK). The bleach lines are designated
by mill and by "h" or "s" for hcirdwood or softwood, respectively.
These graphs show, generally, with increasing lignin removal as
estimated by K-CEK, there is increasing formation of 2378-TCDD
and 2378-TCDF. The data for the hardwood bleach line at Mill E
(Figure VII-1) does not fall within the general trend observed
for most of the other bleach lines. If more softwood pulp had
been sampled during the short-term, 4-hour composite sample at
this line, than was estimated from a review of the log sheets,
the actual K-CEK for the pulp sampled would have been greater,
thus causing the plotted point for that bleach line to fall
closer to those for the softwood bleach lines for Mills A and E.
The same type of change would occur in Figure VII-2 for 2378-TCDF.
The limited data were evaluated with a curve fitting program to
determine whether any linear, exponential, log, or power functions
might describe the results. For Figure VII-1 (2378-TCDD vs.
K-CEK), the r2 value (coefficient of determination) for each
function was less than 0.5, indicating the data do not fit any of
the functions. For Figure VII-2 (2378-TCDF vs. K-CEK) the results
were about the same. Clearly, substantial additional data from
other mills are needed to examine these relationships.
Nonetheless, these limited data appear to provide some support
to the hypothesis that bleaching of kraft softwood pulps results
in greater formation of 2378-TCDD and 2378-TCDF than bleaching of
kraft hardwood pulps. Because of the possible significance of
the results, additional research into this question through
full-scale sampling at other mills is warranted. Care should be
taken to insure that the sampling programs are conducted in a
manner to clearly isolate sampler of hardwood and softwood pulps
on bleach lines that process both types of pulps.
b. Degree of chlorination
The amount of lignin remaining in the brownstock pulp is a
major determinant of the amount of chlorine required in the first
stage chlorination reactor. It was also theorized that the gross
amount of chlorine applied to the pulp may have a substantial
effect on the amounts of 2378-TCDD and 2378-TCDF formed. The
formation of 2378-TCDD and 2378-TCDF at the five mills was evaluated
with respect to applications of chlorine and chlorine derivatives
as follows:
(1) The rate of application of chlorine and chlorine equiva-
lents (Ibs/ton air dried of brownstock pulp) in the first
stage chlorination reactor.
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(2) The rate of application of chlorine and chlorine equiva-
lents (Ibs/ton air dried of brownstock pulp) in the entire
bleaching sequence.
The chlorine equivalents were computed on the basis of the
weight percent composition of chlorine in chlorine dioxide and
sodium hypochlorite (C12EQWT), and on the basis of the chlorine
equivalent oxidizing power of chlorine dioxide and sodium hypo-
chlorite (Cl^EQOX). Table VII-15 presents a summary of the
chemical application rates derived as described above for the
chlorination stage at each bleach line and the total for all stages
of bleaching at each bleach line. The chlorine dioxide and
sodium hypochlorite application rates presented in Table VII-5
were used to compute the chlorine equivalents presented in Table
VII-15. Note that chemical application data presented in Table
VII-15 are averages over the sampling period for each bleach
line. Reference is made to Table VII-5 for the range of values
recorded during the surveys. For the hardwood bleach line at
Mill E, the residence time in the bleach line was taken into
account to the extent possible when computing chemical application
rates to adjust for the short-term (4-hour) sampling period.
This was judged not necessary at the other bleach lines where
24-hour sampling was conducted and the production grades did not
change during the sampling surveys. A two-hour gap in the process
data for the Mill E hardwood bleach line occurred just prior to
the change over. This made determination of actual chemical
application rates during that period impossible.
Figures VII-3 and VII-4 are plots of 2378-TCDD and 2378-TCDF
formed in each bleach line (Ibs x 10~^/ton of air dried brownstock
pulp) vs. the degree of chlorination in the first stage bleaching
tower (Ibs Cl2 applied per ton of air dried brownstock pulp).
Figures VII-5 and VII-6 are similar plots of the formation of
2378-TCDD and 2378-TCDF vs. the equivalent chlorine oxidizing
power (C12EQOX) applied in the first stage chlot: ination reactor,
thus taking into account the oxidizing power of chlorine dioxide
applied in the chlorination stages at certain bleach lines.
Plots of the equivalent chlorine applied in the C-stages on a
weight composition basis (C12EQWT) were also prepared, but are
similar to Figures VII-3 and VII-4 and are not presented here.
The data presented in Figures VII-3 through VII-6 show to a
limited extent, that the bleach lines with higher rates of
chlorination in the C stages produce more 2378-TCDD and 2378-TCDF
in the entire bleach lines. However, there are no quantitative
relationships evident (r2 values for linear, exponential, log,
and power functions were less than 0.5 for Figures VII-3 through
VII-6). Note that these plots deal with the chemical applications
-------
-96-
TABLE VI1-15
CHLORINATION STAGE AND BLEACH LIME CHLORINE APPLICATIONS
(Ibs/ton of Air Dried Brownstock Pulp)
Bleaching Chlorination Stage Bleach Line
Mill Wood Type Sequence Cl2 C12EQWT Cl^EQOX ClpEQWT C12EQOX
Softwood
Hardwood
CE0HH
CE0H
J- — >HHP
75
66
66
75
66
66
75
66
66
115
81
83
235
125
132
B Softwood CDEHHD
82
83
84
98
147
C Hardwood C[}EOD
50
51
61
55
130
D Softwood CEH
Softwood CEH
69
73
69
73
69
73
90
1274
154
2894
Softwood
Hardwood
CDE0D
CDE0D
148
93
149
93
157
98
157
102
208
156
NOTES: (1) Cl2 - Chlorine
(2) C12EQWT - Equivalent chlorine applied based upon the
weight percent composition of Cl2 in C102
and NaOCl:
(C102 x 0.256) and (NaOCl x 0.238)
(3) C12EQOX - Equivalent chlorine oxidizing power applied
based upon oxidizing power of C102 and NaOCl:
(C102 x 2.53) and (NaOCl x 0.952)
[Reference 6]
(4) For the Mill D second softwood bleach line/ H stage
sodium hypochlorite usage is unusually high due to
caustic carryover from an undersized caustic washer.
Mill personnel estimate that roughly one-half of the
sodium hypochlorite applied may be consumed to neutral-
ize excess aklalinity. Accordingly, the following
chlorine equivalents were estimated for this bleach
line and used in subsequent analyses:
C12EQWT - 102 Ibs/ADT
CL2EQOX - 181 Ibs/ADT
-------
-97 -
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-101-
in chlorination stages only while the 2378-TCDD and 2378-TCDF
data are for each bleach line as a whole. Rigorous mass balance
studies around the C and E stages at a number of mills would be
necessary to determine to what extent there is a direct relationship
between first stage chlorination and formation of 2378-TCDD and
2378-TCDF.
Figures VII-7 and VII-8 are plots of formation of 2378-TCDD
and 2378-TCDF vs. the chlorine equivalents (C12EQOX) for the
entire bleaching sequence at each mill. Figure VII-7 shows a much
clearer relationship between the application of chlorine and
chlorine derivatives and formation of 2378-TCDD (r2 0.60 for
exponential function; r2 0.72 for power function). The Mill E
hardwood line appears as the only outlier in Figure VII-7. As
noted earlier, sampling at that mill was conducted for only a
short time after a change over from softwood to hardwood pulp
bleaching. Thus, the pulp sample obtained was a mixture of
undetermined amounts of softwood and hardwood pulp. Also, the
log sheet for that line had a two-hour gap in data just prior to
the change over, making a determination of actual chemical
application rates for the pulp sampled impossible. Discounting
data from that line, the r2 values for the remaining data are
0.87 (linear function); 0.70 (exponential function); 0.78 (log
function;, and 0.80 (power function). These data suggest the
possibility of a quantitative linear relationship between dioxin
formation and the rate of chlorine equivalents applied across
entire bleach lines. In Figure VII-8, the plot for 2378-TCDF is
somewhat skewed by the data for the hardwood line at Mill E and
the softwood line at Mill A. The latter line had the highest
rate of formation of 2378-TCDF. Those data do not fit any of the
above cited functions particularly well (r2 0.45-0.63).
The data presented earlier (Tables VII-8 through VII-12) and
in Figures VII-3 through VII-8, indicate that although most of
the formation of 2378-TCDD and 2378-TCDF may be occurring in the
first stage of chlorination, the formation of 2378-TCDD and
2378-TCDF across the bleach lines is more closely correlated to
the application of chlorine and chlorine derivatives across
entire bleach lines rather than chemical application in the first
stage of chlorination.
-------
-102-
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c. Chlorine dioxide substitution in chlorination stage
In a survey of United States pulp mills, it is reported that
C1C>2 is substituted for some fraction of the chlorine in C-stages
at 82 of 95 bleach lines. 7 The rates of application were reported
to be above 10 Ibs/ton for 16 mills and below 10 Ibs/ton for 66
mills.
Reproduced below is a sunmary of chlorine dioxide (C102)
substitution practiced at Mills B, C, and E during the field surveys
at each mill. Chlorine dioxide is not used at Mills A and D.
C-Stage Chemical Application
Ibs/ton Air Dried BS Pulp Chlorine Dioxide
Mill Bleach Line Chlorine Chlorine Dioxide Substitution
B Softwood 84 0.6 1.8%
C Hardwood 50 4.3 18.4%
E Softwood 147 3.4 5.7%
Hardwood 93 1.9 5.1%
Another hypothesis is that substantial substitution of C102
in C-stages would give rise to lower rates of formation of 2378-TCDD
and 2378-TCDF. The data from bhis survey are far too limited to
validate or disprove this hypothesis. However, it is noteworthy
that 2378-TCDD was not detected in bleached pulp or bleach line
wastewaters at Mill C, with the highest C1C>2 substitution (and
overall lowest chlorine usage in the C-stage). The rates of
formation of 2378-TCDD and 2378-TCDF at Mill E are substantially
higher than at Mill B despite C1C>2 substitution about three times
greater. However, chlorination rates at Mill E were both 11% higher
(Mill E hardwood) and 75% higher (Mill E softwood) than at Mill B.
While data from other mills might be helpful in reviewing this
question, the impact of C102 substitution on formation of 2378-TCDD
and 2378-TCDF can best be studied with controlled laboratory
experiments.
d. Oxidative extraction
Nationally, out of 95 bleach lines for which data were reported,
49 include oxygen addition to caustic extraction stages.7 Of the
eight bleach lines included in this study, oxidative extraction is
practiced at Mill A (softwood and hardwood), Mill C (hardwood),
and Mill E (softwood and hardwood). Sodium hypochlorite is also
added to the caustic extraction stage at the Mill A softwood
bleach line. There are no discernible relationships regarding
formation of 2378-TCDD and 2378-TCDF among the bleach lines at
-------
-105-
these mills or between those bleach lines with or without oxidative
extraction. Since it appears that 2378-TCDD and 2378-TCDF are
principally formed in the C-stages, the impact of different
downstream processes such as oxidative extraction may be of
lesser significance than chemical reactions and environmental
conditions in the C-stages. Here again the impact of oxidative
extraction can best be studied with controlled laboratory or mill
experiments.
e. Recycle of bleach line filtrates
For the five mills included in this study, recycle of bleach
line wash waters is practiced to a significant extent only at
Mill B. As shown in Figure III-5, the D-stage filtrate is recycled
to the C-stage seal tank and the first and second hypochlorite
stage filtrates are recycled to the E-stage seal tank. The
impact of this practice on formation of 2378-TCDD and 2378-TCDF
at Mill B is not known, but thought to be not significant. It is
possible, however, that recycle of bleach line filtrates in
certain circumstances might be significant. For example, should
minor amounts of E-stage filtrates be used for shower water
additions on C-stage washers, process conditions at the point of
addition (high pH with free chlorine and potential dioxin precursor
compounds present) might be conducive to formation of 2378-TCDD
and 2378-TCDF. Review of data from other mills and laboratory
scale research are needed to further explore this question.
Based upon these analyses, it is apparent that the formation
of 2378-TCDD and 2378-TCDF is in some manner related to the degree
of chlorination and lignin content of the brownstock pulp.
However, the limited data and limitations regarding the accuracy
of chemical application data preclude a more rigorous analysis
here. There are undoubtedly other factors that may affect forma-
tion of 2378-TCDD and 2378-TCDF in the bleaching of kraft pulp.
Following is a limited list of possible factors:
(1) Process conditions in the chlorination stage (pH, tempera-
ture, residence time, pulp consistency, and viscosity).
(2) Presence of specific precursor compounds in unbleached
pulp that may be attributable to certain wood species or
pulping practices.
(3) Efficiency of brownstock and partially bleached pulp
washing.
-------
-106-
(4) Efficiency of chemical mixing with unbleached or partially
bleached pulp.
(5) Bleach plant filtrate recycle(s)
vat dilution, or stock dilution.
used for shower water,
(6) Delignification with chemicals other than chlorine prior
to chlorine bleaching,,
An analysis of total mill exports of 2378-TCDD and 2378-TCDF is
presented later in this section. Total mill exports are comprised
of 2378-TCDD and 2378-TCDF contained in bleached pulp, treated
wastewater effluent, and wastewater treatment sludges.
-------
-107-
D. Paper Machine Wastewaters, Utility Ashes, and Landfill Leachates
1. Paper Machine Wastewaters
Paper machine Wastewaters were sampled at each mill at loca-
tions of combined wastewater flow or at individual paper machine
wastewater discharges which were flow-composited into one sample
for analysis after collection. Mill E receives paper machine
Wastewaters from a nearby nonintegrated paper mill for treatment.
The data from that mill are included in this section. Paper machine
wastewater flows were obtained from primary flow measuring devices
or from estimates by mill personnel.
Table VII-16 presents a summary of combined paper machine
wastewater concentrations and mass flow rates for 2378-TCDD and
2378-TCDF. 2378-TCDD was detected in four of six combined paper
machine wastewater samples, ranging from 0.053-0.10 ppt. 2378-TCDF
was detected in each combined paper machine wastewater sample
ranging from 0.015-0.35 ppt. The source of 2378-TCDD and 2378-TCDF
in these wastewaters is assumed to be the bleached pulp slurry fed
to the paper machines. The 2378-TCDD and 2378-TCDF on fine
particulates or in solution is passed from the pulp slurry to the
wastewaters. Except for Mill C where 2378-TCDD was not detected
in bleach line wastewaters, the concentrations and mass discharges
of 2378-TCDD and 2378-TCDF from paper machine wastewaters are
quite small when compared to combined bleach plant wastewaters.
As noted earlier, a possible contributing source of 2378-TCDD
found in wastewater sludges at Mill C may be purchased bleached
softwood pulp used at that mill.
2. Utility Ashes
A selected number of utility samples were analyzed for 2378-
TCDD and 2378-TCDF. These data are presented in Attachments E
and F. 2378-TCDD was not detected in fly ash from Mill A or in
bottom ash and fly ash at Mill E at detection levels ranging from
0.28-0.66 ppt. 2378-TCDF was not detected in these samples at
detection levels ranging from 0.18-0.35 ppt. Ash samples from
the other mills were not analyzed. At some mills, primary and/or
secondary wastewater sludges are disposed of by incineration in
hog fuel boilers. However, this is not practiced at any of the
five mills included in this study.
3. Landfill Leachates
Landfill leachate samples were collected at four mills and a
sludge lagoon effluent sample was collected at Mill D. The
landfill leachate at Mill A is a noncontinuous flow and is composed
of sludge landfill leachate, landfill surface runoff, and ground
-------
•-108-
TABLF: vii-16
COMBINED PAPER MACHINE WASTEWATERS
2378-TCDD
2378-TCDF
Mill
A
B
C
D
E
MEAN
MEDIAN
Mass Loading
Concentration Ibs/day
(PPt,pg/gm) (kg/day) x!0-6
0.
ND
0.
ND
0.
0.
0.
0.
021 0.73(0.33)
(0.0051)
011 0.73(0.33)
(0.0060)
053 8.3(3.8)
10a 2.1(0.93)
031 2.0(0.91)
016 0.73(0.33)
Concentration
(PPt,pg/gm)
0.
0.
0.
0.
0.
0.
0.
0.
19
11
20
015
17
35
17
18
Mass Loading
Ibs/day
(kg/day) x!0-6
6.9
6.2
14
1.2
27
7.2
10
7.1
(3.
(2.
(6.
(0.
(12
(3.
(4.
(3.
1)
8)
D
53)
)
3)
5)
2)
NOTES; (a) Nonintegrated paper mill wastewater
discharged to Mill E for treatment.
(b) ND - Not detected at stated analytical
detection level ( ) .
-------
-109-
water. Leachate wastewater streams are returned for wastewater
treatment at Mills A, C, and E. T,he sludge lagoon sample from
Mill D and the leachate sample from Mill B are discharged directly
to surface waters. Table VII-17 presents a summary of 2378-TCDD
and 2378-TCDF concentrations and mass loadings for landfill
leachates. The data show that only one sample/ Mill A, had a
detectable level of 2378-TCDD (0.025 ppt). The other 2378-TCDD
results were not detected at detection levels ranging from
0.003-0.008 ppt. 2378-TCDF was detected in all but one sample
(Mill C). Positive 2378-TCDF findings ranged from 0.011-0.11 ppt
for the leachate samples. The mass discharges are not significant
when compared to the untreated wastewater loadings from other
pulp and paper mill sources, and relatively small when compared
to treated process wastewater effluent discharges for those mills
with detected levels of 2378-TCDD or 2378-TCDF in treated
effluents.
TABLE VII-17
LANDFILL LEACHATES
2378-TCDD
2378-TCDF
Concentration
Mill (ppt,pg/gm)
A 0.025
B ND(0.004)a
C ND(0.006)
Dc ND( 0.003)
E ND(0.008)
Mass Loadings
Ibs/day
(kg/day)xl0-8
3.8(1.7)
Concentration
(PPt/pg/gm)
0.11
0.011
ND(0.009)
0.016
0.064
Mass Loadings
Ibs/day
(kg/day)x!0-8
17(7.5)
b
7.9(3.6)
3.8(1.7)
NOTES; (a) ND - Not detected at stated analytical
detection levels ( ) .
(b) Flow negligible at time of survey (est
(c) Sludge lagoon effluent.
<50 gal/day)
-------
-110-
E. Wastewater Treatment System Findings
A principle objective of this study was to (a) quantify the
loadings of 2378-TCDD, 2378-TCDF, and other PCDDs and PCDFs to the
general wastewater sewer; (b) determine the removal efficiency in
wastewater treatment; and (c) examine their distribution in the
three wastewater treatment plant export vectors (treated effluents,
combined dewatered sludges, and landfill leachates).
Because of the prolonged residence time in wastewater treatment
systems compared to the general mill sewer flows, the wastewater
treatment system effluents were sampled over a different time
frame to account for the time lag in wastewater treatment. The
specific time lags incorporated into the effluent sampling programs
were as follows:
Mill A None
Mill B -12 hours
Mill C 36 hours
Mill D -16 hours
Mill E -24 hours
The sampling locations selected for the wastewater treatment
systems are identified in Figures III-4, III-?, 111-10, 111-13,
and 111-16. In general the sampling plan for each mill included
the following locations:
1. influent to primary clarifiers or treatment system,
2. effluent discharged to receiving stream, and
3. dewatered sludge (combined or separate).
All five of the mills have activated sludge treatment. Hence,
both primary and secondary sludges were designated as sampling
locations. Discrete sampling of these sludges was physically
possible at Mills A, B, and D,, Mill B did not have a combined
dewatered sludge but did add polymer to the secondary sludge to
aid dewatering. The sludge was sampled prior to and after polymer
addition. The sample without polymer was analyzed.
A number of other special conditions were identified and
incorporated into the sampling plan. The acid sewer from the
bleach plants at Mills B and E bypassed primary clarification.
The influent to wastewater treatment was defined as the sum of the
acid sewer plus the general mill sewer. At Mill B a composite
-------
-Ill-
sample was generated by combining both streams based upon flows.
At Mill C, a 2 MGD portion of the final effluent was recycled
back into the mill as process water. This particular flow was
sampled in the same time frame as the nill process sewers.
Mill D chlorinated a portion of the secondary sludge recycled
to the primary clarifier. This sludge was sampled before and
after chlorination. Mill E treated the wastewater from a nearby
nonintegrated paper mill. This 2.5 MGD flow was also sampled.
Landfill leachates were sampled from four mills and included in
the mass balance for those flows that were returned to the
wastewater treatment.
During and immediately preceeding the sampling program, Mill A
was experiencing upset conditions in the wastewater treatment
system which resulted in significantly higher effluent suspended
solids discharges.
The major results of these analyses are noted in the following
tables. They are grouped according to sample type. The concen-
trations (ppt, pg/gm) presented represent the average of all
analyses (laboratory duplicates and/or field duplicates). The
mass numbers (Ibs/day, kg/day) are based upon the sewer flows
and/or sludge tonnages noted in Attachment F.
1. Influents to Wastewater Treatment
The 2378-TCDD and 2378-TCDF results for influents to wastewater
treatment are shown in Table VII-18. The data are presented for
actual treatment system influents as monitored during the sampling
surveys and as a summary of mass loadings from individual wastewater
sources at the mills. Note that in two cases the influent analysis
resulted in nondetectable 2378-TCDD concentrations at low (ppq)
detection limits. However, when individual flows that make up
this flow were analyzed, detectable concentrations were found.
It is hypothesized that dilution in the combined influent sewer
sample was responsible for reducing the 2378-TCDD concentrations
to levels either at or below the established detection limits for
this matrix. In further use of these values for mass balance
calculations, the influent sample analysis was used unless this
analysis resulted in a nondetectable concentration. In this
case, the influent mass loading to the wastewater treatment plant
(WWTP) was assumed equal to the sum of the loading found in
tributary process sewers. Detection limits were not used or
assumed to be equal to the WWTP influent sample concentration.
Nondetected (ND) concentrations were treated as 0.0 ppt in the
mass balance calculations.
-------
-112-
TABLE VI1-18
SUMMARY OF RESULTS FOR
INFLUENT TO W'ASTEWATER TREATMENT
2378-TCDD
2378-TCDF
Mill A
Concentration
(ppt or pg/gm)
Influent to WWTP1 0.14
Sum of Sources
Mill B
Influent to WWTP2
Sum of Sources
Mill C
Influent to WWTP
Sum of Sources
Mill D
Influent to WWTP
Sum of Sources
Mill E
Influent to WWTP3
Sum of Sources
ND(0.006)
ND(0.003)
0.028
Mass Loading
Ibs/day (kg/day)
2.3(1.0)xl0-5
2.8(1.3)xl0-5
5.3(2.4)xl0-6
7.2(3.3)xl0-7
4.4(2.0)xl0-6
1.0(Q.47)xl0-5
2,l(0.95)xl0-4
I.l(0.52)xl0-4
Concentration Mass Loading
(ppt or pg/gm) Ibs/day(kg/day)
1.9
0.11
0.036
0.063
3.2(1.5)xl0~4
4.9(2.2)xl0-4
3.4(1.5)xl0-5
2.9(1.3)xl0-5
9.5(4.3)xl0~6
3.0(1.4)xl0-5
1.0(0.45)X10-5
2.1(0.97)xl0-5
10.3(4.7)xl0~4
4.8(2.2)xl0~4
NOTES;
(1) Mass loading from influent to WWTP at primary clarifier (DE020921).
Negligible mass loading from landfill leachate (DE020821) discharged
to UNOX system not included.
(2) Synthetic flow weighted sample created from process sewer and acid sewer.
(3) Mass loading includes combined acid sewer (RG1-86388) which bypasses
primary treatment and primary treatment influent (RG1-86386/02).
-------
-113-
2. Wastewater Treatment Sludges
The combined dewatered sludge, primary sludge, and secondary
sludge concentrations and mass loadings for both 2378-TCDD and
2378-TCDF are shown in Table VII-19. In all cases where both
primary and secondary sludges were analyzed, the secondary sludges,
comprised principally of biological solids, contained much higher
concentrations of 2378-TCDD and 2378-TCDF than primary sludges.
The secondary sludges, which are lower in volume than primary
sludges, also contained the greater mass of 2378-TCDD and
2378-TCDF.
3. Treated Process Wastewater Effluents
The final treated effluent concentrations and mass loadings
for both 2378-TCDD and 2378-TCDF are presented in Table VII-20.
With few exceptions, the effluent mass loadings are less than the
estimates of untreated wastewater loadings presented in Table
VII-18. There is no evidence to suggest that 2378-TCDD and
2378-TCDF are destroyed in the wastewater treatment systems.
Rather, it appears that any removal across the treatment systems
is simply mass transfer to the wastewater treatment sludges
(Table VII-19). Estimates of wastewater treatment system removals
(transfer to sludges) for 2378-TCDD and 2378-TCDF were made by
comparing the treated effluent mass loadings with the greater of
the influent mass loadings determined from monitoring at a central
wastewater collection point prior to treatment, or the influent
mass loadings determined from summing the mass loadings from
individual bleach plant streams and other soures such as paper
machine wastewaters (see Table VII-18). The results are presented
in Table VII-20. As noted above, 2378-TCDD and 2378-TCDF treatment
system removals constitute mass transfer from the wastewaters to
the sludges rather than destruction or degradation to other
compounds.
These data show variable results for the five mills. At
Mill A, where effluent suspended solids during the sampling
survey were higher than normal, about 15% of the detected 2378-
TCDD and 2378-TCDF were removed or transferred to the sludges.
The data for Mill B show about 13% removal of the detected 2378-TCDD
and about a 10% increase in 2378-TCDF across the treatment system.
At Mills C and D, where untreated wastewater loadings of 2378-TCDD
and 2378-TCDF were relatively low and effluent suspended solids
were relatively low, nearly all of the detected influent 2378-TCDD
and 2378-TCDF were removed across the treatment systems. Finally
at Mill E, with the highest influent loadings of 2378-TCDD and
2378-TCDF, treatment system removals were estimated at 86%.
-------
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-116-
4. Wastewater Treatment System Mass Balances
The mass balances for the wastewater treatment systems are
summarized in Tables VII-21 and VII-22 for 2378-TCDD and 2378-
TCDF, respectively. The mass balances were based upon the influent
to the wastewater treatment system, the combined dewatered sludge
(primary plus secondary for Mill B) , and the final treated effluent.
TABLE VII-21
SUMMARY OF WASTEWATER TREATMENT MASS BALANCES FOR 2378-TCDD
2378-TCDD Mass
Mill A1
Mill B1
Mill Cl
Mill D
Mill E
Input
(Ibs/day)
2.8 xl0-5
5.3 xl0~6
0.72x10-6
4.4 x!0-6
2.1 x!0-4
Exports
(Ibs/day)
3.0xl0~5
9.0xl0-6
1.4xl0-6
2.2xl0-6
6.2xl0-5
% Exports
Accounted for
by Inputs
95%
59%
51%
200%
340%
NOTES
(D
Influent based upon sum of individual
process sewer mass loadings to wastewater
treatment.
TABLE VII-22
SUMMARY OF WASTEWATER TREATMENT MASS BALANCES FOR 2378-TCDF
2378-TCDF Mass
Mill A1
Mill Bl
Mill Cl
Mill D
Mill E
Input
(Ibs/day)
4.9 xl0-4
3.4 x!0-5
3.1 x!0-5
1.0 x!0~5
1.0 xl0~3
Exports
(Ibs/day)
5.3 xl0~4
7.2 x!0-5
1.9 xl0~5
4.2 x!0~6
2.8 xl0~4
% Exports
Accounted for
by Inputs
92%
47%
160%
240%
370%
NOTES: (1) Influent based upon sun of individual
process sewer mass loadings to wastewater
treatment,.
-------
-117-
The significance of the mass balance calculations shown in
Tables VI1-21 and VII-22 should be reviewed in the context of
both the precision in the 2378-TCDD and 2378-TCDF measurements and
the process sewer flow rates and sludge tonnage values. Section
VI of this report provides a detailed discussion of the quality
assurance/quality control results for each of the major matrices
included in this study. For the sludge and final treated effluent
matrices, the measurement precision estimates were ±15% and
±20%, respectively. The uncertainty associated with the sludge,
effluent, and influent flow rates could not be quantified. The
effluent flow estimates, however, are probably fairly reliable
(<±10%) since the mills are required to monitor flow for NPDES
reporting purposes. The sludge tonnage data, however, are likely
the least reliable and could easily be in error by another ±10%
to 15%.
Furthermore, two of the wastewater treatment influents (Mills B
and C) and two of the treated effluents (Mills C and D) had
nondetectable (ND) 2378-TCDD concentrations. Mill D also had a
nondetected 2378-TCDF concentration in the treated effluent. In
all of these cases, the effluent ND was treated as 0 ppt for the
purposes of the mass balance calculations. The influent masses
for Mills B and C were computed from the sum of less dilute
internal process flows that entered the sewers going to primary
treatment. These flows included both bleach plant and paper
machine white water sources. The large discrepancy at Mill E may
also have been due to the sample collection timing sequence. At
this mill, the influent streams to wastewater treatment were
sampled over a 0 to 24-hour period while the effluent sample
collection was lagged by 24 hours to account for the residence
time in wastewater treatment and collected during the 24- to
48-hour time frame. During the initial 24-hour period, however,
significant process changes occurred relating to the wood species
being bleached. The hardwood bleach line was sampled over a
4-hour period after the 24-hour mill composite sample period for the
balance of the bleach plant and the internal process sewers.
During the 24-hour composite sampling period for the mill, both
softwood and hardwood pulps were bleached on the hardwood bleach
line. The hardwood bleach line filtrates were not sampled during
that period. Thus, the data used for mass balances from the
short-term composite samples obtained on the hardwood line may
not be representative of effluent and sludge conditions during
the 24-hour mill sampling.
In summary, the various possible sources of error noted above
could easily account for the generally poor mass balance calcula-
tions observed for all five mills. Given the low concentrations
-------
-118-
and inherent measurement difficulties at these levels, the mass
balance calculations for both 2378-TCDD and 2378-TCDF were judged
reasonable.
As noted in Table VII-19, the final wastewater effluent
concentrations of 2378-TCDD ranged from ND in two samples (0.003,
0.007 ppt) to 0.12 ppt; and 2378-TCDF ranged from ND (0.007 ppt)
to 2.20 ppt. Because of the significance of this vector, these
values were further examined in the context of a mass balance
between the final effluent and the concentrations of both isomers
of dioxin and furan in the secondary sludges.
It was assumed that the 2373-TCDD and 2378-TCDF associated with
the final treated effluent comes from the unsettled mixed liquor
suspended solids (MLSS) and is partitioned primarily to the solid
phase. An estimate of the final effluent concentration can,
therefore, be calculated from a knowledge of the effluent suspended
solids and the secondary sludge concentrations. The results of
these calculations are summarized in Tables VTI-23 and VII-24.
Suspended solids levels in the final effluents ranged from 14 to
104 ppm (mg/1) and represented nominal wastewater treatment plant
performance at each of the five mills, with the exception of Mill A
which had higher than normal suspended solids discharges during
the sampling survey.
It is interesting to note that the calculated effluent
2378-TCDD and 2378-TCDF concentrations were lower than the measured
concentrations in seven cases but of similar order of magnitude.
In three other cases, nondetectable concentrations of both com-
pounds were observed and the calculated values were lower than
the reported detection limits and also of similar order of
magnitude. Within the limits of the analytical capability for
these measurements (both GC/MS and suspended solids), these cal-
culations suggest that the unsettled mixed liquor suspended solids
(MLSS) could be the major source of 2378-TCDD and 2378-TCDF in
the final treated effluents. Furthermore, since the calculated
concentrations were always lower than the corresponding measured
values, the liquid phase must also contribute some mass to this
export vector. This observation was judged reasonable based upon
the fact that random experimental errors in both suspended solids
and 2378-TCDD and 2378-TCDF measurements would likely produce a
less biased result with some calculated 2378-TCDD and 2378-TCDF
concentrations higher than the measured values.
-------
-119-
TABLE VII-23
APPROXIMATION OF TREATED EFFLUENT 2378-TCDD
CONCENTRATIONS USING SECONDARY SLUDGE ASSUMPTION
Mill A
Mill B
Mill C
Mill D
Mill E
Effluent
Suspended
Solids
(ppm)
104
40
26
14
89
Secondary
Sludge
2378-TCDD
(PPt)
710
90
11
36
500
Calculated
Effluent
2378-TCDD
(PPt)
0.074
0.004
0.0003
0.0005
0.045
Measured
Effluent
2378-TCDD
(PPt)
0.12
0.015
ND(0.003)
ND(0.007)
0.088
Mill
Mill
Mill
Mill
Mill
TABLE VII-24
APPROXIMATION OF TREATED EFFLUENT 2378-TCDF
CONCENTRATIONS USING SECONDARY SLUDGE ASSUMPTION
B
C
D
E
Effluent
Suspended
Solids
(ppm)
104
40
26
14
89
Secondary
Sludge
2378-TCDF
(PPt)
10,900
810
75
78
2,100
Calculated
Effluent
2378-TCDF
(PPt)
1.1
0.032
0.002
0.0011
0.188
Measured
Effluent
2378-TCDF
(ppt)
2.2
0.12
0.011
ND(0.007)
0.42
5. Distribution of 2378-TCDD and 2378-TCDF in Wastewater
Treatment System Effluents and Sludges
A final observation on the distribution of 2378-TCDD and
2378-TCDF in the wastewater treatment plant export vectors is
illustrated in Table VII-25. These data indicate that both
compounds are distributed differently in the sludge and effluent
vectors from mill to mill but consistently within each mill. The
reasons for these differences are not understood. Activated
sludge wastewater treatment with fairly conventional residence
times, aeration capacity, and secondary sludge recycles is provided
at each mill.
-------
-120-
TABLE VII-25
DISTRIBUTION OF 2378-TCDD and 2378-TCDF
IN WASTEWATER TREATMENT EXPORT VECTORS
2378-TCDD 2378-TCDF
% Effluent % Sludge % Effluent % Sludge
Mill A 80% 20% 79% 21%
Mill B 51% 49% 52% 48%
Mill C ~0% -100% 14% 86%
Mill D -0% -100% -0% -100%
Mill E 48% 52% 51% 49%
F. Pulp and Paper Mill Exports
For purposes of this study, export vectors were defined as
the final treated effluent, clewatered sludges, and the final
bleached pulp. At some mills landfill leachates are discharged
separately from the treated process wastewater effluents. The
mass discharges from leachates were not significant compared to
those from other vectors and thus were not considered in this
analysis. In one pathway or another, these materials enter the
environment. Summaries of the results for each mill are presented
in Tables VII-26 and VII-27 for 2378-TCDD and 2378-TCDF, respec-
tively. The most obvious feature of the data shown in these
tables is the variable distribution of 2378-TCDD and 2378-TCDF in
the three export vectors across the mills. The distributions of
2378-TCDD and 2378-TCDF were consistent within each mill.
The distributions in the treated effluents were apparently
related to the final effluent suspended solids content as noted
in Table VII-28. The data in this table suggest a casual relation-
ship between the effluent suspended solids concentration and the
relative distribution of 2378-TCDD and 2378-TCDF in the wastewater
treatment plant export vectors (treated effluent, wastewater
sludge). Generally, higher suspended solids contents resulted in
a greater fraction of the 2378--TCDD and 2378-TCDF associated with
the effluent rather than the sludge.
-------
-121-
TABLE VII-26
MASS AND
Mill A
Mill B
Mill C
Mill D
Mill E
MASS AND
Mill A
Mill B
Mill C
Mill D
Mill E
DISTRIBUTION
Dewa tared
Sludges
% of
Total
16
17
-100
-70
28
DISTRIBUTION
Dewatered
Sludges
% of
Total
17
20
35
-69
27
OF 2378-TCDD
Final
Effluent
% of
Total
65
17
-0
-0
26
TABLE VII
OF 2378-TCDF
Final
Effluent
% of
Total
64
23
6
-0
28
IN TOTAL MILL
Bleached
Pulp
% of
Total
19
66
-0
-30
46
-27
IN TOTAL MILL
Bleached
Pulp
% of
Total
19
57
59
-31
45
EXPORT VECTORS
Total Mass in
Export Vectors
Ibs/day (kg/day)
3.7 (1.7)xl0-5
2.6 (1.2) xl0~5
1.4 (0.64) x!0~6
3.2(1.5)xl0~6
I.l(0.51)xl0-4
EXPORT VECTORS
Total Mass in
Export Vectors
Ibs/day (kg/day)
6.6 (3.0) xl0~4
1.7 (0.75) xl0~4
4.7 (2.1) xl0-5
6.1(2.8) x!0~6
5.1(2.3)xl0-4
-------
-122-
TABLE VI1-28
FINAL TREATED EFFLUENT TCDD/TCDF DISTRIBUTION IN EXPORT VECTORS
VS. EFFLUENT SUSPENDED SOLIDS CONCENTRATION
Effluent
Suspended % of Total % of Total
Solids TCDD in Effluent TCDF in Effluent
(ppm) Export Vector Export Vector
Mill D 15 ~0 ~0
Mill C 36 -0 6
Mill B 40 17 23
Mill E 89 26 28
Mill A 104 65 64
The total mass of 2378-TCDD and 2378-TCDF in the export
vectors (Tables VII-26 and VII-27) can be accounted for by those
process sewers related to the bleach plant. The summaries shown in
Tables VII-29 and VII-30 illustrate the results of these mass
balances. Note that at Mill C, 2378-TCDD was not detected in any
bleach plant samples, although it may be present at less than
detectable levels. The positive findings in paper machine
wastewaters at this mill may be due to papermaking with purchased
bleached softwood pulp.
-------
-123-
TABLE VII-29
FRACTION OF 2378-TCDD FOUND IN
TOTAL MILL EXPORT VECTORS ATTRIBUTED TO
BLEACH PLANT SOURCES
2378-TCDD
from Bleach Plant
Ibs/day(kg/day)
Mill A 3.5(1.6)X10-5
Mill B 2.3(1.0)x!0-5
Mill C 7.3(3.3)x!0-7(l)
Mill D 1.1(0.50)x!0-5
Mill E 1.7(0.77)xl0~4 (3)
2378-TCDD
in Export Vectors
Ibs/day(kg/day)
3.7(1.7)xl0~5
2.6(1.2)xl0-5
1.4(0.64)xl0-6
3.2(1.5)xl0-6 (2)
1.2(0.51)xl0~4
% Accounted
for by Bleach
Plant Sources
94%
86%
0%
360%
140%
NOTES; (1) 2378-TCDD was not found in bleached pulp or bleach
plant wastewater streams. This mass was found in
paper machine wastewaters and may be associated with
purchased bleached softwood pulp used for paper making.
(2) 2378-TCDD was found in the wastewater treatment plant
influent and sludge but not in the effluent. Hence,
the effluent ND(0.007) ppt was assumed to be 0.0 ppt.
2378-TCDD was not found in one bleach line bleached
pulp ND(1.2). This export vector source was also
assumed to be 0.0 ppt.
(3) Sampling was
and softwood
were assumed
not done at the same time on hardwood
bleach lines but the bleach line masses
to be additive to reflect mix of total
mill production during the sampling survey,
-------
-124-
TABLE VII-30
FRACTION OF 2378-TCDF FOUND IN
TOTAL MILL EXPORT VECTORS ATTRIBUTED TO
BLEACH PLANT SOURCES
Mill A
Mill B
Mill C
Mill D
Mill E
NOTES:
2378-TCDF
from Bleach Plant
Ibs/day(kg/day)
6.1(2.8)x!0-4
1.2(0.54)xl0~4
3.2(1.4)xl0~5
2.2(1.0)xl0-5
7.3(3.3)x!0-4 (1)
2378-TCDF
in Export Vectors
Ibs/day(kg/day)
6.6(3.0)x!0-4
1.7(0.75)x!0™4
4.7(2.1)x!0-5
6.1(2.7)X10-6
5.6(2.5)x!0-4
% Accounted
for by Bleach
Plant Sources
92%
70%
68%
360%
130%
(1) Sampling was _n_ot done at the same time on hardwood
and softwood bleach lines but the bleach line masses
were assumed to be; additive to reflect total mill
production during the sampling period.
The footnotes to the tables qualify a number of the sampling
and calculation assumptions made in computing the mass balances.
Given the various possible sources of error discussed earlier in
this section, it is reasonable to conclude that the 2378-TCDD and
2378-TCDF formed are attributable to bleach plant sources in each
mill. The small amounts of 2378-TCDF found in unbleached pulp
from two mills were not significant.
As noted earlier in Section VII.C., the mass formation rates
for both 2378-TCDD and 2378-TCDF in the bleach plants were related
in some manner to the mass amounts of equivalent chlorine (C12EQOX)
applied to the brownstock pulp. Higher chlorine application
rates in the bleach plant generally resulted in greater amounts
of 2378-TCDD and 2378-TCDF formed. Similar correlations are
presented for the total mill export vectors (pulp, sludge, and
treated effluent) in Figures VII-9 and VII-10 for 2378-TCDD and
2378-TCDF, respectively. The /-axis represents the mass of each
isomer found in all three export vectors divided by the brownstock
pulp production. The x-axis represents the total mass amount of
chlorine and chlorine derivatives expressed as equivalent chlorine
(C12EQOX) used in all stages of bleaching. The computations of
-------
- 125-
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-127-
2378-TCDD and 2378-TCDF formed and chemical use were based upon a
production weighted basis for mills with multiple bleach lines.
Since 2378-TCDD and 2378-TCDF are not destroyed or eliminated in
the wastewater treatment systems, these two graphs basically
repeat the correlations shown in Figures VII-7 and VII-8. This
observation is consistent with the fact that the formation of
2378-TCDD and 2378-TCDF is principally attributed to bleach plant
sources.
G. Chlorinated Phenolics
of the five mills, samples were taken at selected
bleach plant, and WWTP locations to be analyzed for
phenols, guaiacols, and vanillins. A list of the
phenolics is found in Table VII-31. Analytical data
for these samples are presented in Attachment G along with several
data summary sheets tabulated by sample type.
At each
background,
chlorinated
chlor inated
TABLE VII-31
CHLORINATED PHENOLIC ANALYTES
Chlorophenols
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
1,4/2,5-Dichlorophenol
3,4-Dichlorophenol
2,5-Dichlorophenol
2,3-Dichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
Chloroguaiacols
4,5-Dichloroguaiacol
3,4,5-Trichloroguaiacol
4,5,6-Trichloroguaiacol
Tetrachloroguaiacol
C h 1 o r o v a n i 11 i n s
5-Chlorovan ill in
6-Chlorovanil1 in
5,6-Dichlorovanillin
Table VII-32 presents chlorinated phenolics mass loading
summaries based upon the analytical results for treated intake
process waters, WWTP influents, and WWTP effluents for the five
mills. Table VII-33 presents a summary of chlorinated phenolics
mass loadings in the bleach plant wastewaters sampled in the five-
mill study. Tables VII-34 and VII-35 present wastewater treatment
system and bleach plant mass loadings normalized to production on
the basis of air-dried brownstock pulp.
The data indicate that none
detected in any of the five mill
detection levels estimated to
of the chlorinated phenols were
treated intake process waters at
be in the 1 to 3 ppb range.
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-129-
TABLE VII-33
CHLORINATED PHENOLICS IN BLEACH PLANT WASTEWATERS
Mass Loadings - Ibs/day (kg/day)
Number: of
Sources
Sum of Chlorophenols
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
Range
ND-0.53(ND-0.24)
0.16-2.3 (0.073-1.3)
ND-0.06(ND-0.027)
ND
Median
0.09(0.41)
0.63(0.29)
0.02(0.009)
ND
Mean
0.17(0.077)
0.92(0.42)
0.03(0.014)
ND
Sum of Chloroguaiacols
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
0.09-2.1 ((3.041-0.95)
2.1-26 (0.95-12)
0.40-0.67(0.18-0.30)
ND-0.18(ND-0.081)
0.25 (0.11)
16 (7.3)
0.50 (0.23)
0.025(0.011)
0.69(0.31)
13 (5.9)
0.52(0.24)
0.06(0.027)
Sum of Chlorovanillins
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
ND-1.9 (ND-0.86)
0.57-13 (0.26-5.9)
0.20-0.43(0.091-0.19)
ND-0.01(ND-0.005)
0.18(0.082)
5.2 (2.4)
0.34(0.15)
0.39 (0.18)
5.5 (2.5)
0.33 (0.15)
0.003(0.0014)
Sum of All Analytes
C-Stages
E-Stages
H-Stages
D-Stages
8
7
4
4
0.13-4.0 (0.059-1.8)
3.1-41 (1.4-19)
0.61-1.1 (0.28-0.50)
ND-0.18(ND-0.082)
9.61(0.28)
22 (10)
0.85(0.39)
0.03(0.014)
1.2 (0.54)
20 (9.1)
0.87(0.39)
0.06(0.027)
-------
-•130-
TABLE VII-34
WWTP MASS LOADINGS - SUM OF CHLORINATED PHENOLICS
[10-3 Ibs/ton (kg/kkg) of brownstock pulp bleached]
Mill
Influent
Effluent
A
B
C
D
E
9.4
15
9.1
33
45
6.4
5.6
0.17
13
1.9
Range
Mean
Median
9.1-45
22(11)
15(7.5)
0.17-6.4
5.4(2.7)
5.6(1.3)
NOTE: Sum of chlorinated phenolics includes chlorinated
phenols, chlorinated guaiacols, and chlorinated
vanillins.
TABLE VII-35
BLEACH PLANT MASS LOADINGS - SUM OF CHLORINATED PHENOLICS
C-STAGE AND E-STAGE FILTRATES
[10-3 Ibs/ton (kg/kkg) of brownstock pulp bleached]
Mill
A-HW
A-SW
B-SW
C-HW
D-SW-A
D-SW-B
E-SW
E-HW(3)
Range
Mean
Median
NOTE: (1)
(2)
(3)
C-Stage
0.51
0.81
3.6
4.0
2.1
4.6
1.8
0.55
0.51-4.6
2.2 (1.1)
1.9 (0.95)
E-Stage
8.8
29
25
34
49(2)
49(2)
46
20
8.8-49
33 (17)
32 (16)
Sum of
C and E Stages
9.3
30
29
38
51
54
48
21
9.3-54
35 (17)
34 (17)
Sum of chlorinated phenolics includes chlorinated
phenols, chlorinated guaiacols, and chlorinated
vanillins.
Common E-stage mass loading allocated equally to
A and B lines.
The Mill E hardwood bleach line filtrate samples
were obtained when an undetermined amount of
softwood pulp was being processed on the line.
-------
-131-
The wastewater treatment plant influent data for chlorophenols
show three chlorophenols were detected at four of the five mills.
with 2,4-dichlorophenol (and 2,4/2,5-dichlorophenol coelution)
making up 99% of the combined five-mill influent chlorophenols
mass loadings. Pentachlorophenol was detected at one mill. Of
the three chlorovanillins analyzed, 6-chlorovani11 in was predomi-
nant and detected at each mill, accounting for about 63% of the
combined five-mill chlorovanillin influent mass loading. Chloro-
guaiacols were found at each mill in more evenly distributed
patterns than the chlorophenols or chlorovanillins. From Table
VII-34, the mean of all chlorinated phenolic influent mass loadings
was 22 x 10~3 Ibs/ton of air-dried brownstock pulp bleached.
Chlorinated phenolic effluent data presented in Table VII-32
show a similar distribution between the various analytes. The
overall reduction of the sum of all chlorinated phenolics across
the wastewater treatment facilities at the five mills was about
82%. From Table VII-34 the mean of all chlorinated phenolic
effluent mass loadings was 5.4 x 10~3 Ibs/ton of air-dried
brownstock pulp bleached.
With respect to internal bleach plant sources of chlorinated
phenolic wastewater streams, the data summarized in Tables VII-33,
VI1-35, and G-10 in Attachment G show that the E-stages accounted
for most of the mass loadings of chlorinated phenolics in the
bleachery samples analyzed in the five-mill study. These findings
are similar to those for 2378-TCDD and 2378-TCDF. (see Section
VII.C.3). The distribution of chlorophenols in the E-stage
wastewater streams generally was similar to that for the WWTP
influents. 2-Chlorophenol was detected in the E-stage wastewaters
at one mill (Mill E, A side) in a trace amount.
With the limited data correlations were not attempted between
chlorinated phenolics and levels of 2378-TCDD and 2378-TCDF present
in wastewater treatment system influents or effluents. Since
chlorinated phenolics were only analyzed on the water matrix, an
evaluation of chlorinated phenolics in bleach plant or total mill
exports could not be made. With the limited and incomplete
wastewater data, mass balance calculations between internal bleach
plant filtrates and wastewater treatment system influents were
not attempted.
H. Total Suspended Solids and Biochemical Oxygen Demand
Selected samples were analyzed for total suspended solids (TSS)
and biochemical oxygen demand (8005). The TSS and BOD5 analyses
were conducted primarily to determine whether there were any
abnormal wastewater treatment system operations during the sampling
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events. Analytical results for TSS and 8005 for the five mills
are presented in Attachment G. Tables VII-36 and VII-37 summarize
TSS and BOD data for the wastewater treatment plant influents and
effluents.
The effluent mass loading data from the five-mill study were
reviewed with respect to typical loadings and percent removals
presented in Section III (Tables III-3, 6, 9, 12, and 15).
Effluent mass loadings for TSS generally were within typical
ranges with the exception of Mill A. As noted in Section VII.E. ,
during and immediately preceding the sampling period, Mill A was
experiencing upset conditions in the wastewater treatment system
which resulted in higher than normal mass loadings in the effluent.
Monthly sewer and WWTP operating reports for Mill A were obtained
for the sampling period and reviewed. According to Mill A
personnel, failure of the white liquor clarifier and disposal
of lime mud into the primary clarifier resulted in an overload of
solids in the wastewater treatment system which took months to
recover a suitable balance in the system. Based upon Mill A
sewer operating reports, fiber losses during the sampling period
were about 30% higher than the yearly average prior to the date
of sampling.
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TABLE VII-36
WASTEWATER TREATMENT PLANT
TOTAL SUSPENDED SOLIDS SUMMARY
Mill
A
B
C
D
E
Cone .
mg/L
654
—
540
875
680
Influent
Mass Loading
Ibs/day (kg/day)
109,700 (49f800)
52,8001(23,900)
141,900 (64,400)
137,600 (62,400)
210,000 (95,200)
Cone
mg/L
104
40
36
15
89
TABLE VII
Effluent
Mass Loading
Ibs/day (kg/day)
20,100 (9100)
12,800 (5800)
8,900 (4000)
2,200 (1000)
30,500 (13,800)
-37
% Removal
82%
76%
94%
98%
86%
WASTEWATER TREATMENT PLANT
BOD5 SUMMARY
Mill
A
B
C
D
E
Cone.
mg/L
175
--
301
232
340
Influent
Mass Loading Cone.
Ibs/day (kg/day) mg/L
29,300 (13,300) 29
48,100! (21,800) 5
79,100 (35,900) 9
36,500 (16,600) 13
105,000 (47,600) 16
Effluent
Mass Loading
Ibs/day (kg/day)
5,600 (2500)
1,500 (680)
2,200 (1000)
2,000 (910)
5,500 (2500)
% Removal
81%
97%
97%
95%
95%
NOTES: (1) Mill B influent mass loadings calculated
from data from two process sewers.
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VIII. FINDINGS AND CONCLUSIONS
A. Data Quality and Data Limitations
1. The analytical protocol foc 2378-TCDD and 2378-TCDF developed
for this study was found to be satisfactory for isomer-specific
determinations of 2378-TCDD and 2378-TCDF in selected pulp and
paper mill sample matrices. Intra-laboratory method validation
experiments for pulp, sludge, and wastewater effluent samples
indicate the performance of the analytical method with respect to
precision and spike recovery is demonstrably uniform. The method
performance does not appear to be sensitive to any specific
matrix or chemical effects which might be associated with the
manufacturing processes at a given mill. Limited inter-laboratory
comparisons incorporating different sample preparation, cali-
bration standards, and analytical methods confirmed the presence of
2378-TCDD and 2378-TCDF in selected samples. However, a consistent
bias was observed for quantitation of both 2378-TCDD and 2378-TCDF.
2. With few exceptions, the data quality assurance objectives
established for this study for 2378-TCDD and 2378-TCDF were
achieved.
(a) Laboratory precision expressed as relative percent differ-
ence between duplicate analyses for thirty-five 2378-TCDD
determinations was 15 percent mean (range 1-138 percent);
and for thirty-three 2378-TCDF determinations, 16 percent
mean (range 0-62 percent).
(b) Field precision for eight 2378-TCDD determinations was
14 percent mean (range 4-19 percent); and for nine 2378-
TCDF determinations, 22 percent mean (range 0-99 percent).
(c) For thirty-five 2378-TCDD determinations, accuracy ex-
pressed as percent spike recovery was 103 percent mean
(range 66-168 percent); and for thirty-five 2378-TCDF
determinations, 102 percent mean (range 58-153 percent).
(d) Including results from intra-laboratory method validation
experiments, 97 percent of the analyses met the quality
assurance objectives for laboratory precision and accu-
racy. Ninty-five percent of 133 determinations for
2378-TCDD and for 2378-TCDF resulted in analytical data
suitable for project objectives.
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(e) Target analytical detection levels of 1 ppt for solid
samples were achieved for all but one sample for 2378-TCDD
and all but one sample for 2378-TCDF (different samples).
Target analytical detection levels of 0.01 ppt for liquid
samples were achieved for all but three samples for 2378-
TCDD and all but two samples for 2378-TCDF (different
samples) .
3. Mass flow calculations for 2378-TCDD and 2378-TCDF combine
analytical results with mass flow rates of solid materials (pulps,
sludges) and liquids (waters, wastewaters). The mass flow rates
for pulps and final treated wastewater effluents are considered
to be accurate within less than ±10% while mass flow rates for
sludges, within less than ±10% to 15%. Mass flow rates for
internal plant wastewaters were generally based upon best engi-
neering estimates and are considered accurate to less than ±20%
to 25%. The reliability of reported bleach plant chemical
application rates varied considerably from mill to mill, and in
two cases, were best engineering estimates. The calculations and
analyses presented in this report should be viewed accordingly.
B. PCDDs and PCDFs Found in Pulp and Paper Mill Matrices
1. Analyses of samples obtained at a number of bleached kraft
pulp and paper mills for polychlorinated dibenzo-p-dioxins (PCDDs)
and polychlorinated dibenzofurans (PCDFs) uniformly show that
2,3,7,3-tetrachlorodibenzo-p-dioxin (2378-TCDD) and 2,3,7,8-tetra-
chlorodibenzofuran (2378-TCDF) are the principal PCDDs and PCDFs
found. This is particularly evident when the data are considered
in light of USEPA's 2378-TCDD toxic equivalents approach for
dealing with mixtures of PCDDs and PCDFs.
2. Data for the five mills included in this study show there is
a characteristic 2378-TCDF/2378-TCDD ratio associated with indi-
vidual bleach lines and individual mills, ranging from about 2 to
about 18. This observation suggests that once 2378-TCDD and 2378-
TCDF are formed, they are not altered in further processing or in
wastewater treatment. Factors accounting for the differences in
2378-TCDF/ 2378-TCDD ratios across bleach lines and across mills
have not been determined, nor has the possible process significance
been formulated.
C. Sources of 2378-TCDD and 2378-TCDF
1. 2378-TCDD and 2378-TCDF are formed during the bleaching of
kraft hardwood and softwood pulps with chlorine and chlorine
derivatives at mills included in this study.
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2. 2378-TCDD was not detected in seven unbleached kraft pulps
collected at the five mills at detection levels ranging fronti 0.3
ppt to 1.0 ppt. 2378-TCDF was not detected in four of seven
unbleached pulps at detection Levels less than 0.3 ppt, but was
found in three pulps collected at two mills at levels ranging
from 1.1 to 2.3 ppt. The positive 2378-TCDF findings in unbleached
pulps may be attributed to reuse of contaminated paper machine
white waters for brownstock pulp washing or dilution.
3. 2378-TCDD was found in seven of nine bleached pulps collected
at the five mills at concentrations ranging from 3 to 51 ppt and
2378-TCDF was found in eight of nine bleached pulps at levels
ranging from 8 to 330 ppt. The median and mean concentrations
are presented below with nondetects counted as zero:
2378-TCDD 2378-TCDF
Median 5 ppt 50 ppt
Mean 13 ppt 93 ppt:
4. 2378-TCDD and 2378-TCDF were found in most untreated bleach
line filtrates sampled from the five mills. Wastewaters from
caustic extraction stages (E and Eo) generally contained the
highest concentrations and mass discharges from the bleach lines
sampled.
5. The distributions of 2378-TCDD and 2378-TCDF in bleach line
exports (bleached pulp and bleach plant wastewaters) were found
to be highly variable from bleach line to bleach line. However,
2378-TCDD and 2378-TCDF were jparti t ioned similarly to bleached
pulps and bleach plant wastewaters within each bleach line.
6. 2378-TCDD was found in paper machine wastewaters from three
of five mills and 2378-TCDF was found in paper machine wastewaters
from each mill. The levels of 2378-TCDD and 2378-TCDF found in
paper machine wastewaters were significantly less than found in
the respective bleach plant wastewaters at four of five mills.
The source of 2378-TCDD and 2378-TCDF in paper machine wastewaters
at these mills is believed to be the bleaching operations. At
one mill, 2378-TCDD was not detected in any bleach plant sources
but was found in paper machine wastewaters. Purchased bleached
pulp used at that mill may be ci possible source.
7. 2378-TCDD was found in one; of five sludge landfill leachate
or runoff samples at 0.025 ppt, while 2378-TCDF was found in four
of five samples at levels ranging from 0.01 to 0.11 ppt. 2378-TCDD
and 2378-TCDF were not detected in coal-fired power boiler ash
samples from two mills at detection levels less than 1.0 ppt.
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-137-
8. 2378-TCDD and other TCDDs were detected in a blue dye collected
during preliminary sampling at Mill A at levels of 3.4 and 53 opt,
respectively. 2378-TCDF and other TCDFs were not detected in
that sample.
D. Formation of 2378-TCDD and 2378-TCDF
1. The rates of formation of 2378-TCDD and 2378-TCDF were
normalized on a production basis to Ibs/ton (kg/kkg) of air dried
brownstock pulp. The rates of formation computed from bleach
line exports (bleached pulps and bleach plant wastewaters) and
from total mill exports (bleached pulp, treated wastewater
effluents, and combined wastewater sludges) are summarized below:
10-8 Ibs/ton (kg/kkg) of Brownstock Pulp
Bleach Line Exports Total Mill Exports
(eight bleach lines) (five mills)
2378-TCDD
Range ND-20(10) 0.14(0.07)-11(5.5)
Median 4.1(2.0) 3.0(1.5)
Mean 8.0(4.0) 4.4(2.2)
2378-TCDF
Range 2.6(1.3)-360(180) 1.5(0.75)-130(65)
Median 12.5(6.3) 19(9.5)
Mean 68 (34) 41(21)
The range computed from bleach plant exports exceeds that
computed from total mill exports because of the integration of
results from mills with multiple bleach lines in the mill export
calculations. For three out of five mills, the calculations
using export vectors resulted in values less than computed from
individual bleach lines. The extent to which these data are
representative of long-term operations at the five mills, or are
representative of the bleached kraft industry as a whole is not
known.
2. Although the data from this study are limited, the results
suggest casual relationships between the formation of 2378-TCDD
and 2378-TCDF and (1) the degree of bleaching across bleach lines as
estimated by the chlorine and chlorine equivalents applied to the
unbleached pulp, and (2) the amount of lignin removed in the pulp
across chlorination and caustic extraction stages as estimated by
-------
-138-
the difference in permanganate number (K) and CEK (permanganate
number after caustic extraction). Attempts were made to develop
statistical correlations with the limited data. However, the
results were generally poor. Data from several additional mills
would be necessary to confirm these relationships.
3. Bleach lines processing exclusively softwood pulps had higher
rates of formation of 2378-TCDD and 2378-TCDF than bleach lines
processing exclusively hardwood pulps. However, bleaching condi-
tions on the softwood and hardwood bleach lines were different,
and thus, it is not possible to conclude that the general wood
species bleached is the determinant variable in formation of 2378-
TCDD and 2378-TCDF.
E. Wastewater Treatment System Findings
1. 2378-TCDD was found in treated wastewater effluents from three
of five mills at levels ranging from 0.015 to 0.12 ppt and 2378-
TCDF was found in four of five effluents at levels from 0.011 to
2.2 ppt. The mass discharges are summarized below:
10~5 Ibs/day (kg/day)
2378-TCDD 2378-TCDF
Range
Median
ND-3.0(1.4) 0.46(0.21)
Range
ND-42(19)
Median
3.7(1.7)
2. 2378-TCDD and
sludges collected
levels:
2378-TCDF
from each
were found
of the five
in wastewater
mills at the
treatment
following
Primary Sludges
Secondary Sludges
Combined Sludges
2378-T
17
11
3.
Range
- 24
-710
3-180
ppt
ppt
ppt
CDD
Med
19
89
37
ian
ppt
ppt
ppt
2378-TCDF
Range
32-
75-10,
34-
380
900
760
ppt
ppt
ppt
Med
100
810
330
ian
ppt
ppt
ppt
3. Mass balance calculations around the wastewater treatment
systems for three mills showed that about 50% to 80% of the 2378-
TCDD and 401 to 60% of the 2378-TCDF found in treatment system
exports (treated effluent, wastewater sludge) can be accounted
for by treatment system inputs. For two mills the treatment
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-139-
system input loadings exceeded the export loadings by more than
200%. The poor mass balances are attributed to uncertainties in
sludge, influent, and effluent flow rates, the sequencing of
sampling at certain mills, and, to some extent, analytical varia-
bility associated with trace level analyses near method detection
1imits.
4. There is no evidence to suggest that 2378-TCDD and 2378-TCDF
are destroyed in wastewater treatment systems. Rather, they are
transferred, to varying degrees, to wastewater treatment sludges.
At two mills, about 10% to 15% of the 2378-TCDD and 2378-TCDF
contained in untreated wastewater streams was transferred to the
sludges in the wastewater treatment systems, while at the remaining
three mills more than 80% transfer to sludges is indicated.
5. The distributions of 2378-TCDD and 2378-TCDF between wastewater
treatment exports (treated effluents and wastewater sludges) were
highly variable from mill to mill. However, the partitioning of
2378-TCDD and 2378-TCDF between treated effluents and wastewater
sludges was consistent within each mill. Mills with higher total
suspended solids in effluents had higher levels of 2378-TCDD and
2378-TCDF partitioned to the effluent rather than to the sludge.
F. Pulp and Paper Mill Exports
1. The distributions of 2378-TCDD and 2378-TCDF among pulp and
paper mill exports (bleached pulp, treated effluents, wastewater
sludges) were highly variable from mill to mill, but the
partitioning of 2378-TCDD and 2378-TCDF to the exports was
consistent within each mill.
2. Mass balance calculations indicate that bleach plant sources
accounted for about 90% to 140% of 2378-TCDD measured in mill
exports at three mills and more than 300% at another mill.
2378-TCDD was not detected at bleach plant sources at one mill.
For 2378-TCDF, bleach plant sources were found to account for 70%
to 130% of the amount measured in mill exports at four mills, and
more than 300% in the last mill. The poor mass balance results
at some mills are attributed to uncertainties in mass flow rates
of wastewater, sludge, and pulp, and, to some extent, analytical
variability associated with trace level analyses near method
detection limits.
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G. Chlorinated Phenolics
1. For this study, chlorinated phenolics include selected chlori-
nated phenols, chlorinated guaiacols, and chlorinated vanillins.
Chlorinated phenolics were formed in the bleaching process at
each of the five mills. These compounds were not detected in
treated intake process waters but were found in bleach plant
filtrates and wastewater treatment system influents and effluents.
Chlorinated phenolics were distributed differently at each mill.
2. Wastewaters from caustic extraction stage (E and Eo) washers
accounted for most of the chlorinated phenolics. This finding is
similar to findings for 2378-TCDD and 2378-TCDF in bleach line
filtrates.
3. The amounts of chlorinated phenolics found in C-stage and
E-stage filtrates were normalized to Ibs/ton (kg/kkg) of air-
dried brownstock pulp and are sjmmarized below:
10~3 Ibs/ton (kg/kkg) of Air-Dried Brownstock Pulp
Sum of C-Stage and
Sum of Chlorinated E-Stage Filtrates
Phenolics (eight bleach lines)
Range 9.3-54 (4.2-24)
Mean 35 (17)
Median 34 (17)
4. With the limited data available, correlations between the
presence of chlorinated phenolics and 2378-TCDD or 2378-TCDF in
wastewater treatment system influents or effluents were not
attempted. Because chlorinated phenolics were analyzed only for
the water matrix, an evaluation of total chlorinated phenolics
exports from bleach plants (i,,e., pulp and wastewaters) could
not be made. With the limited and incomplete wastewater data
available, mass balance calculations between internal bleach
plant filtrates and wastewater treatment system influents were
not attempted.
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REFERENCES
1.
2.
3.
4.
United States Environmental Protection Agency (USEPA), The
National Dioxin Study, Tiers, 3, 5f 6, and 1, EPA 440/4-87-
003, Office of Water Regulations and Standards, Washington,
D.C., February 1987.
United States Environmental Protection Agency (USEPA), Interim
Procedures for Estimating Risks Associated with Exposures to
Mixtures of Chlorinated Dibenzo-p-Dioxins and Dibenzofurans
(CDDs and CDFs) , EPA 625/3-87/012,
Washington, D.C., October 1986.
Risk Assessment Forum,
Memorandum - PCDD/PCDF Determination in Pulp/Paper Mill
Sludge, from Douglas W. Kuehl, Research Chemist, USEPA,
Duluth, Minnesota (to Howard Zar, USEPA, Chicago, Illinois),
April 14, 1986.
Consolidated Papers,
Environmental Studies
November 25, 1987.
Inc., "Dioxin/Furan
Report
Wisconsin
In-Mill
Rapids,
Source and
Wisconsin,
5.
6.
7.
Swanson, S.E., C.
Emissions of PCDDs
Rappe, K.P. Kringstad, and
and PCDFs from the Swedish
J. Malmstrom,
Pulp and Paper
Industry, Presentation at Seventh International Symposium on
Chlorinated Dioxins and Related Compounds, Las Vegas, Nevada,
October 1987.
White, G.C., Handbook of Chlorination, Van Nostrand Reinhold,
New York, New York, 1972.
Duley, M. and Freeman, M. , Pulp and Paper, San Francisco,
California, July 1987.
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-142-
GLOSSARY
A. Chemical Terminology, Abbreviations, Units
BOD--Biochemical oxygen demand is a measure of biological
decomposition of organic matter in a water sample. It is determined
by measuring the oxygen required by microorganisms to oxidize the
organic contaminants of a water sample under standard laboratory
conditions. The standard conditions include incubation for five
days at 20°C. BOD^-Biochemiccil oxygen demand, measured after
five-days.
CDDs—Chlorinated dibenzo-p-dioxins; chemical family con-
sisting of eight homologues (monochlorinated through octachlori-
nated) and 75 congeners. PCDDs-Polychlorinated dibenzo-p-dioxins.
2378-TCDD—2,3,7,8-Tetrachlorodibenzo-p-dioxin.
TCDDs--Tetrachlorodibenzo-p-diox ins; homologue comprised of 22
isomers of TCDOs.
PeCDDs--Pentachlorodibenzo-p-diox ins; homologue comprised of 14
isomers of PeCDDs.
HxCDD_s--Hexachlorod ibenzo-p-d iox ins; homologue comprised of 10
isomers of HxCDDs.
HpCDDs--Heptachlorodibenzo-p-dioxins; homologue comprised of 2
isomers of HpCDDs.
OCDD--Octachlorodibenzo-p-cl iox in; homologue consisting of a
single isomer.
CDFs—Chlorinated dibenzofurans ; chemical family consisting
of eight homologues (monochlorinated through octachlorinated) and
135 congeners. PCDFs-Polychlorinated dibenzofurans.
2378-TCDF--2,3,7,8-Tetrachlorodibenzofuran.
TCDFs--Tetrachlorodibenzofurans; homologue comprised of 38
isomers of TCDFs.
PeCDFs--Pentachlorodibenzofurans; homologue comprised of 28
isomers of PeCDFs.
HxCDFs--Hexachlorodibenzofurans; homologue comprised of 16
isomers of HxCDFs.
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-143-
HpCDFs--Heptachlorodibenzofurans; homologue comprised of 4
isomers of HpCDFs.
OCDF--Octachlorodibenzofuran; homologue consisting of a
single isomer.
Congener--Any one particular member of the same chemical
family; e.g., there are 75 congeners of chlorinated dibenzo-p-
dioxins. A specific congener is denoted by unique chemical
notation. For example, 2,3,7,8-tetrachlorodibenzofuran is re-
ferred to as 2,3,7,8-TCDF or, in this report, ,2378-TCDF.
GC_--Gas chromatograph.
GC/MS--Gas chromatography/mass spectrometry.
Homologue--A group of structurally related chemicals that
have the same degree of chlorination. For example, there are
eight homologues of CDDs , monochlorinated through octochlorinated .
Isomer—Substances that belong to the same homologous class.
For example, there are 22 isomers that constitute the homologues
of TCDDs.
ppm--Parts per million (equal to milligrams per liter, mg/1,
when the specific gravity is one for aqueous samples; and equal
to micrograms per gram, ug/gm, for solid samples).
ppb--Parts per billion (equal to micrograms per liter, ug/1,
when the specific gravity is one for aqueous samples; and equal
to nanograms per gram, ng/gm, for solid samples).
ppt--Parts per trillion (equal to nanograms per liter, ng/1,
when the specific gravity is one for aqueous samples; and equal
to picograms per gram, pg/gm, for solid samples).
ppq—Parts per quadrillion (equal to picograms per liter, pg/1,
when the specific gravity is one for aqueous samples; and equal
to femtograms per gram, fg/gm, for solid samples).
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-144-
B. Pulp and Paper Industry Terms
Active Chlor ine--That portion of chlorine in chemical com-
pounds available to c3o useful work in the chlorination of mill
water supply and in the bleaching of pulp. (See also Available
Chlorine)
Additives—Chemicals or any other materials added to pulp
stock slurry to impart special physical and visual properties to
the paper sheet or board made from it. (See Paper Additive)
Air Dr ied--Reference to puljp and paper when dried artificially
with the use of heated air in appropriate type dryers.
Air Dry (AD)--Refers to weight of moisture-free pulp or paper
plus 10% moisture based on a traditional assumption that this
amount of moisture exists when they come into equilibrium with
the atmosphere, which in actuality is dependent on the conditions
of the atmosphere to which it is exposed. Air-dried weight is
determined by dividing the oven-dried weight by a factor of 3.9.
Alkali Extraction—The second stage in a pulp bleaching
sequence where the first stage is chlorination (in which chlorine
is added and allowed to react with the pulp slurry) . The resulting
chlorinated fiber residuals and other alkali-soluble constituents
are then dissolved in the second or "alkali" extraction stage; also,
caustic extraction stage, or "E"-stage.
Alum- -A papermaking chemical , A12 (804) 3 '14^0, A12 (SO^) 3 "1 8H20
or a mixture of these hydrates, commonly used for precipitating
rosin size onto the pulp fibers to impart water-resistant
properties (when used for water treatment) to the paper made from
it. Also called aluminum sulfate or papermaker's alum.
Available Chlorine--A term used in rating chlorinated lime,
hypochlor i tes , chlorine dioxide, and other chlorine derived
chemicals (usually used in water treatment and pulp bleaching
operations) as to their total oxidizing power; C12-EQOX, as used
in this report. (See also Active Chlorine)
Back wash ing- -The operation of cleaning a rapid sand or
mechanical filter by reversing the flow of water or liquid that
is being filtered.
Bark--The rind covering of stems, branches, and roots of
trees and plants. Technically, all tissues of woody plants which
are outside the cambium layer.
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Bark Boiler--A furnace designed especially to burn bark as a
fuel"^ It is usually equipped with Dutch ovens.
Batch Digester—A cooking vessel, usually pressurized, in
which predetermined, specific amounts of wood and cooking liquors
are heated so that the wood conversion to pulp is completed and
removed before the cycle repeats, as opposed to a continuous
d igester.
Batch System—A pulp and paper manufacturing unit process
consisting of a series of operating units which processes pre-
determined specific amounts of materials and carries the process
to completion before starting another cycle.
Black Liquor--Liquor from the digester to the point of its
incineration in the recovery furnace of a sulfate chemical recovery
process. It contains dissolved organic wood substances and
residual active alkali compounds from the cook.
Black Liquor Evaporators--Multiple-effeet combination of
steam pressure and vacuum vessels in which black liquor is
concentrated. They are arranged in such a way as to minimize the
amount of steam used to carry on the process of water evaporation.
Black Liquor Recovery Boiler—A boiler designed especially
to recover heat by burning concentrated black liquor (from the
cooking of wood by the sulfate process) and to use the heat for
steam generation.
Black Liquor Recovery Furnace--A furnace or combustion chamber
especially designed to recover desirable chemicals from burning
concentrated spent black liquor from the cooking of wood by the
sulfate process.
Bleach--(1) A chemical used to purify and whiten pulp. It is
usually of the oxidizing or reducing type, such as chlorine-based
solution, oxygen, and similar chemicals. (2) The process of
purifying and whitening pulp by chemically treating it to alter
the coloring matter and to impart a higher brightness to the pulp.
Bleach Plant--That portion of a pulp mill where the bleaching
process is performed. It usually adjoins the brownstock washing
operation but sometimes is contained in a separate building.
Occasionally, this area is referred to as a bleachery or the
bleaching plant. It also refers to the area where hypochlorite
bleach solutions are prepared.
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Bleach Tower--A tall, cylindrical retention chest where pulp,
mixed with the bleaching agent, is retained the required time for
the bleaching action to be completed in a continuous system of
pulp bleaching. An upflow-type is used when bleaching low
consistency pulp, and a downflow-type is used when bleaching
medium and higher consistency palp. Also referred to as bleaching
tower.
Bleach Washer--A filter (washer) located after a bleach tower
in the bleaching sequence of pulp where the pulp is washed free
of the residual bleaching agent and the products of the bleaching
action.
Bleached Pulp--Pulp that has been purified or whitened by
chemical treatment to alter coloring matter and has taken on a
higher brightness characteristic.
Bleaching--The process of purifying and whitening pulp by
chemical treatment to remove or change existing coloring material
so that the pulp takes on a higher brightness characteristic. It
is usually carried out in a single stage or a sequence of several
stages. Chlorine, peroxides, calcium hypochlorite, carbon di-
oxide, and, lately, oxygen are most generally used to bleach
chemical pulps. For groundwood pulp, sulfur dioxide and sodium
peroxide are used.
Bleaching Agent--A variety of chemicals used in the bleaching
of wood pulp such as chlorine (Cl2), sodium hypochlorite (NaOCl),
calcium hypochlorite [Ca(OCl)2], chlorine diox ide (C1C>2) , peroxide
(H2^2) • sodium chlorite (NaClC>2) , oxygen (02) , and others. Also
referred to as bleaching chemical.
Bleaching Stage—One of the unit process operations in which
one of the bleaching chemicals is added in the sequence of a
continuous system of bleaching pulp.
Bone Dry (B.D.) — (1) A descriptive term for the moisture-free
conditions of pulp and paper. See Oven Dry (O.D.). (2) Refers
to air containing absolutely no vapor.
Caustic Extraction—A stage in the pulp bleaching sequence (E)
that normally follows the chlorination stages to remove alkali-
soluble, chlorinated lignins. (See Alkaline Extraction and
Extraction Stage)
Caustic Extracted K. No. (CEK)--A measure of the bleachability
of pulp tested immediately after the caustic extraction stage in
a pulp bleaching process. (See Permanganate Number and K Number)
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Causticizing--Convert ing green liquor to white liquor by the
use of slaked lime [Ca(OH)2l which reacts with the sodium carbonate
(Na2CC>3) in the green liquor to form active sodium hydroxide
(NaOH) in the white liquor. Also called recausticizing.
Cellulose--The chief substance in the cell walls of plants
used in pulp manufacturing. It is the fibrous substance that
remains after the nonfibrous portions, such as lignin and some
carbohydrates, are removed during the cooking and bleaching
operations of a pulp mill.
t
Chemical Pulp--The mass of fibers resulting from the reduction
of wood or other fibrous raw material into its component parts
during the cooking phases with various chemical liquors, in such
processes as sulfate, sulfite, soda, NSSC, etc.
Chemical Recovery--The recovery of chemicals in sulfate
cooking liquor after it is used to cook wood in the digester
(spent liquor). It is expressed as a percentage determined by
dividing the total alkali to the digesters, minus the sodium
sulfate added to liquor, by the total alkali in the cooking
liquor going to the digester after correcting for any change in
liquor inventory.
Chip Pile--Chips that are stored outside in a mound type of
structure usually located near the pulp mill so that chips can be
conveniently conveyed from it to the digester storage.
Chipper--A piece of equipment in the woodyard/pulp mill area
used to "chip" whole logs. It consists of an enclosed, rapidly
revolving disk fitted with surface-mounted knives against which
the logs are dropped in an endwise direction in such a manner
that they are reduced to chips, diagonally to the grain.
Chlorination—(1) The mixing and reacting of chlorine water
or gas with pulp in the bleaching operation. (2) The application
of chlorine to mill water supply and sewage for disinfection or
oxidation of undesirable compounds.
Chlorination Stage--The step in a multi-stage bleaching
process ("C" stage) where chlorine water or gas is mixed, allowed
to react, and then washed as an initial operation in a complete
pulp bleaching system.
Chlorinator--A device for adding a chlorine-containing gas or
liquid to mill wastewater. Sometimes the term is also used to
refer to the chlorine mixer in the bleach plant.
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Chlor ine--A greenish-yellow, poisonous, gaseous chemical
element (Cl2) used in bleaching pulp and water purification in a
pulp and paper mill.
Chlorine Consumption—Actual amount of chlorine consumed to
bleach pulp, expressed as pounds of chlorine used per air dry ton
of pulp bleached, or a percentage on the same basis. Tf may also
be expressed on a bone dry basis.
Chlorine Dioxide Solution--A very unstable water solution of
chlorine dioxide gas (C1C>2) produced in the chemical preparation
area of a pulp mill. It is used in the pulp bleaching process.
Chlorine Dioxide Stage--The step or steps in a multi-stage
bleaching process ( "D"-stages) where chlorine dioxide solution is
mixed with pulp, allowed to react, and then washed as one of the
operations making up a complete pulp bleaching system.
Chlorine Evaporator--A specially constructed, thermostatically
controlled vessel using hot water or steam to vaporize liquid
chlorine transferred from tank cars to a pulp mill bleach plant.
This vaporized product is used in the chlorination stage of a
bleaching process, as well as to make up hypochlorite bleaching
liquor. Also called chlorine vaporizer.
Chlorine Mixer--A mixing device used in the bleach plant to
mix chlorine water or gas with unbleached pulp.
Chlorine Requirement—The amount of elemental chlorine
required to achieve a specified final brightness level of pulp in
the bleaching process. it is supplied in the form of elemental
chlorine and/or bleaching agents such as hypochlor ites , chlorine
dioxide, etc.
Chlorolignin--The product of reaction between lignin in
unbleached pulp and chlorine in the chlorination stage of a multi-
stage pulp bleaching system.
Clay—A naturally occurring, earthy, fine-grain material
compsed of a group of crystalline clay minerals with a natural
basic structure of aluminosil icates whose hydrous chemical form
is 2\\2Q' A12°3 * 2si°3* Ifc i-s commonly used in the paper industry
to make up paper filling and coating materials. Clays are
sometimes altered by further refining, heat treatment, etc., to
enhance or extend their end uses, eg., calcined clay and delaminated
clay.
Coated Paper—A term applied to any type of paper whose
surface has been treated in such a way as to apply a coating in
order to enhance its finish characteristics.
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Coating—(1) The process of treating a sheet of paper or
paperboard so that a coating material layer of a clear film is
applied to its surface. (2) Refers to the coating material or
film substance before coating. (3) The coating layer that is
formed on the paper and paperboard sheet.
Consistency—(1) A measure of the fibrous material in pulp
solutions, e.g., pulp and water, or stock (pulps and additives)
and water. It is expressed as a percentage of this material in
the solution, in terms of bone dry (BD) , oven dry (OD) , or air
dry (AD) weight. (2) That property of adhesives or other coating
material related to viscosity, plasticity, etc., that makes it
resistant to deformation or flow.
Continuous Digester--A wood-cooking vessel in which chips are
reduced to their fiber components in suitable chemicals under
controlled temperature and pressure in a continuous operation.
Continuous Pulping Processes--Any pulping process in which
the fibrous raw material and cooking chemicals move through the
successive processing phases in a continuous fashion.
Converting Mill—A name sometimes applied to a paper or paper-
board mill which does not produce the pulp it uses on site.
Countercurrent Washing--(1) method of washing pulp by running
the wash water countercurrent to the flow of pulp through the
process. Examples include countercurrent intra-stage washing in
a multi-stage bleaching process (to minimize effluent) and the
countercurrent flow of wash water to pulp flow on vacuum-type
brownstock washers (to minimize water use and maximize black
liquor recovery). (2) The washing of pulp within a Kamyr continuous
digester (before blowing) in which the wash water flows counter-
current to the pulp flow in the process.
Delignificat ion--The separation of the lignin component from
the cellulose and carbohydrate materials of wood and woody
materials by chemical treatment, such as the cooking of chips and
the bleaching of pulp.
Dewater--(1) The tendency of solids in a slurry to aggregate
and cause the draining of water from standing or flowing sludge
or pulp slurry in a pipeline, sometimes to the point where the
remaining solids become thick enough to make removal difficult,
or to obstruct free flow through the line or a restriction such
as a valve. (2) The process by which some of the water is removed
from the pulp stock, increasing the consistency.
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Digester--(1) A pressure vessel used to chemically treat
chips and other cellulosic fibrous materials such as straw,
bagasse, rags, etc., under elevated temperature and pressure in
order to separate fibers from each other. It produces pulp.
(2) In a waste treatment plant, it is a closed tank that decreases
the volume of solids and stabilizes raw sludge by bacterial
action.
Dye--(1) A natural or synthetic, organic or inorganic substance
used to make up materials to Impart a color to pulp slurries or
the paper or paperboard shee b in papermaking, or to make up
coating material to color their surfaces. The name is used
interchangeably with the common paper mill term, dyestuff. (2) The
act of coloring (or changing the color of) any material (stock,
paper, etc.) by bringing it into contact with another material
(dye) of a different color in such a manner that the resulting
color will be more or less permanent.
Extraction Stage—That stage in a multi-stage pulp bleaching
operation("E"-stage), usually following the chlorination stage,
in which sodium hydroxide (NaOH) is used to remove water insoluble
chlorinated lignin and other colored components not removed in an
intermediate washing operation. Also referred to as the caustic
stage or alkaline extraction stage.
Fine Papers--High-quality writing, printing, and cover-type
papers having excellent pen and ink writing surface charac-
teristics .
First Stage--A pulp mill reference to the chlorination
stage (C-stage) of a multistage pulp bleaching operation, which
traditionally has been the first step. Recent technological
developments have introduced other chemicals for use in the first
step.
Free Chlorine--Elemental chlorine in the pulp bleaching pro-
cess which is in solution and not compounded with lignin elements
in chlorinated pulp slurries.
Green Liquor—A liquid that is formed during the sulfate
chemical recovery process by dissolving smelt from the recovery
furnace in a dissolving tank. The clear liquid takes on a greenish
tinge.
Green Liquor Clarification--The removal of suspended solids
(dregs) from green liquor, prior to causticizing in a pulp mill,
by settling it in any one of several types of sedimentation units
after flocculation.
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Groundwood--Pulp and paper made up of mechanical fibers
produced by the grinding of pulpwood.
Groundwood Pulp--A fibrous slurry produced by mechanically
abrading the fibers from barked logs through forced contact with
the surface of a revolving grindstone. It is used extensively in
the manufacture of newsprint and publication papers.
Hardwood--Pulpwood from broad-leaved dicotyledonous deciduous
trees.
Hardwood Pulp--Pulp produced from the wood of broad-leaved
dicotyledonous deciduous trees.
High Density Storage--The storage of pulp slurries in a high
consistency condition, usually after the bleaching proccess and
just prior to the stock preparation.
High Temperature Bleaching--0perating the bleaching stages
(hypochlorite or chlorine dioxide) of a multistage pulp bleaching
system at temperatures higher than considered conventional.
High Temperature Chlorination--0perating the first bleaching
stage (chlorination) of a multistage pulp bleaching process at
higher temperatures (usually 110°F to 120°F) than considered
conventional (less than 80°F).
Hog Fuel--Raw bark, wood waste, and other extraneous materials
which are pulverized and used as a fuel for power boilers in a mill.
Hydrated Lime (CaOH2)—Partially slaked lime produced by
adding water to lime (CaO).
Hypochlori te--Reducing-type of bleaching chemical, usually in
the form of calcium hypochlorite or sodium hypochlorite, used
extensively in the bleaching of chemical pulps.
Hypochlorite Stage--The step or steps ("H"-stages) in a multi-
stage bleaching process in which hypochlorite bleaching chemicals
(usually calcium or sodium hypochlorite) are mixed, allowed to
react, and washed.
K Number--A value, also called permanganate number, which is
the result of a laboratory test for indirectly indicating the
lignin content, relative hardness, and bleachability of pulps
usually having lignin contents below 6 percent. It is determined
by the number of milliliters of tenth normal permanganate solution
(0.1 KMnC>4) which is absorbed by 1 gram of oven dry pulp under
specified conditions.
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Kappa Number--A value obtained by a laboratory test procedure
for indirectly indicating the lignin content, relative hardness,
or bleachability of higher l.ignin content pulps, usually with
yields of 70 percent of more. It is determined by the number of
milliliters of tenth normal permanganate solution (0.1 KMnC>4)
which is absorbed by 1 gram of oven dry pulp under specified
conditions, and is then corrected to 50 percent consumption of
permanganate .
Kraft Process — The sulfate chemical pulping process. Also
any equipment used as well as any intermediate or final products
derived from the process. It means "strength" in German, and is
a common pulp mill name for the sulfate process.
Kraft Cooking Liquor — A chemical mixture consisting primarily
of sodium hydroxide (NaOH) and sodium sulfide (Na2S) . It is used
to cook wood chips and convert them into wood pulp. Sometimes
called sulfate cooking liquor.
Kraft Digester—A pulpwood cooking vessel in which sulfate
cooking liquor, consisting of sodium hydroxide (NaOH) and sodium
sulfide (Na2S) active chemicals, is used as the cooking medium.
Kraft Paper--High-streng th paper made from sulfate pulp. It
is usually made with a naturally brown color using unbleached
pulp, but it can also be made of bleached pulp and dyed to other
colors. Also known as sulfate paper.
Kraft Pulp--Wood pulp produced by the sulfate chemical process
using cooking liquor. It is made up primarily of sodium hydroxide
(NaOH) and sodium sulfide (Na2$) / using basically softwood species
of pulpwood. Also known as sulfate pulp.
Kraft Pulping Liquor--A cooking chemical solution made up of
sodium-based chemicals such as NaOH, Na2$, Na2C03, and
Kraft Recovery Cycle--The series of unit processes in a
sulfate pulp mill in which the spent cooking liquor is separated
from the pulp by washing, concentrated by evaporation, supplemented
to make up for lost chemicals, and burned to recover other
chemicals. These recovered chemicals are converted to new cooking
liquor by reacting them with fresh and recovered lime in a
causticizing operation.
Lignin--A brown-colored organic substance which acts as an
interfiber bond in woody materials. It is chemically separated
during the cooking process to release the cellulose fibers to
form pulp, and is removed along with other organic materials in
the spent cooking liquor during subsequent washing and bleaching
stages .
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Lignin Content--The amount of lignin present in the composition
of the raw fibrous materials used in pulping and in the pulp
after cooking and washing.
Lime (CaO)—A pulp mill chemical obtained by burning limestone
(CaCoJ)and used to prepare cooking and bleaching liquors. It is
also used in causticizing sulfate and soda cooking liquors, and
to make up milk of lime [Ca(OH)2l for the sulfite cooking process.
See also Limestone.
Lime Kiln—A refractory lined, open-end, inclined steel
cylinder located in the lime recovery area of a pulp mill and
mounted on rollers. It is rotated about its longitudinal axis as
lime mud (CaCC>3) is fed in the higher end, and burned to form
lime (CaO) as it travels to the lower discharge end.
Lime Milk—The calcium hydroxide [Ca(OH)2] formed by the
reaction of lime (CaO) with water (H20).
Lime Mud--The sludge which is primarily calcium carbonate
(CaCO^) that settles out and is separated from the white liquor
during the clarification operation in the causticizing process in
a pulp mill recovery cycle prior to pumping over to the lime
recovery area. Also called white mud.
Limestone (CaCO-^)--A naturally occurring mineral which is
heated to form lime. It is used by pulp mills in preparing
cooking and bleaching liquors, causticizing of sulfate and soda
cooking liquors, and other uses. See also Lime.
Mechanical Pulp--Pulp produced by reducing pulpwood logs and
chipsintotheir fiber components by the use of mechanical energy,
via grinding stones, refiners, etc.
Medium Consistency—A generalized reference used to describe
pulp slurries having consistencies within the approximate range
of 6 to 15 percent, although it may vary somewhat depending
on where in the pulp and papermaking process the reference is made.
Multistage Bleaching—Any pulp-bleaching process consisting of
two or more stages of operation in continuous series, rather
than in one single step.
Oven Dry (OP)—Moisture-free conditions of pulp and paper and
other materials used in the pulp and paper industry. It is
usually determined by drying a known sample to a constant weight
in a completely dry atmosphere at a temperature of 100°C to 105°C
(212°F to 221°F). Also called bone dry (BD).
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Paper--A homogeneous sheet of felted cellulose fibers, bound
together by interweaving and by the use of bonding agents, and
made in a variety of types. It is used for a multitude of purposes
such as writing, printing, wrapping, clothing, industrial, domes-
tic, sanitary, etc.
Paper Additive—Chemical or other material added to paper,
paperboard, or their stock slurries to impart specific physical
and visual properties to the sheet, such as wet strength, water
repellency, and fire resistence. See also Additives.
Paper Machine—Thee primary machine in a paper mill on which
slurries containing fibers and other constituents are formed into
a sheet by the drainage of water, pressing, drying, winding into
rolls, and sometimes coating.
Paper MJ11--A factory or plant location where various pulps
in slurry form are mechanically treated, mixed with the proper
dyes, additives, and chemicals, and converted into a sheet of
paper by the processes of drainage, formation, and drying on a
paper machine. Some paper mills also finish the paper in various
ways.
Permanganate Number—A value, also known as K number, that
indicates the relative hardness or bleachability of chemical pulp
usually having lignin contents below 6 percent. It is determined
by the number of milliliters of one-tenth normal potassium
permanganate solution (KMnC>4) that is absorbed by 1 gram of oven
dry pulp under specified and carefully controlled conditions.
Peroxide--A short name for sodium peroxide (Na2C>2) or hydrogen
perox ide (H22) which are used to made up bleach liquor for
bleaching mechanical-type pulps.
Peroxide Bleaching Stage--A sodium or hydrogen peroxide
bleaching step or steps ("P"-stages) sometimes used in the later
part of the multi-stage chemical-bleaching sequence as one of the
operations making up the complete pulp-bleaching system.
Process Water—Any water in a pulp and paper mill that is
used to dilute, wash, or carry raw materials, pulp, and any other
materials used in the process of making pulp and paper.
Pulp--A fibrous material produced by mechanically or chemically
reducing woody plants into their components parts from which
pulp, paper, and paperboard sheets are formed after proper slushing
and treatment, or used for dissolving purposes (dissolving pulp
or chemical cellulose) to make rayon, plastics, and other synthetic
products. Sometimes called wood pulp.
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Pulp Bleaching--The process of purifying and whitening pulp
in a pulp mill by chemically treating it to alter the coloring
matter and to impart a higher brightness to the pulp.
Pulp Cooking--The process of reacting fiber-containing mate-
rials with suitable chemicals, usually under high temperature and
pressure, in order to reduce them into their component parts with
the fiber portion separated in the form of pulp. More commonly
known as pulping.
Pulp MJ11--A plant in which pulp is mechanically or chemically
produced from fibrous materials such as woody plants, together
with other associated processes such as pulp washing and bleaching.
Chemical preparation and cooking chemical recovery operations are
also conducted there.
Pulp Washer--A piece of pulp mill equipment designed to
separate soluble, undesirable components in a pulp slurry from
the acceptable fibers, usually by some type of screening method
combined with diffusion and displacement with wash liquids,
utilizing vacuum or the natural force of gravity.
Pulping Processes—Processes for converting fibrous raw mate-
rial into pulp. They are usually classified by either the nature
or degree of the chemical and/or mechanical treatments used in
the pulping action.
Recovery Boiler—A combination unit in a pulp mill used to
recover the spentchemicals from cooking liquor and to produce
steam.
Recovery Furnace--The unit in a sulfate pulp mill in which
concentrated spent cooking liquor (black Liquor) is burnt to a
smelt to recover inorganic sodium salts and to generate steam.
Recovery Plant--The area, building, or buildings where all of
the process units considered to be included in the chemical
recovery cycle of a pulp mill are located.
Rosin--A material made up of a suspension and used for internal
sizing of paper and paperboard. It is obtained as a residue from
the distillation of gum from resinous southern pines. Sometimes
called colophony.
Rosin Size--Rosin made up as a suspension and used for internal
sizing of paper and paperboard to enhance its ability to repel
moisture and water.
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Salt Cake--A form of natural sodium sulfate (Na2S04) added to
the thick black liquor just prior to incineration in a sulfate
recovery furnace where it is converted to sodium sulfide (Na2S)
to provide one of the active chemicals in the subsequent makeup
of raw cooking liquor in the sulfate pulping process. Also
referred to as glauber's salt.
Seal Tank--A receiving tank located beneath vacuum-type
washers and filters. The watei: drops into it through a pipeline
and forms a seal to create a vacuum in the sheet-forming cylinder
portion of the unit. Sometimes referred to as a seal pit.
Sediment—Any material thaL settles out of pulp slurries,
liquid solution, treated water, wastewater, and other fluids.
Semibleached Kraft (SBK)—Pulp made by the sulfate process
which has not been bleached to the extent that normally fully
bleached pulp has. It is used to make up end products considered
of lower quality.
Semibleached Pulp--Pulp which has been only lightly bleached
to what is ordinarily considered a very low brightness range.
3howers--Water jets or sprays used throughout pulp and paper
mills to wash wire mesh screens, wires, wet felts, and pulp pads
on paper machines, cyl indrical-type washers, pulp screens, pulp
drainers, etc.
Slaking/Causticizing--A two-stage chemical process in the
causticizing plant of an alkaline pulp mill in which the sodium
carbonate (Na2CC>3) in the green liquor is converted to sodium
hydroxide (NaOH) to produce white liquor. The first stage is
slaking, which consists of the addition of lime (CaO) to green
liquor where is reacts with water to form calcium hydroxide
[Ca(OH)2l. The second stage is causticizing, in which the calcium
hydroxide reacts with the sodium carbonate to form sodium
hydroxide. Both stages overlap.
Slime--An undesirable slippery, glutinous film formed by
microorganisms and the agglomeration of nonbiological matter. It
is found throughout the pulp and paper stock flow and storage
system.
Siimicide--Toxic chemical substance added to the pulp and
paper process to inhibit the growth of undesirable microorganisms
that cause slime.
Sodium Hydroxide (NaOH)--A strong alkali-type chemical used
in making up cooking liquor in alkaline pulp mills. It is commonly
referred to in the mill as caustic, caustic soda, or lye.
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Sodium Hypochlorite (NaOCl)--A chemical used as one of the
bleaching agents in multi-stage pulp mill bleach plants.
Softwood--Wood obtained from evergreen, cone-bearing species
of trees,such as the pines, spruces, hemlocks, etc., which are
characterized by having needles.
Softwood Pulp—Pulp produced from the wood of evergreen coni-
ferous species of trees, such as pines, spruces, hemlocks, etc.
Spent Liquor (SL)--Used cooking liquor in a chemical pulp
mill which is separated from the pulp after the cooking process.
It contains the lignins, resins, carbohydrates, and other extracted
substances from the material being cooked. Usually, this liquor
is processed through a recovery cycle to produce fresh cooking
liquor and steam for process use and/or power generation.
Sulfate Process--An alkaline pulp manufacturing process in
which the active components of the liquor used in cooking chips in
a pressurized vessel are primarily sodium sulfide (Na2S) and
sodium hydroxide (NaOH) with sodium sulfate (N32S04) and lime
(CaO) being used to replenish these chemicals in recovery opera-
tions. Sometimes referred to as the kraft process.
Sulfate Pulp--Fibrous material used in pulp, paper, and paper-
board manufacture, produced by chemically reducing wood chips
into their component parts by cooking in a vessel under pressure
using an alkaline cooking liquor. This liquor consists primarily
of sodium sulfide (Na2S) and sodium hydroxide (NaOH). Also
referred to as kraft pulp.
Unbleached Pulp--Pulp that has not been treated in a bleaching
process and can be used as is in inferior grades of paper and
paperboard.
Washer—Pulp mill equipment designed to separate soluble,
undesirable components in a pulp slurry from the acceptable
fibers. It usually consists of some type of screening method
combined with diffusion and displacement with wash liquid,
utilizing vacuum, or the natural force of gravity.
Water Supply--The primary source of natural water used in a
pulp and paper mill, such as streams, rivers, lakes, and wells.
White Liquor—Cooking liquor formed by refortifying green
liquor in the causticizing operation of an alkaline-type pulp
mill so that it contains the active chemicals that will reduce
chips into their fiber components by dissolving the lignin
cementing material during the digester operation, thereby producing
pulp.
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White Liquor Clarification---The removal of calcium carbonate
(CaCC>3) and other impurities fron the causticizing liquor, usually
by gravity sedimentation in units called clarifiers. This takes
place in the liquor recaustici zing process of a pulp mill in
order to obtain a clear liquor for cooking wood.
White Water—Mill waters which have a white, cloudy appearance
due to a very fine dispersion of fibers picked up when separated
from pulp suspension on paper machines, washers, thickeners, save-
alls, and other pulp-filtering equipment. It may also contain
fine suspensions of sizing, dyestuffs, and filling materials, and
it is reused in the papermaking process or it is refiltered to
reclaim the suspended fibers.
Wood—That part of the stem of a plant, located between the
bark and the pith, which is one of the primary sources for fiber
used in the manufacture of pulp and paper.
All definitions for Section B and some definitions in Section C
were obtained from Pulp and Paper Dictionary, Lavigne, John R.,
Miller Freeman Publications, 1936.
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C. Utilities and Wastewater Treatment
Activated Sludge--The settled solids after treatment of pulp
and paper mill effluent by aeration with microorganisms. The
solids are collected at the bottom of a clarifier tank after
mixing with oxygen in an aeration tank. Part of the sludge is
recycled back to the aeration tank to maintain high solids
concentrations and efficient treatment.
Activated Sludge Process--The treatment of pulp and paper
miLl effluent with air to oxygenate the biological mass. See
Activated Sludge.
Aerated Lagoon--A natural or artificial wastewater treatment
pond in which mechanical or diffused-air aeration is used to
supplement the oxygen supply.
Biological Effluent Treatment--Process in which living micro-
organisms are mixed with incoming wastewater to a paper mill
wastewater treatment plant, and use the biologically degradable
organics in waste as food-stuffs or an energy source, thus
effectively removing them from applied wastewater.
Biological Oxidation--Breaking down (oxidizing) organic carbon
by bacteria that utilize free dissolved oxygen (aerobic) or
"chemically bound" oxygen (anaerobic).
Boiler--Broad or general term for a steam-generating unit.
It is referred to as an industrial boiler when primarily used to
generate steam for process requirements such as in a pulp and
paper mill, or as a recovery boiler when used in the chemical
recovery cycle of a pulp mill.
Boiler Slowdown—Per iod ic or continuous drains from the drum
and/or waterwall headers to remove spent precipitated feedwater
treatment chemicals from the unit.
Clarification-- (1) The removal of turbidity and suspended
solids by settling in mill wastewater treatment. (2) In the
causticizing plant in a pulp mill, it refers to the settling out
of suspended materials from green and white liquors.
Clarifiers--Storage tanks in which suspended solids are
allowed to settle and be removed from green and white liquors in
the causticizing areas of a pulp mill. Tank used in wastewater
treatment for separation of settleable solids.
Effluent--Pulp or paper mill wastewater discharges to receiving
waters including streams, lakes, and other bodies of water.
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-160-
Fly Ash--Entrained, partially burned dust, soot, and other
materials and chemicals that are carried over with the flue gases
emitted from the smoke stacks of power and recovery furnaces.
gpm--Gallon per minute.
Influent—Mill wastes, water, and other liquids, which can
be raw or partially treated, flowing into a treatment plant,
reservoir, basin, or holding pond.
Leachate--Liquid containing dissolved chemicals picked up by
flowing the liquid through a material, such as water through the
contents of a landfill.
MGD--MJ11ion gallons per day.
MLSS--Mixed-liquor suspended solids.
MLVSS--Mixed-liquor volatile; suspended solids.
Outfall—The mouth of conduit drains and other conduits from
which a mill effluent discharges; into receiving waters.
Primary Sludge—The settlings removed from the first stage of
a wastewater treatment plant which consists of a sludge settling
tank. The sludge is normally dried over vacuum filters and
disposed of in landfills or dried and burned in the power furnace.
Primary Treatment--The removal of suspended matter from mill
wastewater by sedimentation. It is usually the first stage in a
multistage wastewater treatment process, where substantially all
floating or settleable solids are mechanically removed by screening
and sedimentation.
Secondary Wastewater Treatment--Biological treatment of some
pulp and paper mill effluents after sedimentation in a primary
wastewater treatment plant.
Sedimentation—The settling of suspended solids from pulp
slurries, liquid solutions, treated water, wastewater, and other
fluids. It is usually accomplished by reducing the velocity of
the liquid below the point where it can transport the suspended
material.
Sedimentation Basin—A large container in which wastewater is
retained so that any suspended solids will settle by gravity and
then can be removed.
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-161-
Sludge--Solid material filtered out of mill wastewater which
is either disposed of in landfill operations or burned in power
bo ilers.
Vacuum Filter--Any type of slurry filter in which suction is
employed to deposit and form a pad of solids on the surface of a
separating material (screen) with the liquid flowing through it.
Wastewater--Water carrying waste materials from a mill. It
is a mixture of water, chemicals, and dissolved or suspended solids.
Water Softener--Apparatus designed to remove the dissolved
calcium and magnesium minerals that produce hardness from water
to prevent scaling in power and recovery boilers.
Water Treatment--The processing of mill source waters from
rivers, lakes, and streams to remove impurities by sedimentation,
filtration, and the addition of chemicals including alum, sodium
carbonate and chlorine.
-------
ATTACHMENT A
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
JUNE 20, 1986
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6/20/86
USEPA/PAPSR INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
Background and Project Introduction
Results from the National Dioxin Study indicate that 2378-TCDD has been
.Detected in fish and river sediments collected downstream from sane pulp and
paper mills located in various parts of the country. The Petenwell Flowage in
Wisconsin, the Rainy River in Minnesota, and the Androscoggin River in Maine
"have been identified as areas containing levels of dioxin to date. Current
wastewater treatment plant sludges from some Maine, Minnesota, and Wisconsin
mills contain parts per trillion (ppt) levels of 2378-TCDD and other PCDDs and
PCDFs. Available EPA data indicate that, within the paper industry, bleached
kraft mills have the highest levels of 2378-TCDD in wastewater sludge. This
would indicate that current process operations may be responsible. However,
there are currently no data to document potential process sources of dioxins
nor to explain the wide range of sludge concentrations at bleach kraft mills.
The paper industry has initiated a sampling program for paper nri.ll wastewater
treatment plant sludges. At this writing, paper industry data are not available.
The U.S. Environmental Protection Agency (USEPA), the American Paper
Institute (API) and the >fational Council of the Paper Industry for Air and Stream
Improvement (NCASI), have decided to conduct a cooperative screening study of
five bleached kraft mills to determine possible process sources of PCDDs and
PCDFs and quantify raw waste, sludge, and final effluent loadings of PCDDs and
PCDFs. The cooperative screening study is being conducted to determine the
formation and fate of PCDDs and PCDFs in bleached kraft pulp and paper making
operations and respective wastewater treatment facilities. The cooperating
parties believe a screening study of this nature can most efficiently be con-
ducted by combining the knowledge and resources of federal and state governments
and industry.
On March 5, 1986, the USEPA sent a formal request for information and
cooperation to the Boise-Cascade Corporation with respect to its International
Falls, Minnesota, mill. Since this cooperative screening study is expected to
generate information fully satisfying that asked for in USEPA1 a March 5, 1986,
request, USEPA hereby agrees to withdraw that request pending satisfactory
execution of the cooperative screening study.
Screening Study Objectives
1. Determine, if present, the source or sources of 2378-TCDD and other PCDDs
and PCDFs at five bleached kraft pulp and paper mills.
2. Quantify the untreated wastewater discharge loadings, final effluent
discharge loadings, sludge concentrations, and wastewater treatment
system efficiency for 2378-TCDD and other PCDDs and PCDFs. Determine raw
wastewater and final effluent levels of selected other organic compounds.
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A-2 6/20/86
General Project Organization and Responsibilities
1. Joint USEPA and Industry Responsibilities
Responsible for: (1) study design? (2) field coordination of sanpling
collection program; (3) providiiig personnel and equipment for sanpling;
(4) providing quality assurance review of analytical data from all
sarrples; (5) development of final report; (6) public, local government,
and media relations.
2. USEPA
Responsible for: (1) approval of sanpling locations; (2) contract
analytical support; (3) coordination of field sanpling with participating
State Agencies; (4) selection and prioritization of sarrples for analysis;
(5) providing confidential treaiunent of process related information in
accordance with Agency regulaticxis; (6) preparation of final report, and
(7) public, local government, and media relations as necessary. For
USEPA the study will be directed through the Office of Water Regulations
and Standards, Industrial Technology Division and Monitoring and Data
Support Division.
3. Industry
API and NCASI will each direct jxnrtions of the industry efforts, with the
assistance of the five mills participating in the study.
Responsible for:
(1) providing study sites and a proposed sanpling plan for each site;
(Participating Mills and NG^SI)
(2) contracting for analytical support; (NCASI)
(3) providing access to facilities, processes and production information
to USEPA; (Participating Mills)
(4) public, local government, and media relations as necessary.
(API and Participating Mills)
(5) Should a step in the kraft pulp and papermaking process be isolated
as a major source of dioxin, the industry agrees to undertake a
further investigation in attempt to determine its source and formation.
General Field Sanpling Plan
A complete set of samples at each mill will be obtained during a single sanpling
event. Individual samples will be collected over a 24-hour period or other
suitable composite sanpling period. Where appropriate, process additives may
be grab sampled. The approximate level of detail of sanpling to be conducted
at each mill is presented in Table 1 along with analytical requirements. The
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A-3 6/20/86
outline presented in Table 1 will be used as a guide for developing specific
sanpling plans for each mill. .Ml sanples will be collected with appropriate
documentation, coding, and custody procedures. Samples will be kept chilled
•luring collection and shipment to the analytical laboratory. Process operating
conditions and production records iuring the survey will be recorded and made
available to study participants at the conclusion of each mill-specific sanpling
event.
General Analytical Plan
Table 1 also presents a general analytical plan, and Table 2 presents
additional detail on sanple prioritization. Sanples and analyses are prioritized
to conserve analytical resources. Priority 1 analyses will be conducted and
reviewed prior to initiating Priority 2 analyses. USEPA, NCASI, and industry
participants will consult to select Priority 2 sanples and analyses. Analytical
costs for each mill will be shared on the basis of 25 percent funding by USEPA
and 75 percent funding by industry for all Priority 1 sanples and up to a
maxinun of 15 Priority 2 sanples. Industry's share of the total analytical
cost for the screening study shall not exceed $150,000.
Quality Assurance Review
The coded analytical data will be forwarded from the contract laboratory
simultaneously to the EPA and the NCASI quality assurance managers. The quality
assurance managers will complete timely reviews of the data, consult with each
other and transmit the data to the EPA and NCASI project managers. Should the
quality assurance managers disagree as to whether certain sanples require
reanalyses or followup analyses, the matter will be referred to the USEPA and
NCASI project managers for resolution. Analytical costs associated with further
analyses beyond that normally conducted by the analytical laboratory to resolve
analytical problems will be shared by USEPA and industry on the same basis noted
above. An outline of the Quality Assurance Project Plan for this screening study
is presented as Attachment 1.
Confidentiality
Section 308(b) of the Clean Water Act, 33 USC § 1318(b), provides that
confidential treatment may be afforded to trade secrets which are contained
in information collected by, or submitted to, USEPA except that confidential
treatment is precluded for "effluent data." Information collected pursuant to
this dioxin screening study can be afforded such confidential treatment in
accordance with 40 CFR Part 2. The participating companies may make claims of
confidentiality on information submitted to USEPA as specified in 40 CFR §
2.203(b). USEPA will treat such submitted information in accordance with its
regulations found at 40 CFR Part 2.
USEPA shall choose the appropriate manner in which to release the report
for this dioxin screening study after considering the confidentiality provisions
in the Clean Mater Act and Agency regulations and after consultation with the
participating mills, NCASI, and API.
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A4 6/20/86
Other Matters
Any other matters regarding study design, study implementation, analytical
issues, etc., will be referred to the USEPA and industry project managers in a
timely fashion as they arise for resolution with other parties.
Final Report
The cooperating parties agree that the final report of this screening
study will be limited to a technical document responsive to study objectives.
USEPA will have primary responsibility for preparation of the final report.
NCASI and API will provide input to the development of the final report and have
the opportunity to provide comments on review drafts. In the event industry
participants do not agree with EPA's evaluation and conclusions regarding the
data resulting from this screening study, NCASI and API may provide separate
views regarding the data for inclusion in the final report.
The undersigned signatories consent to, and approve this USEPA/Paper
Industry Cooperative Dioxin Screening Study:
Michael C. Farrar
Vice President
Environment and Health
American Paper Institute
Isaiah Gellman
Executive Vice President
National Council
of the Paper Industry for
Air and Stream Improvement
Alexander C. McBride, Chief
Water Quality Analysis Branch
Monitoring and Data Support Division
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6/20/86
TABLE 1
GENERAL SAMPLING PLAN AND ANALTYICAL REQUIREMENTS
ANALYTICAL PACKAGE
A. Background Samples
Treated River Water 2,3,4,5,6
Treated River Water Sludge 1
Wood Chips 1
B. Pulping Process
Combinel Process Wastewaters 2,5
C. Chemical Recovery Plant
Recovery Plant Contdned Wastewaters 2
Recovery Plant Waste Solids (Lime Mud) 1
D. Bleach Plant
Pulp (Bleached and Unbleached) 1 or 2
Individual Sewered Streams from Bleachines 1 or 2
Contained Bleach Plant Process Wastewaters 2,5
Bleaching Agents Or Solutions 1
E. Paper Machines
Combined Paper Machine Wastewaters 2,5
Process Additives (Alum, Clay, Dyes, Other Chemicals) 1
Slimicides 1 or 2
F. Utilities, Wastewater Treatment
Powerhouse Wastewater 2,5
Powerhouse Ash to Treatment 2
Wastewater Treatment Primary Sludge 2
Wastewater Treatment Secondary Sludge 2
Wastewater Treatment Composite Sludge 2
Combined Untreated Process Wastewater 2,3,4,5,6
Final Treated Process Wastewater Effluent 2,3,4,5,6
Other Wastewater Streams to Treatment 1,5
(e.g. landfill Leachates)
Analytical Packages
1. Isomer specific analyses for TCDDs and TCDFs
2. Package 1 plus 2378-substituted and selected bioaccumulative PCDDs and
PCDFs
3. Suspected precursor compounds: Chlorinated phenols, vanillins, and
guaiacols
4. Non-polar compounds: HRGC scan for non-polar compounds
5. TSS: Total suspended solids
6. BODg: Five-Day biochemical oxygen demand
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A6 6/20/86
TABLE 2
ANALYTICAL PRIORITIES
Estimated
PRIORITY 1 - Samples to be analyzed at all plants Number of Sanples
a. Process Relatel
Pulp (in - out) 2-6
Bleach Plant Wastewaters 4-12
Powerhouse Ash to Treatment 1
Selected Additives 2
b. Effluent Related
Combined Bleach Plant Wastewaters 1
Combined Untreated Process Wastewaters 1
Final Treated Process Wastewater Effluent 1
Composite Wastewater Sludge 1
Priority 2 - Sanples to be selected from Table 1 15
for analysis based upon Priority 1 results
-------
A 7
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460
JJi 16
OFFICE OF
WATER
Michael C. Farrar
Vice President
American Paper Institute
1250 Connecticut Avenue, N.W.
Washington, D.C. 20036
Dear Mr. Barrar:
This letter is to inform you of a minor modification to the analytical
scope of our cooperative dioxin screening study. Specifically, EPA and NCASI
participants in the study have agreed to eliminate the analyses for certain
selected bioaccumulative PCDFs and for the non-polar compounds, both of which
were listed in the agreement. The reasons for eliminating these analyses
were 1) they were not directly related to the objectives of the study, 2)
they would require additional analytical methods development and resulting
costs, and 3) they could delay completion of the analytical efforts which are
directly related to the study objectives. Attached is an amended version of
Table 1 from the agreement showing the changes.
The study appears to be progressing well. Jim McKeown and Ray Whittemore
of NCASI attended a meeting of our regional coordinators for the study on
July 8, 1986, in Boston. At this meeting we were able to review what we had
learned from the Boise Cascade sampling effort and to develop a tentative
schedule for the remainder of the study. We hope to be able to complete the
field work this calendar year and the analytical work within two or three
months after that.
Sincerely,
Alec McBride, Chief
Water Quality Analysis
Branch (WH-553)
Attachment
cc: Russ Blosser, NCASI
Gary ~
Tom O'Farrell
-------
A 8
TA'JLE i
GENERAL SAMPLING PLAN AND AMALIYICAL REQUIREMENTS
ANALYTICAL PACKAGE
A. Background Sanples
Treate.1 River Water 2,3,^5,6
Treated River Water Sludge 1
Wood Chips 1
B. Pulping Process
Combinei Process Wastewaters 2,5
C. Chemical Recovery Plant
Recovery Plant Combined Wastewaters 2
Recovery Plant Waste Solids (lime' Mud) 1
D. Bleach Plant
Pulp {Bleached and Unbleached) 1 or 2
Individual Sewered Streams from Eleachines 1 or 2
Combined Bleach Plant Process Wastewaters 2,5
Bleaching Agents Or Solutions 1
E. Paper Machines
Combined Paper Machine Wastewaters 2,5
Process Additives (Alum, Clay, Dyes, Other Chemicals) 1
Slimicides 1 or 2
F. Utilities, Wastewater Treatment
Powerhouse Wastewater 2,5
Powerhouse Ash to Treatment 2
Wastewater Treatment Primary Sludge 2
Wastewater Treatment Secondary Sludge 2
Wastewater Treatment Composite Sludge 2
Combined Untreated Process Wastewater 2,3,V^5,6
Final Treated Process Wastewater Effluent 2,3,Jt5,6
Other Wastewater Streams to Treatment 1,5
(e.g. Landfill Leachates)
Analytical Packages
1. Isomer specific analyses for TCDDs and TCDFs
2. Package 1 plus 2378-substituted and BBlaptoai TalBaeeuiimluUim PCDDs and
PCDFs
3. Suspected precursor conpounds: Chlorinated phenols, vanillins, and
guaiacols
5. TSS: Total suspended solids
6. 8005: Five-Day biochemical oxygen demand
-------
A9
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460
PR>P
JUL I 6 i986
OFFICE OF
WATER
Isaiah Gellman
Executive Vice President
National Council of the Paper Industry
for Air and Stream Inprovement, Inc.
260 Madison Avenue
New York, N.Y. 10016
Dear Mr. Gellman:
This letter is to inform you of a minor modification to the analytical
scope of our cooperative dioxin screening study. Specifically, EPA and NCASI
participants in the study have agreed to eliminate the analyses for certain
selected bioaccumulative PCDFs and for the non-polar compounds, both of which
were listed in the agreement. The reasons for eliminating these analyses
were 1) they were not directly related to the objectives of the study, 2)
they would require additional analytical methods development and resulting
costs, and 3) they could delay completion of the analytical efforts which are
directly related to the study objectives. Attached is an amended version of
Table 1 from the agreement showing the changes.
The study appears to be progressing well. Jim McKeown and Ray Whittemore
of NCASI attended a meeting of our regional coordinators for the study on
July 8, 1986, in Boston. At this meeting we were able to review what we had
learned from the Boise Cascade sampling effort and to develop a tentative
schedule for the remainder of the study. We hope to be able to complete the
field work this calendar year and the analytical work within two or three
months after that.
Sincerely,
Alec McBride, Chief
Water Quality Analysis
Branch (WH-553)
Attachment
cc: Russ Blosser, NCASI
Gary Amendolai/
Tom O'Farrell
-------
TABLE 1
Gf-NERAL SAMPLING PIJ^I AND ANALTYICAL REQUIREMENTS
ANALYriCAL PACKAGE
A. Background Samples
Treated River Water 2,3,^5,6
Treated River Water Sludge 1
Wood Chips 1
B. Pulping Process
Combinel Process Wastewaters 2,5
C. Chemical Recovery Plant
Recovery Plant Combined Wastewaters 2
Recovery Plant Waste Solids (Lime Mud) 1
D. Bleach Plant
Pulp (Bleached and Unbleached) 1 or 2
Individual Sewered Streams from Bleachines 1 or 2
Combined Bleach Plant Process Wastewaters 2,5
Bleaching Agents Or Solutions 1
E. Paper Machines
Combined Paper Machine Wastewaters 2,5
Process Additives (Alum, Clay, Dyes, Other Chemicals) 1
Slimicides 1 or 2
F. Utilities, Wastewater Treatment
Powerhouse Wastewater 2,5
Powerhouse Ash to Treatment 2
Wastewater Treatment Primary Sludge 2
Wastewater Treatunent Secondary Sludge 2
Wastewater Treatment Composite Sludge 2
Combined Untreated Process Wastewater 2,3,\^5,6
Final Treated Process Wastewater Effluent 2,3,^5,6
Other Wastewater Streams to Treatment 1,5
(e.g. landfill Leachates)
Analytical Packages
1. Isomer specific analyses for TCDDs and TCDFs
2. Package 1 plus 2378-substituted nni aal»rt>a TiiaiitaiummluUiii'u PCDDs and
PCDFs
3. Suspected precursor compounds: Chlorinated phenols, vanillins, and
guaiacols
5. TSS: Total suspended solids
6. BODj: Five-Day biochemical oxygen demand
-------
A9
UNITED STATES ENVIRONMENTAL' PROTECTION AGENCY
j'^*° WASHINGTON. D.C. 20460
JUL I 6 £86
OFFICE OF
WATER
Isaiah Gellman
Executive Vice President
National Council of the Paper Industry
for Air and Stream Improvement, Inc.
260 Madison Avenue
New York, N.Y. 10016
Dear Mr. Gellman:
This letter is to inform you of a minor modification to the analytical
scope of our cooperative dioxin screening study. Specifically, EPA and NCASI
participants in the study have agreed to eliminate the analyses for certain
selected bioaccumulative PCDFs and for the non-polar compounds, both of which
were listed in the agreement. The reasons for eliminating these analyses
were 1) they were not directly related to the objectives of the study, 2)
they would require additional analytical methods development and resulting
costs, and 3) they could delay completion of the analytical efforts which are
directly related to the study objectives. Attached is an amended version of
Table 1 from the agreement showing the changes.
The study appears to be progressing well. Jim McKeown and Ray Whittemore
of NCASI attended a meeting of our regional coordinators for the study on
July 8, 1986, in Boston. At this meeting we were able to review what we had
learned from the Boise Cascade sampling effort and to develop a tentative
schedule for the remainder of the study. We hope to be able to conplete the
field work this calendar year and the analytical work within two or three
months after that.
Sincerely,
Alec McBride, Chief
Water Quality Analysis
Branch (WH-553)
Attachment
cc: Russ Blosser, NCASI
Gary Amendolai/
Tom O'Farrell
-------
TABLE 1
GPNEKAL SAPLING P!^VI ,VJD ANrXLTYICAL REQULRSHENTS
ANALYTICAL PACKAGE
A. Background Samples
Treated River Water 2,3,^5,6
Treated River Water Sludge 1
Wood Chips 1
B. Pulping Process
Combined Process Wastewaters 2,5
C. Chemical Recovery Plant
Recovery Plant Combined Wastewaters 2
Recovery Plant Waste Solids (Lime Mud) 1
D. Bleach Plant
Pulp (Bleached and Unbleached) 1 or 2
Individual Sewered Streams from Bleachines I or 2
Combined Bleach Plant Process Wastewaters 2,5
Bleaching Agents Or Solutions 1
E. Paper Machines
Combined Paper Machine Wastewaters 2,5
Process Additives (Alum, Clay, Dyes, Other Chemicals) 1
Slimicides 1 or 2
F. Utilities, Wastewater Treatment
Powerhouse Wastewater 2,5
Powerhouse Ash to Treatment 2
Wastewater Treatment Primary Sludge 2
Wastewater Treatment Secondary Sludge 2
Wastewater Treatment Composite Sludge 2
Combined Untreated Process Wast.ewater 2,3,\^5,6
Final Treated Process Wastewater Effluent 2,3,^5,6
Other Wastewater Streams to Treatment 1,5
(e.g. Landfill Leachates)
Analytical Packages
1. Isoner specific analyses for TCDDs and TQDFs
2. Package 1 plus 2378-substituted ami eali»fr«i teJ8a8«umulalii»B PCDDs and
PCDFs
3. Suspected precursor compounds?: Chlorinated phenols, vanillins, and
guaiacols
r^**"""""" — - - y~ _ — — ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
5. TSS: Total suspended solids
6. BODj: Five-Day biochemical o;i
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ATTACHMENT B
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
SAMPLING PROCEDURES, SAMPLE PRESERVATION, AND SAMPLE HANDLING
-------
ATTACHMENT B
USEPA/PAPER INDUSTRY COOPERATIVE DIOXIN SCREENING STUDY
SAMPLING PROCEDURES, SAMPLE PRESERVATION, AND SAMPLE HANDLING
A. Haters, Wastewaters, Pulps, High Moisture (Liquid) Sludges
1. Definitions
Grab Sample - A discrete sample collected manually over a period of
time not to exceed 15 minutes.
Composite Sample - A sample formed by combining grab samples taken at
periodic time intervals over a specified sampling period. In
order to form a representative composite, the volumes of the
individual grabs may be proportioned according to the time intervals
or according to the total flows occurring during the time intervals.
Sampling Container - The precleaned stainless steel or glass container
used to obtain grab samples from the flow of material at the
sampling site.
Sampling Device - The apparatus to which the sampling container is
attached to collect grab samples. One gallon for liquids and
slurries and one quart for solids.
Composite Sample Bottle - The precleaned glass bottle which becomes
the final repository of the composite sample for shipment to the
analytical laboratory.
Aliquot Bottles - Precleaned glass containers into which grab samples
are apportioned for the purpose of providing the appropriate
volumes of the grab sample for preparing composite samples where
more than one composite sample bottle is required at a sampling
site.
2. Precleaning of Sampling Containers, Aliquot Bottles, Composite Sample
Bottles, and Sampling Devices
Prior to the survey, the sampling containers, aliquot bottles, composite
sample bottles, and that portion of the sampling device that will
contact the sample shall be cleaned as follows:
Water and Detergent Wash
Water Rinse (deionized)
Methylene Chloride Rinse or Hexane Rinse
Oven Dry or Air Dry
For transport to the field, sampling devices shall be wrapped in aluminum
foil, shiny side in. Precleaning of aluminum foil is not required.
Any cleaning in the field shall be in accordance with the above.
Bl
-------
B2
3. Passivation of Sampling Containers, Aliquot Bottles, and Composite
Sample Bottles
Prior to initiation of sampling, each sampling container, aliquot
bottle, and composite sample bottle must be prerinsed with the material
to be sampled to passivate any adsorptive sites on the containers or
bottles. This shall be done at the outset of the survey and prior to
use of any new sampling containers or aliquot bottles that are introduced
due to breakage or modification of the sampling plan. Passivation of
sampling containers or sample bottles is not necessary for solids
samples.
4. Pretreatment and Preservation of Selected Samples
During reconnaissance prior to the survey, sites containing or having
the potential to contain total residual chlorine and pH values outside
the neutral range shall be identified. An additional portion of
each sample suspected of having a chlorine residual or requiring pH
adjustment shall be transported to a field laboratory for analysis of
chlorine residual and/or pH. For each grab sample at such sites, the
total residual chlorine shall be determined amperometrically or by wet
chemical methods and recorded. The residual chlorine shall then be
neutralized as soon as practical with crystalline, reagent grade sodium
or potassium thiosulfate (35 irig/ppm Cl2/liter) prior to adjustment of
pH with 6 M sulfuric acid.
For composite samples designated for analysis of selected chlorinated
phenolic compounds the pH of each grab sample shall be adjusted to less
than 2 standard units, using 6 M sulfuric acid, prior to addition to
the composite sample bottle. The pH of the composite sample shall be
checked at the conclusion of the survey to insure that a pH less than 2
has been achieved. All sample;; shall be chilled from time of collection
through delivery to the analytical laboratory.
5. Sampling Procedures
Prior to obtaining each grab sample, the sampling container and sampling
device shall be rinsed twice with the material to be sampled. Sufficient
volume of grab sample shall be obtained at one time to fill the aliquot
bottles for all composite sample bottles at a sampling site. For liquid
samples, the grab sample must be thoroughly mixed (manually shaken)
while preparing the aliquots. Each aliquot bottle shall be filled from
the sampling container in quarter-volume increments on a rotating basis
to insure that each composite sample bottle receives a representative
portion of the grab sample. For pulp samples, each sample shall be
collected manually with a rubber or latex glove and dewatered by manual
squeezing upon collection prior to introduction to the sample container.
Where necessary, for safety reasons a pulp sampling device such as a
stainless steel spoon or wooden paddle dedicated to that site may be
used to collect the individual grab samples.
-------
B3
If it is not feasible to obtain sufficient volume of liquid sample with
one grab sample, multiple grab samples may be obtained. In these
cases, the aliquot bottles shall be filled with equal portions of each
grab sample obtained. When not in use, the sampling container and
aliquot bottles shall be kept in the ice chest designated for that site
or otherwise secured and protected from contamination.
6. Sample Identification and Coding
Each composite sample bottle shall be identified with a gummed label
bearing a sample identification number unique to the sampling site.
The composite sample bottles shall be placed in ice chests which shall
be clearly identified by sample number and sample site name for the
duration of the sampling survey. Samples from a given sampling station
shall be retained in an ice chest or ice chests dedicated to that
sampling station only. Each composite sample bottle for analysis of
selected chlorinated phenolic compounds shall be distinguished with a
bright yellow tag for identification during the sampling event. Sample
identification by site shall not be provided to the analytical
laboratory.
7. Sample Handling and Shipping
Upon completion of the survey, a second tag bearing the sample
identification number and the analytical package required shall be
attached to each composite sample bottle. The composite sample bottles
shall be sorted by site into Priority 1 and Priority 2 analysis groups
and packaged in ice chests accordingly. The ice chests shall be clearly
marked as Priority I or Priority 2. The ice chests shall be packed to
prevent sample breakage and iced to maintain low sample temperatures.
B. Composite Wastewater Sludge (Semi-Solid)
1. Definitions
Grab Sample - A discrete sample collected manually over a period of
time not to exceed 15 minutes.
Composite Sample - A sample formed by mixing grab samples taken at
periodic time intervals.
Sampling Device - Precleaned stainless steel spoon, attached to a pole,
if necessary.
Grab Sample Preparation Pan - Precleaned aluminum pan used for field
homogenization of sludge grab samples prior to introduction of
aliquots into the composite sample bottles.
Composite Sample Bottle - The precleaned glass bottle which becomes
the final repository of the composite sample for shipment to the
analytical laboratory.
-------
B4
2. Precleaning of Composite Sample bottles and Sampling Devices
Prior to the survey, the composite sample bottles, the grab sample
preparation pans, and the sampling devices shall be cleaned as follows:
Water and Detergent Wash
Water Rinse (deionized)
Methylene Chloride Rinse or Hexane Rinse
Oven Dry or Air Dry
For transport to the field, sampling devices shall be wrapped in aluminum
foil, shiny side in. Precleaning of aluminum foil is not required.
Any cleaning in the field shall be in accordance with the above.
3. Passivation of Composite Sample Bottles and Sampling Devices
Passivation of composite sample bottles and sampling devices for sludges
is not essential. Prior to initiation of sampling, composite sample
bottles, grab sample preparation pans, and sampling devices may be
prerinsed with final treated wastewater effluent to passivate any
adsorptive sites on the containers or devices. This may be done at the
outset of the survey and prior to use of any new containers or sampling
devices that are introduced due to breakage or modification of the
sampling plan.
4. Preservation of Samples
Composite samples shall be iced from collection to delivery to the
analytical laboratories.
5. Sampling Procedures
The stainless steel spoon shall be used to obtain a sludge grab sample
of sufficient volume to make up aliquots for all composite samples at
a given site. The sludge shall be placed in the grab sample preparation
pan and mixed with the stainless steel spoon until a uniform appearance
is evident. The mass shall be quartered and requartered. A rotating
system shall be used to add the proper volume aliquot to each composite
sample bottle.
6. Sample Identification and Coding
Each composite sample bottle shall be identified with a gummed label
bearing a sample identification number unique to the sampling site.
The composite sample bottles shall be placed in ice chests which shall
be clearly identified by sample number and sample site name for the
duration of the sampling survey. Sample identification by site shall
not be provided to the analytical laboratory.
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B5
7. Sample Handling and Shipping
Upon completion of the survey, a second tag bearing the sample
identification number and the analytical package required shall be
attached to each composite sample bottle. The composite sample bottles
shall be sorted by site into Priority 1 and Priority 2 analysis groups
and packaged in ice chests accordingly. The ice chests shall be clearly
marked as Priority 1 or Priority 2. The ice chests shall be packed to
prevent sample breakage and iced to maintain low sample temperatures.
Process Additives
1. Definitions
Grab Sample - A discrete sample collected manually over a period of
time not to exceed 15 minutes.
Grab Sampling Container - The precleaned glass or stainless steel
container used to obtain the grab sample. In many cases a glass
sampling container may be the final grab sample bottle.
Sampling Device - The apparatus to which the sampling container is
attached to collect grab samples. One gallon for liquids and
slurries and one quart for solids.
Final Grab Sample Bottle - The precleaned glass bottle which becomes
the final repository of the grab sample for shipment to the
analytical laboratory.
2. Precleaning of Grab Sampling Containers, Final Grab Sample Bottles, and
Sampling Devices
Prior to the survey, the grab sampling containers, final grab sample
bottles, and that portion of the sampling device that will contact the
sample shall be cleaned as follows:
Water and Detergent Wash
Water Rinse (deionized)
Methylene Chloride Rinse or Hexane Rinse
Oven Dry or Air Dry
For transport to the field, sampling devices shall be wrapped in aluminum
foil, shiny side in. Precleaning of aluminum foil is not required.
Any cleaning in the field shall be in accordance with the above.
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B5
3. Passivation of Grab Sampling Containers and Final Grab Sample Bottles
Passivation of grab sampling containers and final grab sample bottles
for liquid samples shall consist of a rinse with the material to be
sampled. Grab sampling containers and final grab sample bottles for
solid samples shall not be passivated.
4. Pretreatment and Preservation of Samples
Samples shall not be pretreated or chemically preserved, except that
any samples with residual chlorine shall be .treated with sodium or
potassium thiosulfate as soon as practical to neutralize the chlorine.
Samples shall be kept chilled from collection to delivery to the
analytical laboratory.
5. Sampling Procedures
Representative grab samples shall be obtained as appropriate.
6. Sample Identification and Coding
Each final grab sample bottle shall be identified with a gummed label
bearing a sample identification number unique to the sampling site.
The final grab sample bottles shall be placed in ice chests which shall
be clearly identified by sample number and sample site name for the
duration of the sampling survey. Sample identification by site shall
not be provided to the analytical laboratory.
7. Sample Handling and Shipping
Upon completion of the survey, a second tag bearing the sample
identification number and the analytical package required shall be
attached to each final grab sample bottle. The final grab sample
bottles shall be sorted by site into Priority 1 and Priority 2 groups
for analysis and packaged in ice chests accordingly. The ice chests
shall be clearly marked as Priority 1 or Priority 2. The ice chests
shall be packed to prevent sample breakage and iced to maintain low
sample temperatures.
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ATTACHMENT C
ANALYTICAL PROTOCOL FOR THE DETERMINATION OF
2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN AND
2,3,7,8-TETRACHLORODIBENZOFURAN IN
PAPER MILL PROCESS SAMPLES AND PAPER MILL EFFLUENTS
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June 12, 1987
REV June 22, 1987
WRIGHT STATE UNIVERSITY, DAYTON, OHIO 45435
ANALYTICAL PROTOCOL FOR THE DETERMINATION
OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN AND
2,3,7,8-TETRACHLORODIBENZOFURAN IN PAPER MILL PROCESS SAMPLES
(WOODCHIPS AND PAPER PULP) AND PAPER MILL EFFLUENTS
(SLUDGE, ASH, MUD, TREATED AND UNTREATED WASTEWATER):
DIOXIN I ANALYSES
I. SUMMARY OF SAMPLE RECEIPT AND HANDLING PROCEDURES
Samples are shipped to Wright State University (WSU),
Dayton, Ohio, via Priority Carrier (such as Federal Express or
UPS Overnight) or are delivered by U.S. EPA personnel and upon
arrival at the WSU Central Receiving Area, the Laboratory Sample
Custodian or his designate is notified. The Sample Custodian
proceeds to Central Receiving, signs the carrier's shipping
documents, and any Chain-of-Custody documentation received with
the samples, takes custody of the shipment, and transports the
shipment to the Laboratory. The samples are then carefully
unpacked within a hood located in a secure room, the condition of
each sample is noted and the individual sample numbers assigned
by the person (s) who collected the samples in the field and the
accompanying descriptions of the samples are recorded in a
Laboratory Sample Log-In Book. Also, at this time, an
Intralaboratory Control Number is assigned to each sample by the
Laboratory Sample Custodian, and this identifying number is
entered in the Laboratory Sample Log Book and is also recorded on
a label affixed to the sample vessel. Subsequently, a Receipt
Memorandum is prepared by the Laboratory Sample Custodian, which
provides a detailed listing and description of the samples
received, and this is. forwarded to the Laboratory Director.
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Accompanying this Sample Receipt Memorandum are Chain-of-Custody
documents and any other pertinent shipping documents which
accompanied the samples. The original Sample Receipt Memorandum
and associated documentation become a permanent component of the
appropriate contract folder which is maintained in this
Laboratory. Copies of the Sample Receipt Memorandum and
associated documentation are ultimately appended to reports
issued by this Laboratory which summarize analytical results
obtained for the samples. If requested by U.S. EPA, signed chain-
of-custody documentation establishing receipt of the samples by
Wright State is provided to the requesting organization.
Samples are stored in locked refrigerators if appropriate,
and samples not requiring refrigeration are stored in locked
cabinets which are located in secure, locked rooms. The Sample
Custodian controls access to the samples, and only authorized
personnel are permitted access to the samples, for the purpose of
obtaining aliquots of the samples for analysis. All Laboratory
Personnel who handle the samples are required to sign the
Intralaboratory Sample Tracking Form which eiccompanies the
samples and extracts prepared therefrom, throughout the
Laboratory, during all phases of preparation and analysis.
II. PROCEDURES UTILIZED FOR STORING AND PREPARING SAMPLES
FOR ANALYSIS, INCLUDING DRYING SOLID SAMPLES
AND FILTERING AQUEOUS SAMPLES
A. Storage of Samples
1. Refrigerate all of the samples (at 5°C) upon receipt in
the Laboratory and proceed with the procedures outlined below as
soon as practical.
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B. Sample Preparation
1. Sludge Samples
a. Open the sample container and using a spatula, break the
sludge into small particles (about 2 cm diameter or less) and
stir the sample vigorously to make it as homogeneous as possible.
Remove an aliquot of this sample (approximately 5 g) for an
"oven-dried solids as-received" determination, using the
procedures described below (Section II.B.l.d.). Remove the
remaining sample from the container and distribute it uniformly
on a stainless steel screen which is supported at a distance of
about 1 cm above a sheet of aluminum foil, both the foil and the
screen being contained within a desiccator containing an
appropriate water sorbent. To minimize the possiblity of
contamination or cross-contamination of the sample, only one
sample at a time is dried in a given desiccator. Allow the
sample to remain in the desiccator until it is essentially dry,
as indicated by the sample color, consistency, and ease of
mixing. For each group of five sludge samples which are
desiccated, prepare a laboratory blank as follows. Place a 15 cm
Whatman #42 filter on a stainless steel screen supported at a
distance of 1 cm above a sheet of aluminum foil contained in a
desiccator and allow the filter to remain in the desiccator for
the same period as that which was used for that sample of the
five which required the longest drying time. Subsequently remove
the filter from the desiccator and continue with the
homogenization, drying, and other sample preparative steps
described below.
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b. When the sample has been dried sufficiently, remove it
from the desiccator and transfer it to a laboratory blender which
is housed within a glove box or similar enclosure. Following
homogenization in the blender, remove an aliquot {approximately 5
g) of the blended solids, accurately weigh this sample aliquot,
and subject it to an oven-dried solids determination, as
described in Section II.B.l.d. of this protocol.
c. Place the remaining desiccated, blended sample into a
clean sample bottle fitted with a Teflon-lined screw cap, and
store the bottle in a refrigerator (5°C). An aliquot of this
desiccated, blended sample is subsequently analyzed for 2,3,7,8-
TCDD and 2,3,7,8-TCDF by applying the extraction and analysis
procedures which are described in Sections IV. and V.,
respectively, of this protocol.
d. Determination of oven-dried-solids on a sample aliquot
is accomplished by placing the weighed aliquot into a tared
aluminum boat which is then placed in an oven maintained at
105°C. After heating for a period of twenty-four hours, the
aluminum boat containing the sample is removed from the oven,
allowed to cool for 30 minutes in a desiccator, and then weighed.
The boat and sample are then returned to the oven for an
additional four-hour period, after which, the boat is again
removed from the oven, allowed to cool and weighed again. The
latter procedure is repeated until the weight of the sample as
indicated by two successive weighings is observed to be constant.
From the observed weight loss upon drying, the percentage of
oven-dried-solids in the original sample can be determined. This
result, as determined for an aliquot of the sample as received,
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is reported as the "initial oven-dried solids as received." The
oven-dried weight loss, as determined for an aliquot of the
previously desiccated sample (a separate aliquot of which is
subsequently analyzed for TCDD/TCDF) is used only to determine
the actual weight of the sample aliquot which is analyzed on the
oven-dried solids basis.
2. Wood Chip Samples
a. Samples of wood chips in which the chips are relatively
large (typically 1-1.5 inches in length) are initially reduced to
smaller particle size (2 cm diameter or less) using a laboratory
mill. This mill is cleaned thoroughly before each sample is
introduced. The pulverized wood sample resulting from this
operation is subsampled and dried using exactly the same
procedures described for sludge samples in the foregoing Section
II.B.I.
3. Ash Samples
a. Ash Samples are prepared using the same procedures as
described above for sludge (Section II.B.l.), with the exception
that these samples cannot be supported on a screen to dry, and
are therefore placed into a shallow, flat dish in order to dry
them in the desiccator. The ash is spread as a thin layer over
the bottom of the dish and is gently stirred periodically during
the drying period.
4. Paper Pulp Samples
a. Remove the pulp sample from the container, and then
express as much water from the sample as possible by compressing
it with a spatula after wrapping the sample in aluminum foil.
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Using the spatula, separate the sample mass into pieces which are
about 2 cm or less in diameter, and distribute these pieces
uniformly on a stainless steel screen supported about 1 cm above
a sheet of aluminum foil, both the screen and the foil being
placed in a desiccator. Allow the sample to remain in the
desiccator until it is essentially dry, as gauged by color and
consistency. For each group of five pulp samples, prepare a
laboratory blank using the procedures described in II.B.I.
Proceed with the subsampling and other drying procedures, as
described for sludge samples, beginning with Section II.B.l.b.
5. Slurry-Type Samples (Secondary Sludge, etc.)
a. Shake the sample bottle vigorously so as to obtain a
uniform suspension of the sample and when the sample is
homogeneous throughout, as judged by visual inspection, remove an
aliquot of the sample and subject it to a Total Suspended Solids
Determination, as described in Standard Methods For the
Examination of Water and Wastewater, 17th Edition, APHA,AWWA,
WPCF, 1986, Method 209C. Allow the remainder of the sample to
stand under refrigeration and when the solids appear to have
totally settled to the bottom of the container, filter the
supernatant using a previously desiccated and tared Gelman Type
A/E filter contained in a glass filtering funnel. Remove the
solids from the sample container using a clean spatula and
utilize three 100 mL aliquots of HPLC water to accomplish three
successive rinses of the sample container, and to effect a
quantitative transfer of the solids from the sample container to
the filter. Following separation of the water from the solid
remove the solid along with the filter paper from the funnel and
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distribute the solids and the filter paper on a stainless steel
screen supported about 1 cm above a sheet of aluminum foil, both
the screen and the foil being placed in a desiccator. Allow the
sample to dry until it is friable. For each group of five
samples, prepare a laboratory blank using the procedures
described in II.B.I. Proceed with the subsampling and other
drying procedures described for sludge samples, beginning with
Section II.B.l.b. Note that the tare weights of all filters used
in the separation of the liquid and solid phases of these samples
must be subtracted from the combined solids-filter weight to
determine the actual weights of the solids samples prepared,
since the filter and solids cannot be readily separated.
6. Water and Wastewater Samples
a. Clean and prepare four new 2 L bottles fitted with
Teflon-lined caps. Mark the 1 gallon bottle containing the
aqueous sample, as received, to show the original level of the
liquid in the bottle. Shake the bottle vigorously until all
solids in the bottle (which may have settled to the bottom of the
bottle if the sample was undisturbed for some time prior to
analysis) are suspended, as visually estimated. Pour
approximately equal portions of the resuspended aqueous sample
from the 1 gallon bottle into each of the four 2 L bottles using
a funnel. To accomplish this transfer, pour small portions from
the 1 gallon bottle into each of the 2 L bottles in succession,
repeating this cycle as many times as necessary to dispense all
of the contents of the 1 gallon container. Following each
pouring step, recap the 1 gallon bottle and shake it vigorously
C7
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to ensure that any particulate in the liquid remains suspended.
b. After all of the contents of the 1 gallon bottle have
been transferred to the four 2 L bottles, rinse the 1 gallon
bottle successively with two 50 mL portions of HPLC grade water,
accumulating these rinses in a 250 mL graduated beaker. Transfer
one-fourth of each of these accumulated water rinses to each of
the four 2 L bottles. Rinse the 250 mL beaker successively with
two 40 mL portions of HPLC water, transferring one-fourth of
these rinses to each of the four 2 L bottles. Recap all four 2 L
bottles and retain for subsequent extraction and analysis.
c. Rinse the original 1 gallon empty sample bottle
successively with two 50 mL portions of methylene chloride,
accumulating these in the 250 mL beaker used earlier. Transfer
these methylene chloride rinses to a clean 250 mL bottle fitted
with a Teflon-lined cap. Rinse the 250 mL beaker successively
with two 50 mL portions of methylene chloride, and pool these
rinses with the other accumulated methylene chloride rinses in
the 250 mL bottle. Reserve the: pooled methylene chloride rinses
for later splitting and combination with the methylene chloride
rinses collected as described in section III.B. below.
d. Select one of the 2 L bottles containing the split
water/wastewater sample, and add to this bottle a solution of the
13Ci2-labelled TCDD and TCDF internal standards, prepared by
combining the 20 pL of Standard 4310-1 with 1.0 mL of acetone in
a glass test tube. Rinse the test tube with 0.5 mL acetone,
followed by a second 0.5 mL portion of acetone, and transfer
these rinses to the aqueous sample.
e. Place a Teflon-coated, magnetic stirring bar in the
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sample container, and stir the aqueous sample using a magnetic
stirplate for 15 minutes to disperse the spiking solution.
Position the stem of a glass filtering funnel to discharge into a
pre-cleaned 5 L round bottom flask and place a filter (Whatman 42
filter, fluted fold) into the funnel.
f. Decant and/or pour the internal standard-spiked water
sample from the 2 L bottle into the filter and collect the
filtrate in the 5 L flask.
g. Rinse the empty 2 L sample container sequentially with
three 100 mL aliquots of HPLC grade water, pouring each rinse
through the filter, and collecting the filtrate in the 5 L
vessel. Check to ensure that all residual particulates and
sediments are removed from the original sample container by the
aqueous rinsing procedure. Retain this filtrate for subsequent
extraction using the procedures described in Section III.
h. Transfer the combined filter and particulate to a clean
Petri dish and place them into a desiccator. Allow these solids
to dry completely (as indicated by constant weight upon
successive weighings). Retain these solids for subsequent
extraction as described in Section IV.B.
i. Rinse the original 2 L sample container sequentially
with three 50 mL aliquots of methylene chloride. Pour the
rinsates through the empty funnel and collect in a clean 1000 mL
glass bottle fitted with a Teflon-lined lid. Retain this for
subsequent combination with the methylene chloride extract of the
aqueous filtrate, obtained as described in Section III.
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7. Exceptional Samples
Some of the samples received may be too wet to dry
efficiently in a desiccator, but may still not contain sufficient
liquid to permit separation of the phases by filtering or other
such means. Such samples will be distributed on sheets of
aluminum foil and allowed to air-dry at ambient temperature on a
bench top. For such samples, the surface area will be recorded,
so that a correction can be made, if this is necessary, for
contamination or cross-contamination of the samples. The extent
of contamination of such samples will be estimated by placing a
filter paper blank in the same area where these samples are air-
dried and this blank will subsequently be analyzed for 2,3,7,8-
TCDD and 2,3,7,8-TCDF. If the blank is found to be positive for
these compounds, the corresponding levels of these compounds in
the samples will be corrected for the levels detected in the
blank.
III. PROCEDURES FOR EXTRACTING 2,3,7,8-TCDD AND 2,3,7,8-TCDF
FROM AQUEOUS FILTRATE
The internal-standard-spiked, aqueous filtrate resulting
from application of the procedures described in Section II.B.6.
is extracted utilizing the following procedures.
A. Add 400 mL of methylene chloride to the aqueous filtrate
contained in the 5 L flask (from the step described in Section
II.B.S.g.). Place a magnetic stirring bar into the 5 L flask,
place the flask on a stir-plate, and stir the liquid in the flask
for 16 hours.
B. Discontinue stirring of the contents of the 5 L flask,
allow the aqueous and organic phases to separate, then remove the
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organic layer using a pipette, and place it in the 1000 mL bottle
containing the accumulated methylene chloride rinsates collected
as described in Section II.B.6.1. At this point, also add to the
contents of this same 1000 mL bottle, one-fourth of the methylene
chloride rinsates collected as described in Section II.B.6.C.
Retain the rest of the latter rinsate for subsequent splitting
among the extracts of the other three splits of the original
aqueous sample, if these are subsequently analyzed.
C. Sequentially, repeat the extraction of the aqueous
filtrate two additional times using a 100 mL portion of methylene
chloride each time, and combine each extract with the original
extract in the 1000 mL bottle. Reserve this pooled extract for
later combination with the Soxhlet extract of the particulate and
filter, as described in Section IV.
IV. PROCEDURES FOR SOXHLET-EXTRACTING 2,3,7,8-TCDD
AND 2,3,7,8-TCDF FROM DRIED BULK SOLIDS
AND FILTERED WASTEWATER SOLIDS
A. Dried Sludges, Ash Samples, Wood Chips and Paper Pulp
Solid samples of these types, prepared as described in
Section II, are extracted using the following procedures.
1. Prepare a glass Soxhlet extraction thimble (90 mm by 35
mm) for use by rinsing it sequentially with methanol, acetone and
methylene chloride. Add silica to form a 3-6 mm layer on the
surface of the glass frit at the bottom of the thimble, and place
a 10 mm layer of glass wool over the layer of silica.
2. Prepare a Soxhlet extraction apparatus, consisting of a
Soxhlet extraction tube, a 250 mL Erlenmeyer flask and a water-
cooled condenser, for use by rinsing it sequentially with
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methanol, acetone, and methylene chloride, and allowing it to
air-dry. Place 175 mL of a solution consisting of 50% benzene
and 50% acetone (by volume), along with about 10 pre-cleaned 2 mm
glass beads, into the Erlenmeyer flask. Place the Soxhlet
thimble (prepared as described in Step IV.A.I.) into the Soxhlet
extraction tube, assemble the Soxhlet-extraction apparatus, heat
the contents of the Erlenmeyer flask to reflux temperature, and
continue the Soxhlet extraction procedure for a period of 3
hours.
3. Remove the heat source from the Soxhlet apparatus, allow
the apparatus to cool, and then decant the benzene/acetone
solution into a clean, 250 mL flint glass bottle and seal the
bottle with a Teflon-lined screw cap. This solution is retained
in case additional analyses are required to check the cleanliness
of the Soxhlet apparatus, as a QC measure.
4. Place a fresh 175 mL aliquot of 50:50 (volume/volume)
benzene/acetone into the Erlenmeyer flask of the Soxhlet
extraction apparatus and re-connect the Soxhlet extraction tube
to the Erlenmeyer flask. Remove the layer of glass wool from the
glass thimble. Transfer an accurately weighed aliquot
(approximately 7-10 grams, depending upon the sample type) of the
previously desiccated solid sample, prepared as described in
Section II, from the sample bottle containing the dried sample to
the Soxhlet extraction thimble.
5. Using a microsyringe, add the appropriate internal
standard solution (Standard Solution 4610-1, described in Section
IV.D.I.) to the solid sample in the Soxhlet extraction thimble.
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Place the previously removed glass wool (Step IV.A.4.) on top of
the sample in the glass thimble. Place the condenser on the
Soxhlet extraction tube and heat the solvent reservoir so that
the extraction solvent refluxes. Soxhlet extract the sample for
a period of 16 hours, then discontinue heating the apparatus and
allow it to cool to ambient temperature.
6. Remove the Soxhlet extractor from the Erlenmeyer flask
reservoir and replace the extractor with a 3-ball Snyder column.
Resume heating the reservoir and concentrate the benzene/acetone
extract to a volume of about 15 mL. Rinse the Snyder column
twice with small quantities of hexane, then continue heating and
concentrating the solution in the reservoir with the column in
place until a final volume of 10 mL is attained.
7. Using a 10 mL disposable pipette, transfer the
concentrated solution obtained in Step IV.A.6. to a pre-rinsed,
125 mL flint glass bottle fitted with a Teflon-lined screw cap.
Rinse the Erlenmeyer flask four times using 10 mL aliquots of
hexane, transferring each rinse solution to the 125 mL bottle, to
effect a quantitative transfer of the concentrate from the
Erlenmeyer flask to the bottle.
8. Proceed with the remainder of the clean-up and
analytical procedures described in Section V.
B. Soxhlet Extraction of Water and Filtered Wastewater Solids
1. Remove the desiccated filter and associated solids
resulting from filtration of a water/wastewater sample containing
particulates , as described in Section II, from its sample
container, and immediately place the filter and solids into a
Soxhlet extraction thimble which has been pre-cleaned, as
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described above in Step IV.A.I.
2. Pre-clean a Soxhlet extraction apparatus as described in
Steps IV.A.2 through IV.A.4.
3. Concentrate the methylene chloride extract resulting
from extraction of the aqueous filtrate which has been pooled
with other methylene chloride rinsates (obtained as described in
Section III.B.) by transferring about 150 mL of the methylene
chloride extract to a 250 mL Erlenmeyer flask, attaching a 3-ball
Snyder column to the flask and heating the flask to concentrate
the methylene chloride. Continue to transfer 150 mL aliquots of
the methylene chloride extract to the Erlenmeyer flask as each
portion is reduced in volume by concentration, until the volume
of the extract is reduced to about 25 mL. Then add 150 mL of
50:50 volume: volume benzene-acetone to the Erlenmeyer flask
containing the residue from the methylene chloride concentration
and reconnect the flask to tne Soxhlet extractor. Note that it
is not necessary to spike this sample with internal standards
since the wastewater sample was previously spiked with internal
standards prior to filtering.
4. Heat the Soxhlet apparatus and extract the filter and
solids for a period of 16 hours, then discontinue heating and
allow the apparatus to cool. Remove and concentrate the extract
as described in Section IV.A.6. Transfer the concentrate to a
new sample bottle, as described in Section IV.A.7.
5. Proceed with the remainder of the clean-up and
analytical procedures described in Section V.
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V. PROCEDURES FOR ISOLATING AND QUANTITATING 2,3,7,8-TCDD
AND 2,3,7,8-TCDF PRESENT IN ORGANIC EXTRACTS
OF PAPER MILL PROCESS AND EFFLUENT SAMPLES
A. Preliminary Separation of 2,3,7,8-TCDD and 2,3,7,8-TCDF
From Other Chemical Residues in the Extracts Obtained As
Described in Sections III, and IV.
Organic extracts obtained utilizing the procedures described
in Sections III. and IV. are subjected to the f rac tionation
procedures which follow.
1. Add 30 mL of aqueous potassium hydroxide (20% w/v) to
the bottle containing the sample extract, seal the bottle and
agitate it for a period of 10 minutes. Aspirate and discard the
aqueous phase, retaining the organic phase.
2. If the aqueous layer from the previous step appears to
be colored following the base extraction procedure, then repeat
this operation (Step V.A.I.).
3. Add 30 mL of double-distilled water to the organic phase
from Step V.A.I., seal the bottle, and agitate the mixture for a
period of 1 minute. Again, aspirate and discard the aqueous
phase, retaining the organic phase.
4. Add 30 mL of concentrated sulfuric acid to the residual
hexane extract from the previous step, seal the bottle, and
agitate it for a period of 10 seconds. If emulsions form,
centrifuge the bottle to achieve separation of the organic and
acidic aqueous phases. Remove and discard the aqueous acidic
layer, retaining the organic layer.
5. Repeat the concentrated sulfuric acid wash (the
foregoing step) this time adding 30 mL of sulfuric acid to the
sample extract, and agitating the acidified sample for 10
minutes. Again, aspirate and discard the aqueous layer. Repeat
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this step until the acid layer is visibly colorless.
6. Repeat Step V.A.3.
7. Add 5 g of anhydrous sodium sulfate to the organic
extract and allow the mixture ^o stand for at least 15 minutes.
8. Quantitatively transfer the organic extract, using
hexane to rinse the sample bottle, to a clean test tube, and
reduce the volume to approximately 5 mL by passing a stream of
pre-purified nitrogen over the extract, while maintaining the
test tube at 55°C in a water bath.
9. Proceed with the liquid column chromatographic
procedures described in Section V.B.
B. Liquid Column Chromatographic Procedures for Isolating
2,3,7,8-TCDD and 2,3,7,8-TCDF From Extracts Previously Washed
with Acids and Bases
1. Fabricate a glass chromatography-columri (20 mm OD x 230
mm long) tapered to 6 mm OD on one end. Pack the column, in
succession, with a plug of glass wool (silanized), 1.0 g silica,
2.0 g silica containing 28% (w/w) I M NaOH, 1.0 g silica, 4.0 g
silica containing 30% (w/w) sulfuric acid, and 2.0 g silica.
2. Quantitatively transfer the concentrated extract
obtained in Step V.A.8., along with two rinsings of the sample
container, using 1 mL portions of hexane each time, to the column
and elute the column with 90 mL of hexane. Collect the entire
eluate and concentrate to a volume of 1-2 mL in a centrifuge
tube.
3. If any layer of the silica gel column implemented in
Step V.B.2. becomes visibly colored as the column is eluted,
repeat Steps V.B.I, and V.B.2.
C16
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4. Prepare a liquid chromatography column (11 mm OD x 120
mm) by packing the constricted end with a plug of silanized glass
wool and then adding three grams of Woelm basic alumina
(previously activated overnight at 600°C in a muffle furnace and
placed in a desiccator for 30 minutes just prior to use).
5. Aspirate the concentrated extract obtained in Step
V.B.2. and transfer it onto the alumina column prepared in Step
V.B.4. Rinse the test tube which contained the concentrate
successively with two 1 mL portions of hexane, each time
transferring the rinse solution to the alumina column.
6. Elute the alumina column as follows: (a) Elute the
alumina column with 10 mL of 3% (v/v) methylene chloride-in-
hexane, taking care not to let the column become completely dry
during the elution, and discard the entire eluate. (b) Elute the
column with 15 mL of 20% (v/v) methylene chloride-in-hexane and
discard the entire eluate. (c) Elute the column with 15 mL of
50% (v/v) methylene chloride-in-hexane, retain this entire
eluate, and reduce the volume to about 1.0 mL by passing a stream
of pre-purified nitrogen over the solution while heating the
solution in a 55°C water bath.
7. Prepare a second alumina column as described in Step
V.B.4., transfer the concentrated eluate obtained in Step V.B.6.
to the column, and elute the column as described in Step V.B.6.
Collect the column eluate and concentrate it to a volume of about
1 mL.
8. Prepare a liquid chromatography column by cutting off a
9-inch disposable Pasteur pipette 1.25 cm above the tip
constriction leaving a straight glass tube with an indentation
C17
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approximately 2.5 cm inch from the top. Insert a filter paper
disk in the tube and position the disk 2.5 cm below the
indentation. Add a sufficient quantity of PX-21 Carbon/Celite
545 (prepared as described in Section V.C. of this Protocol) to
the tube to form a 2 cm length of the Carbon/Celite. Insert a
glass wool plug on top of the Carbon/Celite. Pre-elute the
column sequentially with 2 mL of. a 50% benzene/50% ethyl acetate
solution (v/v), 2 mL of 50% methylene chloride/50% cyclohexane,
and 2 mL of hexane, and discard these eluates. Transfer the
residual sample extract (in 1 mL of hexane) resulting from the
alumina column cleanup (Step V.B.7.) onto the top of the
Carbon/Celite column, along with 1 mL of a hexane rinse of the
original sample vessel. Elute the column with 2 mL of 50%
methylene chloride/50% cyclohexane solution and 2 mL of 50%
benzene/50% ethyl acetate and discard these eluates. Invert the
column and elute it in the reverse direction with 4 mL of
toluene, retaining this eluate. Concentrate the collected column
effluent to a volume of about 1 mL using a stream of pre-purified
nitrogen.
9. Prepare a third alumina column as described in Step
V.B.4., transfer the concentrated eluate from the second alumina
column sequence to this column, elute the column, and collect the
eluate as already described i:a Step V.B.6, in a test tube.
Concentrate the collected eluate to a volume of about 1 mL, then
quantitatively transfer the concentrate to a 3 mL micro-reaction
vessel (Reacti-vial) , using two 1 mL portions of methylene
chloride to rinse the test tube, and also transferring these to
CIS
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the micro-reaction vessel. Concentrate the solution in the
latter vessel just to dryness , using a stream of dry Nz , as
described previously. Rinse the walls of the micro-reaction
vessel using 0.5 mL of methylene chloride, and again concentrate
just to dryness. Seal the vessel and store it in a freezer
(-15°C). Just prior to GC-MS analysis, remove the vessel from
the freezer, allow it to warm to ambient temperature, and
reconstitute the residue in the vessel by adding 10 pL of
Standard 4643-1 to the vial.
C. Reagents and Chemicals
Reagents and chemicals used in implementing the procedures
described herein and the sources of these are described in the
following.
1. Potassium hydroxide, anhydrous, granular sodium sulfate
and sulfuric acid (all Reagent Grade): J.T. Baker Chemical Co.,
Glen Ellyn, IL, or Fisher Scientific Co., Cincinnati, OH. The
granular sodium sulfate is purified prior to use by placing a
beaker containing the sodium sulfate in a 400° C oven for four
hours, then removing the beaker and allowing it to cool in a
desiccator. Store the purified sodium sulfate in a bottle
equipped with a Teflon-lined screw cap.
2. Acetone, hexane, methylene chloride, benzene, ethyl
acetate, methanol, toluene, cyclohexane, isooctane: "Distilled
in Glass" Burdick and Jackson, Muskegon, MI.
3. Dodecane and Tridecane (Reagent Grade): Sigma Chemical
Co., St. Louis, MO.
4. Basic Alumina (Activity Grade 1): ICN Pharmaceuticals,
C19
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Cleveland, OH. Immediately prior to use, the alumina is
activated by heating for at least 16 hours at 600° C in a muffle
furnace and then allowing to cool in a desiccator for 30 minutes
prior to use.
5. Silica (Bio-Sil A 100/200 mesh): Bio-Rad, Rockville
Centre, NY. the Bio-Sil A is conditioned prior to use by
initially placing a 200 g portion of the silica in a 30 mm x 30
cm long glass tube (the silica gel is held i/i place by glass wool
plugs) which is placed in a tube furnace. The glass tube is
connected to a pre-purified nitrogen cylinder through a series of
four traps (stainless steel tubes, 1.0 cm OD x 10 cm long)*.
Trap Number 1 contains a mixture composed of Chromosorb W/AW
(60/80 mesh coated with 5% Apiezon L) , graphite (100 mesh, 1-M-
USP), and activated carbon (50 to 200 mesh), in a 7:1.5:1.5
ratio. Chromosorb W/AW and Apiezon L were obtained from Supelco,
Inc., Bellefonte, Pennsylvania; graphite was obtained from
Ultracarbon Corporation, Bay City, Michigan; activated carbon was
obtained from Fisher Scientific Co., Cincinnati, Ohio. Trap
Number 2 contains Molecular Sieve 13X (60/80 mesh, obtained from
Supelco, Inc., Bellefonte, Pennsylvania). Trap Number 3 contains
silica gel impregnated with 309s (w/w) sulfuric acid (prepared as
described in V.C.6. below). Trap Number 4 contains Carbosieve S
80/100 mesh, (obtained from Supelco, Inc., Bellefonte,
Pennsylvania) . The first step in conditioning the Bio-Sil A
entails heating the glass tube containing the 200 g aliquot of
silica for 30 minutes at 180°C while purging with nitrogen (flow
*. See T. J. Nestrick and L. L. Lamparski, Anal. Chem 53, 122
(1981) for additional details and rationale regarding use of
these traps.
C20
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rate 50-100 mL/minute), subsequently the tube is removed from the
furnace and allowed to cool to room temperature. Methanol (175
mL) is then passed through the tube,, followed by 175 mL methylene
chloride. The tube containing the silica is then returned to the
furnace, the nitrogen purge is again established (50 to 100
mL/minute flow), the tube is heated at 50°C for 10 minutes, then
the temperature is gradually increased to 180°C over a period of
25 minutes and maintained at 180°C for 90 minutes. Heating is
then discontinued but the nitrogen purge is maintained until the
tube cools to room temperature. Finally, the silica is
transferred to a clean, dry, glass bottle and capped with a
Teflon-lined screw cap for storage in a desiccator.
6. Silica Gel Impregnated with Sulfuric Acid (30% w/w) :
Concentrated sulfuric acid (4.4 g) is combined with 10.0 g silica
gel (conditioned as described above) in a screw capped bottle and
agitated to mix thoroughly. Aggregates are dispersed with a
stirring rod until a uniform mixture is obtained. The HzS0«-
silica gel is stored in a screw-capped bottle (equipped with a
Teflon-lined cap).
7. Silica Gel Impregnated with Sodium Hydroxide: IN Sodium
hydroxide (30 g) is combined with 100 g Bio-Sil A (conditioned as
described above) in a screw capped bottle and agitated to mix
thoroughly. Aggregates are dispersed with a stirring rod until a
uniform mixture is obtained. The NaOH-silica gel is stored in a
screw-capped bottle (Teflon-lined cap).
8. Carbon/Celite: A 10.7 g aliquot of PX-21 carbon
(Anderson Development Co., Adrian, Michigan) is combined with 125
C 21
-------
g of Celite 545 (Fisher Scientific Co.) in a 250 mL glass bottle,
fitted with a Teflon-lined cap, and the mixture is shaken to
obtain a uniform mixture. The Carbon/Celite mixture is stored in
the screw-capped bottle.
9. Nitrogen {Pre-purified) and Hydrogen (Ultra High
Purity): Airco, Inc., Montvale, NJ.
D. Calibration and Spiking Standards
Stock standard solutions of the appropriate TCDD and TCDF
isomers, and mixtures thereof, are prepared in a glovebox, using
weighed quantities of the siuthentic isomers. These stock
solutions are contained in appropriate amber bottles and are
stored tightly stoppered in a. refrigerator. Aliquots of the
stock standards are removed for direct use or for subsequent
serial dilutions to prepare working standards. These standards
must be checked regularly (by comparing instrument response
factors for them over a period of time) to ensure that solvent
evaporation or other losses have not occurred which would alter
the standard concentration. The standard solutions which may be
required to perform the quantitative analyses of 2,3,7,8-TCDD and
2,3,7,8-TCDF are listed below.
1. Internal Standard Solution 4610-1. An aliquot of
this solution is added to samples which are to be analyzed for
2,3,7,8-TCDD and 2,3,7,8-TCDF. Prepare a stock solution
containing the following isotopically-labelled TCDD and TCDF
compounds in isooctane at the indicated concentrations: 0.05
ng/pL *3Ci2-2,3,7,8-TCDD, 0.02 ng/pL 37C14-2,3,7,8-TCDD, 0.05
ng/pL 13Ci2 -2,3,7, 8-TCDF, anci 0.02 ng/pL 3 7 Cl« -2 , 3 , 7 , 8-TCDF .
Typically a twenty microliter aliquot of this standard solution
C22
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is added to each sample aliquot prior to preparation and the
13Ci 2-labelled materials serve as internal standards for use in
quantitation. Recovery of these standards is also used to gauge
the overall efficacy of the analytical procedure.
2. Standard Solution 4643-1. Prepare a stock solution
containing 0.05 ng of 1 3 Ci 2 -1, 2 , 3 , 4-TCDD and 0.10 ng of 3 7 C14 -
1,2,7,3-TCDF/ML tridecane. A 10 microliter aliquot of this
standard is added to the final extract obtained for each sample
just prior to GC-MS analysis. When the DB-5 capillary column is
employed, the *3Ci2-1,2,3,4-TCDD is used as an external standard
in the quantitation of the 1 a Ci 2 -2 , 3 , 7 , 8-TCDD and the *• 3 Ci 2 -
2,3,7,8-TCDF internal standards present in the final extract, and
the percent recovery of each of these 13Ci2-labelled internal
standards is calculated on the basis of this quantitative
analysis. The 37C14-1,2,7,8-TCDF external standard is employed
in quantitating the concentration of 13Ci2-2,3,7,8-TCDF when the
hybrid DB-5/DB-225 capillary column is implemented in
quantitating 2,3,7,8-TCDF. These latter results are subsequently
implemented in calculating the percent recovery of the 13 Ci2 -
2,3,7,8-TCDF internal standard achieved during the analysis
performed using the hybrid column.
3. Standard Solutions 4616-1, 4616-2, 4617-1, and 4617-2.
Prepare four separate calibration standards as follows: (a)
Standard 4616-1, 0.2 ng/pL 2,3,7,8-TCDD, 0.2 ng/pL 2,3,7,8-TCDF,
0.05 ng/pL 13C12-2,3,7,8-TCDD, 0.05 ng/uL J3Ci2-2,3,7,8-TCDF,
0.02 ng/uL 37Cl«-2,3,7,8-TCDD, 0.02 ng/pL 3 *Cl<-2,3,7,8-TCDF,
0.05 ng/pL 13Ci2-1,2,3,4-TCDD and 0.10 ng/pL 37Cl«-1,2,7,8-TCDF;
C23
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(b) Standard 4616-2, 0.05 ngr/pL 2 , 3 , 7 , 8 -TCDD , 0.05 ng/pL
2,3,7,8-TCDF plus the same concentration of isotopically-labelled
standards included in 4616-1; {c) Standard 4617-1, 0.01 ng/pL
2,3,7 , 8-TCDD, 0.01 ng/pL 2 , 3 , 7 , 8--TCDF plus the same concentration
of isotopically-labelled standards included in 4616-1; (d)
Standard 4617-2, 0.0025 ng/pL, 2,3,7,8-TCDD, 0.0025 ng/pL 2,3,7,8-
TCDF plus the same concentration of isotopically-labelled
standards included in 4616-1; (e) Standard 4636-1, 2.0 ng/pL
2,3,7,8-TCDD, 2.0 ng 2,3,7,8-TCDF plus the same concentrations of
isotopically-labelled standards included in 4616-1. Aliquots of
these standards are injected to obtain data which is implemented
in constructing the calibration curve used in quantitating
2,3,7,8-TCDD and 2,3,7,8-TCDF.
4. Standard Mixture 109071-1. Prepare an isooctane
solution containing 0.05 ng/pL concentrations of each of the
following TCDD isomers: 1,3,6,8-TCDD; 1,2,3,7-TCDD; 1,2,3,9-
TCDD; 2,3,7,8-TCDD; 1,2,3,4-TCDE and 1,2,8,9-TCDD. Two of the
isomers in this mixture are used to define the gas
chromatographic retention time window for TCDDs (1,3,6,8-TCDD is
the first eluting TCDD isomer and 1,2,8,9-TCDD is the last
eluting TCDD isomer on the DB-5 GC column) . The remaining
isomers serve to demonstrate that the 2,3,7,8-TCDD isomer is
resolved from the other nearest eluting TCDD isomers, and that
the column therefore yields quantitative data for the 2,3,7,8-
TCDD isomer alone.
5. Standard Mixture 4612-2. Prepare a solution
containing 0.250 ng/pL 2,3,7,8-TCDF in tridecane. This standard
is implemented when it is desired to add only native 2,3,7,8-TCDF
C24
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to a sample.
6. Standard Mixture 76179-1. Prepare a solution
containing approximately 0.250 ng/ML of each of the 37 TCDF
isomers (exclusive of 2,3,7,8-TCDF) in isooctane. This standard
is used when it is desired to add all of the TCDF isomers except
2,3,7,8-TCDF to a sample. This standard is also implemented to
determine the relative retention times of the TCDF isomers and,
when this standard is co-injected with an aliquot of standard
4612-2, the efficacy of a particular gas chromatographic column
for separating 2,3,7,8-TCDF from each of the 37 other TCDF
isomers can be ascertained.
7. Standard Mixtures 4614-1 and 4614-2. For Mixture
4614-1, prepare a solution containing 0.025 ng 2,3,7,8-TCDD and
0.025 ng 2,3,7,8-TCDF per microliter of tridecane. For mixture
4614-2, prepare a solution containing 0.005 ng 2,3,7,8-TCDD and
0.005 ng 2,3,7,8-TCDF. These standards are employed when it is
desired to simultaneously add both native 2,3,7,8-TCDD and native
2,3,7,8-TCDF to a sample.
E. Gas Chromatographic-Mass Spectrometric (GC-MS) Procedures for
Quantitating 2,3,7,8-TCDD and 2,3,7,8-TCDF Present in
Sample Extracts
Sample extracts prepared by the procedures described in the
foregoing are analyzed by GC-MS utilizing the instrumentation and
operating parameters listed below. Typically, 1 to 5 pL portions
of the extract are injected into the GC. Sample extracts are
initially analyzed using the DB-5 capillary GC column at a mass
spectral resolution of 1:600 to obtain data on the concentration
of 2,3,7,8-TCDD and to ascertain if 2,3,7,8-TCDF or other isomers
C25
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which coelute with 2,3,7,8-TCDF are present. If the latter are
detected in this analysis, then another aliquot of the sample is
analyzed in a separate run, using a newly developed hybrid column
which consists of a 10 meter length of a 0.25 mm I.D. fused
silica open tubular DB-5 capillary column coupled with a 30
meter section of a 0.25 mm I.D. DB-225 column. Again, the mass
spectrometer is operated at low resolution (1:600). The hybrid
column uniquely separates 2,3,7,8-TCDF from the other 37 TCDF
isomers and therefore yields definitive data on the concentration
of 2,3,7,8-TCDF in the extract which is analyzed. However, in
some instances compounds are present in the sample extract which
give rise to ion masses which, at low (1:600) mass resolution,
interfere with the quantitation of 2,3,7,8-TCDF. In these
instances the analysis of the sample extract can be repeated, at
the option of USEPA/NCASI, using the DB-5/DB-225 hybrid column,
but this time at a mass spectral resolution of 1:6,500. The
instrumentation and operating parameters utilized in these
analyses are as follows.
1. Gas Chromatograph; Perkin-Elmer Sigma III or Varian
3740
a. Injector: Configured for capillary column,
splitless/split injection (split flow on 60 seconds following
injection): injector temperature, 280°C.
b. Carrier gas:
i) For DB-5 column: Hydrogen, 30 Ib. head
pressure (MS-25 jet separator); 18 Ib. head
pressure (MS-30 direct coupled)
C26
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ii) For DB-5/DB-225 column: Hydrogen, 30 Ib. head
pressure (MS-25 jet separator); 18 Ib. head
pressure (MS-30 direct coupled)
c. Capillary Column 1: For quantitation of 2,3,7,8-
TCDD (isomer specific) and 2,3,7,8-TCDF (non-isomer specific), 60
M x 0.25 mm ID fused silica coated with a 0.25 micron film of DB-
5, temperature programmed, see Table 1 for temperature program.
Capillary Column 2: For quantitation of 2,3,7,8-TCDF (isomer
specific), 10 M x 0.25 mm ID fused silica column coated with a
0.25 micron film of DB-5 coupled with a 30 M x 0.25 mm I.D. fused
silica column coated with a 0.25 micron film of DB-225. This
column is temperature programmed as indicated in Table 2.
d. Interface Temperature: 250°C
2. Mass Spectrometer: Kratos MS-30 or Kratos MS-25
a. lonization Mode: Electron impact (70 eV)
b. Static Resolution: 1:600 (10% valley) or 1:6,500
depending upon instrumentation.
c. Source Temperature: 250°C
d. Accelerating Voltage: 2KV or 4KV, depending upon
instrument.
e. Ions Monitored: Computer controlled Selected Ion
Monitoring, See Tables 1 and 2 for list of ion masses monitored
and time intervals during which ions characteristic of 2,3,7,8-
TCDD and 2,3,7,8-TCDF are monitored. Note that in the case of
quantitation of the 2,3,7,8-TCDF, the hexachlorinated
diphenylether molecular ion, which could give rise to an
interference at m/z 304 and 306, is also monitored as indicated
in Table 2.
C27
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3. Calibration Procedures:
a. Calibrating the MS Mass Scale: Perfluorokerosene,
decafluorotriphenyl phosphine, or any other accepted mass marker
compound must be introduced into the MS, in order to calibrate
the mass scale through at lea.st m/z 350. The procedures
specified by the manufacturer l:or the particular MS instrument
used are to be employed for this purpose. The mass calibration
should be rechecked at least at 8 hr. operating intervals.
b. Table 1 shows the GC temperature program typically
used to resolve 2,3,7,8-TCDD from each of the 21 other TCDD
isomers and indicates the ion-masses monitored and the time
analytical sequence implemented for isomer specific quantitation
of 2,3,7,8-TCDD and non-isomer specific quantitation of 2,3,7,8-
TCDF. This temperature program and ion monitoring time cycle must
be established by each analyst for the particular instrumentation
used by injecting aliquots of Standard Mixture 109071-1, as well
as the calibration mixtures (4616-1, 4616-2, 4617-1, and 4617-2)
into the GC-MS. It may be necessary to adjust the temperature
program and ion monitoring cycles slightly based on the
observations from analysis of these mixtures.
c. Checking GC Column Resolution for 2,3,7,8-TCDD and
2,3,7,8-TCDF: Utilize Standard Mixture 109071-1 to check the DB-5
column resolution for 2,3,7,8-TCDD, and utilize a combination of
Standards 4612-2 and 76179-1 to verify that 2,3,7,8-TCDF is
separated from all of the other TCDF isomers on the hybrid DB-5/
DB-225 column. A 25% valley or less must be obtained between the
mass chromatographic peak observed for 2,3,7,8-TCDD and adjacent
peaks arising from other TCDD isomers and similar separation of
C28
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2,3,7,8-TCDF from other neighboring TCDFs is required. Analyze
the column performance standards using the instrumental
parameters specified above and in Table 1 and 2. The column
performance evaluation must be accomplished each time a new
column is installed in the gas chromatograph, and at the
beginning and conclusion of each 8 hour operating period. If the
column resolution is found to be insufficient to resolve 2,3,7,8-
TCDD and 2,3,7,8-TCDF from their neighboring TCDD and TCDF
isomers, respectively, (as measured on the two different columns
used for resolving these two isomers), then a new DB-5 and/or
DB-5/DB-225 hybrid GC column must be installed.
d. Calibration of the GC-MS-DS system to accomplish
quantitative analysis of 2,3,7,8-TCDD and 2,3,7,8-TCDF contained
in the sample extract is accomplished by analyzing a series of at
least three working calibration standards. Each of these
standards is prepared to contain the same concentration of each
of the *3 Ci 2 -2,3,7,8-TCDD and *•3Ci 2-2,3,7,8-TCDF internal
standards used here but a different concentration of the native
2,3,7,8-TCDD and 2,3,7,8-TCDF. Typically, mixtures will be
prepared so that the ratio of the native 2,3,7,8-TCDD and
2,3,7,8-TCDF to the isotopically-labelled TCDD/TCDF ranges
between 0.05 and 4.0 in the four working calibration mixtures.
Prior to injecting aliquots of actual sample extracts, an aliquot
of a standard containing typically 0.2 ng of *3Ci2-1,2,3,4-TCDD
and 0.4 ng of 3 7 Cl< -1, 2,7 , 8-TCDF (Standard 4643-1) is used to
dilute the extract in the sample vials and is therefore co-
injected along with the sample extract, in order to obtain data
C29
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permitting calculation of the percent recovery of the 13 Ci2 -
2,3,7,8-TCDD and *3Ci2-2,3,7,8-TCDF internal standards. When the
analysis of the extract is performed using the DB-5 capillary
column, the *• 3 Ci 2 -1, 2 , 3 , 4-TCDD standard is implemented as the
external standard in quantitating both 1 3Ci 2-2,3,7,8-TCDD and
13Ci2-2,3,7,8-TCDF. However, when the hybrid DB-5/DB-225 column
is employed in analyzing the 2,3,7,8-TCDF, the 37C14-1,2,7,8-TCDF
is implemented in quanitiating the 1 3Ci2-labelled TCDF internal
standard. Equations for calculating relative response factors
from the calibration data derived from the calibration standard
analyses, and for calculating the recovery of the l aCi 2-2,3,7,8-
TCDD and 1 3 Ci 2 -2 , 3 , 7 , 8-TCDF , as well as the concentration of
native 2,3,7,8-TCDD and 2,3,7,8-TCDF in the sample (from the
extract analysis), are summarized below.
Daily checks of the imstrument performance will be
accomplished using Standard 4617-1. This standard will be
injected at the beginning of each work-day (or the beginning of
each 8-hour shift) and RRF values for 2,3,7,8-TCDD and 2,3,7,8-
TCDF will be calculated. If either of these RRF values deviate
from the values contained in the calibration curve by more than
+20%, then a second injection will be made and RRF values for the
two compounds will be again calculated. If either of these RRF
values also fail to agree with the calibration curve by more than
±20%, then the entire series of calibration standards will be
analyzed, new RRF values will be calculated, and a new
calibration curve will be constructed and applied in subsequent
analyses.
C30
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4. Equations Used for Calculating Analytical Results
from the GC-MS Data
a. Equation 1: Calculation of Relative Response Factor for
native 2,3,7,8-TCDD (RRF2) using 13Ci2-
2 , 3,7,8-TCDD as an internal standard.
RRF2 =
where:
(AsCis /Ai sCs )
As
= SIM response for 2,3,7,8-TCDD ion at
m/z 320 + 322
At s = SIM response for * 3 Ci 2 -2 , 3 , 7 , 8-TCDD internal
standard ion at m/z 332 + 334
Ci
= Concentration of the internal standard
= Concentration of the 2,3,7,8-TCDD (pg./pL.)
b. Equation 2: Calculation of Relative Response Factor for
13Ci2-2,3,7,8-TCDD (RRFb)
RRFb
where: At
Ae
Ci
= (Al s Ce s /Ae s Cl s )
= SIM response for 1 3Ci 2-2,3,7,8-TCDD
internal standard ion at m/z 332 + 334
= SIM response for J3Ci2-1,2,3,4-TCDD
external standard at m/z 332 + 334
= Concentration of the 1 3 Ci 2 -2 , 3 , 7,8-TCDD
internal standard (pg./pL.)
= Concentration of the 13 Ci 2-1 , 2 , 3,4-TCDD
standard (pg./jjL.)
C31
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c. Equation 3: Calculation of concentration of native 2,3,7,8-
TCDD using *3Ci2-2,3,7,8-TCDD as internal
standard
Concentration, pg./g. = (As) (Is)/(Ais)(RRFz)(W)
where: As = SIM response for 2,3,7,8-TCDD ion at
m/z 320 + 322
Ais = SIM response for the A3Ci2-2,3,7,8-TCDD
internal standard ion at m/z 332 + 334
Is = Amount of internal standard added to each
sample (pg.)
W = Weight of sample in grams
RRFz = Relative response factor from Equation 1
d. Equation 4: Calculation of % recovery of * 3 Ci 2-2 , 3 , 7 , 8-
TCDD internal standard
% Recovery = 100(At• ) (E» ) / (At» ) (Ii ) (RRFb)
Ais = SIM response for *• 3 Ci 2 -2, 3, 7 , 8-TCDD
internal standard ion at m/z 332 + 334
Aes = SIM response for *3Ci2-1,2,3,4-TCDD
external standard ion at m/z 332 + 334
Es = Amount of l3Ci2-1,2,3,4-TCDD external
standard co-injected with sample extract
Ij = Theor'etical amount of l 3 Ci 2 -2 , 3 , 7 , 8-TCDD
internal standard in injection
RRFb = Relative response factor from Equation 2
C32
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e. Equation 5; Calculation of Relative Response Factor for
native 2,3,7,8-TCDF (RRFc ) using * 3 Ci 2 -
2,3,7,8-TCDF as an internal standard.
RRFc =
where:
(As Ci s /Ai 9Cs )
As
= SIM response for 2,3,7,8-TCDF ion at
m/z 304 + 306
At s = SIM response for l 3 Ci 2 -2 , 3 , 7 , 8-TCDF internal
standard ion at m/z 316 + 318
Ci s = Concentration of the internal standard
(pg./pL. )
Cs = Concentration of the 2,3,7,8-TCDF (pg./gL.)
f. Equation 6: Calculation of Relative Response Factor for
1 3 Ci 2 - 2,3,7,8-TCDF (RRFd) (When analysis is
performed using DB-5 Column)
RRFd
where: Ai s
= (AlsCes /AesCls )
= SIM response for l 3 Ci 2 -2 , 3 , 7 , 8-TCDF
internal standard ion at m/z 316 + 318
= SIM response for * 3 Ci 2 -1 , 2 , 3 , 4-TCDD
external standard at m/z 332 + 334
Ci s = Concentration of the * 3 Ci 2 -2 , 3 , 7 , 8-TCDF
internal standard (pg./pL.)
Ce s = Concentration of the l 3 Ci 2 -1 , 2 , 3 , 4-TCDD
external standard (pg./pL.)
Equation 7: Calculation of Relative Response Factor for
1 3C12 -2,3 ,7, 8-TCDF (RRFe ) (When analysis is
performed using DB-5/DB-225 Hybrid Column)
RRFe = (Al s Ce s /Ae s Cl s )
where Ai s = SIM response for * 3 Ci z -2 , 3 , 7 , 8-TCDF
internal standard ion at m/z 316 + 318
Aes = SIM response for 3 7 Cl< -1 , 2, 7 , 8-TCDF
external standard at m/z 312
Ci s = Concentration of the 1 3 Ci 2 -2 , 3 , 7 , 8-TCDF
internal standard (pg/pL)
Ces = Concentration of the 3 7 C14 -1 , 2 , 7 , 8-TCDF
external standard (pg/pL)
C33
-------
h. Equation 8:
Concentration, pg
where: As
Al 3
W
RRFc
i. Equation 9:
% Recovery =
Ais
RRFd
j. Equation 10;
% Recovery
AlB
Es
RRFe
Calculation of concentration of native 2,3,7,8-
TCDF using L3Ci2-2,3,7,8-TCDF as internal
standard
./g. = (As) (Is )/(Ai3 ) (RRFc ) (W)
= SIM response for 2,3,7,8-TCDF ion at
m/z 304 + 306
= SIM response for the l 3 Ci 2 -2 , 3 , 7 , 8-TCDF
internal standard ion at m/z 316 + 318
= Amount of internal standard added to each
sample (pg.)
= Weight of sample in grams
= Relative response factor from Equation 5
Calculation of % recovery of l3Ci2-2,3,7,8-
TCDF internal standard (When analysis is
performed using DB-5 Column)
100 (Ais ) (Es )/(Aes ) (Ii ) (RRFd )
= SIM response for *3Ci2-2,3,7,8-TCDF
internal standard ion at m/z 316 + 318
= SIM response for *3Ci2-1,2,3„4-TCDD
external standard ion at m/z 332 + 334
= Amount of *•3Ci2-1,2,3,4-TCDD external
standard co-injected with sample extract
= Theoretical amount of *3 Ci 2 -2 , 3 , 7,8-TCDF
internal standard in injection
= Relative response factor from Equation 6
Calculation of % recovery of *3Ci 2-2,3,7,8-TCDF
internal standard (when analysis is performed
using hybrid DB-5/DB-225 column
= 100 (Ais) (Es)/(Aes) (It) (RRFe)
= SIM response for J3Ci2-TCDF internal
standard ion at m/z 316 + 318
= SIM response for 37C14-1,2,7,8-TCDF external
standard ion at m/z 312
= Amount of 37Cl4-1,2,7,8-TCDF external
standard in injection
= Relative response factor from Equation 7
C34
-------
5. Criteria Applied for Qualitative Identification of
2,3,7,8-TCDD and 2,3,7,8-TCDF
a. Mass Spectral responses must be observed at both
the molecular and fragment ion masses corresponding to the ions
indicative of TCDD and TCDF (see Tables 1 and 2) and intensities
of these ions must maximize essentially simultaneously (within +
1 second). In addition, the chromatographic retention times
observed for 2,3,7,8-TCDD and 2,3,7,8-TCDF must be correct
relative to the appropriate stable-isotopically labelled internal
standard.
b. The ratio of the intensity of the response for the
molecular ion, [M] * , to the response for the [M+2]+ ion must be
within ±15% of the theoretically expected ratio for both the
native TCDD and native TCDF signals (for example, 0.77 in the
case of TCDD and TCDF; therefore, the acceptable range for this
ratio is 0.65 to 0.89).
c. The intensities of the ion signals for either
2,3,7,8-TCDD or 2,3,7,8-TCDF are considered to be detectable if
each exceeds the baseline noise by a factor of at least 2.5:1.
d. For reliable detection and quantitation of
2,3,7,8-TCDF, it is also necessary to monitor the molecular ion
of hexachlorinated diphenyl ether which, if present, could give
rise to fragment ions yielding ion masses identical to those
monitored as indicators of the TCDF. Accordingly, in Tables 1
and 2, the appropriate ion-mass for hexachlorinated diphenyl
ether is specified and this ion-mass must be monitored
simultaneously with the 2,3,7,8-TCDF ion-masses. Only when the
C35
-------
response for the diphenyl ether ion-mass is not detected at the
same time as the 2,3,7,8-TCDF ion mass can the signal obtained
for 2,3,7,8-TCDF be considered unique.
F. Quality Assurance/Quality Control Procedures
1. The Quality Assurance and Quality Control procedures
itemized below will be implemented throughout the course of the
Dioxin I analyses:
a. Each sample analyzed is spiked with stable
isotopically-labelled internal standards, prior to extraction and
analysis. Recoveries obtained for each of these standards should
typically be in the range from 40-120%. Since these compounds
are used as true internal standards however, lower recoveries do
not necessarily invalidate the analytical results for native
2,3,7,8-TCDD and 2,3,7,8-TCDF, but may result in higher detection
limits than are desired.
b. Processing and analysis of at least one method
blank sample is generally accomplished for each set of samples.
c. It is desirable to analyze at least one sample
spiked with representative native TCDD/TCDF for each set of
samples. The results of this einalysis provides an indication of
the efficacy of the entire analytical procedure. The results of
this analysis will be considered acceptable if the detected
concentration of the native 2,3,7,8-TCDD and 2,3,7,8-TCDF added
to the sample is within +.50% of the known concentration.
d. At least one of the samples analyzed out of each set is
usually analyzed in duplicate and the results of the duplicate
analysis are included in the report of data.
2. A report describing the results of the analyses
C36
-------
discussed above will, at a minimum, include copies of original
mass chromatograms obtained during analyses of the sample
extracts and associated calibration standards, a description of
the analytical methodology employed, and tabulations of
calculated results. Calculations and manipulation of data are
most efficaciously accomplished using computerized data reduction
techniques. The tabulations of calculated results provided in
the report will include a set of tables showing the
concentrations of 2,3,7,8-TCDD and an additional set of tables
showing the concentrations of 2,3,7,8-TCDF which were measured in
each sample. Also shown in the tables are the quantity of each
sample analyzed; the detection limits for those samples which
were found to contain no 2,3,7,8-TCDD or 2,3,7,8-TCDF; the GC-MS
instrument implemented in the analysis; the date and time of the
analysis; the ratio of the intensities of m/z 320 vs. m/z 322 and
m/z 332 vs. m/z 334 for TCDD and the ratio of the intensities of
m/z 304 vs. m/z 306 and m/z 316 vs. m/z 318 for TCDF; the percent
recovery of the internal standard (l3Ci2-2,3,7,8-TCDD or 1 3Ci 2 -
2,3,7,8-TCDF); and the ion intensities for the following m/z's:
320, 322, 257, 332 and 334 for TCDD, and 304, 306, 241, 316 and
318 for TCDF. Examples of typical tables of the type described
above are provided in Attachment A. Other tabulations of data
shown in Attachment A which will be provided in the report
include a table showing a summary of the calibration data
obtained for 2,3,7,8-TCDD and 2,3,7,8-TCDF, which show the date
of the calibration; the GC-MS instrument implemented; the WSU
identification number of the calibration solution; the calculated
C37
-------
response factors and the mean response factors obtained for
native 2,3,7,8-TCDD, native 2,3,7,8-TCDF, l3CL2-2,3,7,8-TCDD and
13C 12-2,3,7,8-TCDF; and the \ valley observed for the GC separation
of the 2,3,7,8-TCDD from adjacent-eluting TCDD isomers and of the
2,3,7,8-TCDF from adjacent-eluting TCDF isomers. A typical
calibration summary presentation is provided in Attachment A.
Additional tables which present calibration data and results
obtained for each individual sample in a more detailed manner
than that given in the summary tables mentioned earlier are also
shown in Attachment A.
C2,8
-------
I I I I
- <=a
r->
*• x:
c"-»
C3
pt* »~O
o
o tr>
va co
c=»
I t~3
v» «c
bd •*-!
o> ••-«
«n AJ
<0 wt
CO Ul *->
C39
-------
*-» o> ac
rt» O *—*
a .«-H »»-i • •
-.-I *_> C3 ,
b i~. o sc*
»»i O ••-* —•
o. a> -»->
-e E-« o«5 o
O 03
C=3
as i-^-
C^ "•»
=3 >-•
O* BC
<^a
va -a:
CO Q
wU I O>
CO V> SE
.-< as •—t
E-* I «o
<-J =D
«>
CO
as to
• •-* d k«
4> *-»
ca 6-« at
a> AJ
C40
-------
ATTACHMENT A
REPRESENTATIVE TABLES OF DATA OBTAINED IN DIOXIN I ANALYSES
C41
-------
ririsnt State univsrsitv. Davrop. C"iio •»;»55
Ses'jits or 3C/T5 flrialyse; of Extracts for 2. 3. 7. 6-TerraunioroDiDeri:o-:3-3:oxi.'i
Corceritratioris Founa (oicocrs'ss 2er nrsn of ssmoie or aarts-ser-triiiion;
D65 Column ilsoreer £cec:f:c for 2,3.7.3 TCiw)
Ccr.c. "euro
*ei:nt :':'~ I.istr. Ion Irr. -atios * c. Ion Intensities a. 2.
o a. re;;. rC'C 3. ID Date Tiue 313/3; 2 332/33-* Sec. 323 322 2f7
££3.3 ND 3.3112 i"52iH 33l267 la:»£ 3.73 49.1 -<.l£~i!>* -i.7E+39 t '_?•«•( 13,33 ,%D 3.678 r,S2. A 331187 23:23 3.79 5S.4 -i.'iE^ -!.ZE-*-f4 -5.6E-34 3. 12£i36 Lr.t-i-ti
DF32-313 5.53J l/.a p£2frt 331237 l'3:-»2 3. 5J 3.75 7i.5 4. 5H-?5 5. 6*E^o5 3. 35E-I-35 3.23E+K 4. r-fE+K
,;.5i-cS357 7.773 »D 1.82 .r£23A 33l2S7 12:25 3.7S bi.'5 -2.c£-i"r -2.4E^34 -3.aE*3t 3.57Et>rb *.35£t3o
LA5 ff-T-Nri 1-3. 33 Nil 3.635 .rSirn 331257 13:32 3.75 £4.9 -!.3E«-i:"» -9. 3£*33 -i.SE-rJt 3. 23E+36 ".i!Z£-35
lf~f ?LP\K 13.33 ND 1.B4 flbcfH 3312S7 ll:39 3.^5 5£. t -1.3E-34 -l.3E*3f -2. 7E»3t l.bst-i-K i-r^-t'S
a. For natsr ==r;o:°s tr>= wirni of tne saaioie aiicuo: was caicuiatBo bv muuiaiving tne vo!'ri« of wa*sr anaiv:eo bv l.K~f&.
T,-= xeicnt of e=c-; siicucc of siuoge aro ouio nas coc3:rec af~=r ove'i-cfYi^D iiis soiin isee Hr'aivtical Protocoi f:<"
Cven-ur:=3 Soiics D2:srsi:r5a':ion>. ta.-caias recsivsc as 5iurr:r= were fii-,ereE. we soiias ovs."._cnsai3=e H.iaiytica:
Src:ccoi for refer=nc2 co Total SuscerDeo Sohcs Detersinationi, an ahc'jot of -rts ariea soiia w=s tnen removea ~-T^~
wei:ne'3 Dr:or 1:0 araiysis.
D. .^DC = fliniswa Cetectaois Ccncsntration
c. % Sec. = Percent recovEry for 13C12-2. 3.7. 3-TCDD internal star-tare
o. The rio:£:iori used here ro ^esicnate ion intensifies is e.xcoreritiai notation. Trie ntwcer oreceairiO E snouic ce rauuir'-iea
oy a factor of 13 raiseo to tne cower of trie nuraoer foiicwinn £. inerefore tne cssinnation 7.6i£-35 idc:cates 7c3. >r^.
e. (\ necative sicn orscecino tne oeaK intensity value cited iraicates tnat no response was ooserveo at tnat ;n/; v.nicn eyr~C3 tne
noise isvei DV a factor of 2.5 or greater. The r.u'noer foiiomng tne /"iS^ative sinri is tne ooserveo TOISS level at :*a: w:.
C42
-------
TABLE 2
origin 5tar,e univ5rs:v/. Davton. Cmo "f-^S
xesuirs of rC/iTS ^.isivses of Extra-is for 2. 3. 7. 3-7etraCnio'"oiMren:cr|.ir3n
Concentrations ro'jnc loicoaraMS :er sraro of siraote or oarts-cer— iniiionj
D55 Co i 'jcn
E^'A'scer.1 C:r,c. "our.c
:=':j.s *eir,i: .:OT Insrr. Ion Int. ^arios % c. Ion i/n=-s:T:2= s. f.
,Nu:'cer 3 a. reas. 2. ,"iC c. ID Date Tu<'e Z3 -5.5£~.> e.'JaE-ss f. £:£-?i
;63~-ilj 1'373 NJ 3. ii'54 ^£2:^^31067 13:18 I.i5 a. 35 36. S ». f-*£+y-* 3.6-E*^" -3. tE»¥t S.tSE-tfS :.5r£-ib
i£Jc':?J7 553. j if . 3 rtlfH '?3i'i"«7 15:i7 tf. 77 y. 75 53.3 £. 33E*37 d.B2:.~f7 6. l^E-i'b S. !?£*io :. ^£-fe
SGl-HZca 57c. <) 3.l8 MScf^! 331167 15:15 tf. 63 i1. 55 63.5 £. 13E-67 i.o7£-'35 7.13£-io l.-tt£-tf5 3.23E4-i15 3.57£-i'5
D£3ci'3Ij '3. ltd 5'ri I'SIfM V'3li87 i»:3i @. e3 '3. 33 76.6 3. l»£^7 3.'3i£+37 3. li£i-*5 5.6£i*/b 7.ai£*^S
D£iiic33 5.t^3 i:.l «r3ifH 33ii67 ie:27 ».£-+ w.63 £4.3 3. -*7E*i?5 5.A3E-?5 I3.67t*il4 4.6iE*«6 f.77E-t'5
i;5 y.~---4 M.te M 3.b64 fi£i:A S3 11 57 i3:£"3 B.fi4 55.3 -i.bE-«4 -l.s£-*fo -4.:E*i?4 5.S£-3b b.^E^Zs
Dr?i-5i3 ?. :33 33.1 fisii'M '33:587 iw;";: '3.65 '3.76 79.7 £.'3'iEi-?i 2. 3f£iiS 4.7'3£*tf5 5.93E-'3S 7.£-i£-i-i
S-31-J6337 7. 77'3 7. li PIS253 33lc?7 i2:35 3. 71 3.73 67.4 3. Ei'E-MJS 4.93E'-35 1.63E+35 6. 36£^b s. £±£-3b
i-PB ?L.c>;n l'3.i''3 ND 3,465 r£5f.n 331537 13:35 i'.ai 63.5 -9.9E+33 -i.tE^ -4. l£+t'-» 5.5i£i-3b 6.i;£-v5S
Lf5 E'.kvK 13. '30 PsD 3.5ia wSiSfl 33:587 11:35 e.dS 55.^ -5.t£f33 -3. «E+t3 6.5l£Tt''» 2.55E+ib 3. £'•£-<€
3. rc-r_ later ssnaiss tn° v-ei^fii; of ins ssiinio aiicuoi was caic-jiaten bv •ivjitisivirig t.ne voiu.-'e of water snaivrea bv !.3sv3.
The '^ei:nt of ejcn aiicuoc of siucce ar-a ouln KJS oo:-a:r.e2 af'er oven-crvir.c'tne soiia is?3 Anaiyticai Protocol for
Gven-i'r'.=q Soiics L'e:=rMir:atior), Si-caiss rscsr/ea as slurries wer° f:lter=6. tne soiics oven_aneau?5 Hnaivtica;
Protocol for refererce to lorai Sus^erCrd Sohcs CsterairsaiiGn). an aiia'joi; of v'.e ariea EOIIO was men rentovea arc
orior to analysis.
s. The concentrations listed for 5. 3. 7. 3-TCDf couia irciucs contrioutions frosi co-eiuiinn TCDF isoraers.
c. hCC = MinhiuM DetsctaDie Concentration
o. X r.ec. = Percent recovery for 13C15-5. 3.7. 3-TCDf internal 5'ancarc:
e. Tre riotatiori 'jsea nere to aesicnate ion interisities is exnorientiai notation. Tr.e nuncer orececinn £ sncuio re sui*i:i:eQ
oy a factor of 13 raisec to ;r,e 30'ier of trie nurscer foilcwinn £. Tnerefore tr.e cesinnation 7. St'£+'?5 incicates 75^. Jw.
f. fl relative sicn orecscing the :eak iriter.sity vabie citeo indicates tnat no ressonse nas oosers'eo at tnat ra/z wmch evcsscs t~e
noi=? level DV a fac:cr of 5.5 or Greater. The nymoer foilowina the necative sicn is the oDservea noise ievei at tr.s: a/^.
C43
-------
TA3LE 3
nr:cr.; 5;j:s ;jr:ver;:;v. Davsor. uiio
' "~/."b -oa'vc=5 OT -x^.*-'
ID ['at 2 7r.:° 3C*"/3'0':.
"£5:H 331757 IS:;1* $.35
'SifH 23:737 14:es 2,69
** - »n»~ ^ * 7 j-'i'ar^arn '\ A***->ui '•3>*T.^nv*3»s
* :ren of Eavois or r3r:=-:er-*,niiiori)
A y~ H ^ ~, y " ' ~*L>J. ^ i.{'~-^.(j s ~£'--'{2t
./., ...,. .j ... . tJ
i^, / ' /* '" I M»*-*v^S •' /"*• rT-''|i~ •• ^ •'w-*'^j
315
7.£->
-.u..-c.
1.57E-:
i. 8iE-«5
S£5H i?31787 18:4-2
ic'iiETSc :y suiticivinn tns voiyse of 'water arsaivisc: bv i.f=yi
213^0 of tr;2 sa'.ijie aiicuo; was caJ
r['C =
% .".so. = Percent rscoverv for !3C:£-E', 3.7.5-TCD;- internal s'larcjco
Tne notation usec nei"° ro cssirna'e lOfi irneisisies is ?x2o«5','iai no'i^iors. T'rs nfsoer srececirig E =-*.oijic be SUIT: cli=-:
by a factor of i'3 ra:;ea to tne Dcwer of v^= r-'j^:er foiioir.n; E. Thers'cre tr.e c?s:cr>,a":ort 7. 2JE-O ir.aicatss 75 15. t-:?.
5. H rejaTivs si en crecscira me 3S3K irstsnsikV vai^e cued ircica;=5 C.T£: no .~e£r-:r;£5 ^as oc-=srv=a at- :"£i u/2 STI:T r-:r5C
noi=2 i;v=i ay a fac:or of i.5 or gr2ai2r. The n»ra:sr fo.ic*»ir2 tr.s r.scat::v2 5::n is *-.e o:=5rv5C ncis= lavsi a: fa^
C44
-------
TA3I2 4
of 5. 3. 7. 6-TCL'ii. 7CD
c= for '2C-:T5
ID
Measured -,.-
TCDD TCI1
rean Sf
TCjD TCI
^2/1 1/67
'/i. -
£3/17/67
tfZ/l7/i7
i'3'l7/c7
.'l.i'Bl
13/37
13/67
i ra
"C;.Q ^EriX
TCDD i-E'U
i. 5 ;i
TCi!) PE'iiJi
TCLF fEniX
TCI1? -E'-.K
la 52
~CIr -E.'IX
TCDD Pt.iiA
(L, 5 ca
TCDD PE.1U
i1. :6
l.JS
13
15
It
1«
C45
-------
TABLE 5
£3.."; .-':'i No. 7ZF-=:3 file a £7 Sta.'ioara c'jrve ' D-.oxiris 5 f'jrans
Star.carG ID 2 r.s
Da:»: 03/1 ?/S7 _ _" 7i;:e: 16:56
EC/nS S'jn .'
-------
TABLE 12
I .= : •.••.•?!•• 10 L'£?i':tVis_ «Ej ID C.-_a-i7H
'•±->;:? a"a:v;:s for 2375 TC-F. TCjD c.'.iv.I'rf.'
L'i'.s: c. T^F-'-S'.Zo f'.iz s 3!
ii'ois r::e ££?. o ;:i Irrrrv.e.o pT.ount '?.2f'3 of Hanoie
Irs:rj-.-eri: ID ."Si;.-}
±oi.«3 Levels 12C12 ICIF 1231;: TCDO Ii3* TCDD
!.;-ei ,v3 l.tC %G tf.fi v3
Iri;=rrrai Sr.ar.cara 5'j;'ir:'crv
.•"/I rax Tie x TIC ri'io .^=o:on xecive^v
3la brie" 1?3 0.6! IJClc! TCDF :2. •
318 ££6:2 iC'J
^^ '51 '^'tt~ ic'2t TCLD 3cf.
: TIC r.^TIu xEjIC.N VPLLS
3M »;3
3t'b 1^54
i;7 lli'S
TCDD '?. «W tf. 3H2
TABLE 13
C^storsr ID 6t37lli3lB wEu ID
e i-.alvsis for £378 TCDF. TC^D oniy\DB5)
,r: In;ecnvn Pwurt 3.2lO of Samsie
lnsir-:-.erii; ID MSc5A
Soi^e levels j3Cld TCLf 12Cii TCDD i£34 TCDD
i.tti NiJ 1.25 ,NG w.5J sG
lr:r,=rrta\ Stir^aro Suraary
M/Z rax Tic > TIC Ratio Semen _ Secove'-y
3!6 r^Bstf 1W B. 85 i2j"lc: TCDF 38.3 "
3:8 5'3.B3l it^
332 3o9si 93 tf.7b 13CI2 TCDD 3'3.'3
334 363,19 97
232 3«5l S'5 «. 81 !£:34 TCDD £18.5
334 36iG-3 'Yi
2375 Isofi'srs Su.iparv PPT Leveis
,r/Z rfti "1C % TIC SAT ID StblCN VfrJjE XDQ
i"i Ici12 -3i3
3i'4 757 b^
3J€ 52'J 7d 1.25+ TCLF
357 12b8 -30
3£ti 3§! -3«
3c2 a/fa -3a 8.W* TCDD
C47
-------
TABLE 29
a:?: oj./ .•:'-/ ::-e: i!:.:/
'j?i 'c. ~I~-3lI^ riis - ^7
Jib
,"/Z .*H< TIC •• TIC i-PTIG xE'jIC.1-- VV-E
78
TABLE 30
Da* 2: -?2'li/:7 ~i';:e: !5:J"3
Sun ,v., TD,"us;25 file ^ 43
5oije Levels !3Ci2 "CDF
!.cO NG
In'srta: 5;ar;carc Siiv.niarv
.•"/Z ."ax Tic - TIC ^atio .:.=:ion S=CJ/e'
3li 2ic7 Sb 18. ^2 12-i:2 7CT> be. 3
313 2^di 5-3
2376 I sobers Susimarv P^T teveis
ft/I rM TIC ^ TIC rfnTIO SEGIGx V*JL,L-C i
2"! 2?3 21
2tfH 228 57
3*6 2:6 97 0.83 TCDf 14.9 $.&
C48
-------
TABLE 39
WRIGHT STATE UNIVERSITY, DAYTON, OHIO 45435
ADDITIONAL DATA RESULTING FROM ANALYSES OF SAMPLES
FOR EPA/NCASI PAPER MILL STUDY
EPA
I.D.
DF024603
DE020920
DF024513
RGI-S6357
Sample
Type
Sludge
Sludge
Sludge
Slurry
% Moist
As Rece
5.8
61.7
83.3
—
Total
Suspended Solid
5188 mg/L
C49
-------
ATTACHMENT D
NCASI METHODS FOR THE ANALYSIS OF
CHLORINATED PHENOLICS IN PULP INDUSTRY WASTEWATERS
-------
ncasl
technical bulletin
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT. INC, 260 MADISON AVENUE. NEW YORK. N.Y. 10016
NCASI METHODS FOR THE ANALYSIS OF CHLORINATED PHENOLICS
IN PULP INDUSTRY WASTEWATERS
TECHNICAL BULETIN NO, 498
JULY 1986
Dl
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NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT, INC.
260 MADISON AVE. NEW YORK, N.Y. 10016 (212) 532-900(1
Russell O. Blosser
Technical Director
(212) 532 9001
July 25, 1986
TECHNICAL BULLETIN NO. 498
NCASI METHODS FOR THE ANALYSIS OF CHLORINATED PHENOLICS
IN PULP INDUSTRY WASTEWATERS
Analytical measurement method development and evaluation
represents a significant portion of the National Council program.
The attached technical bulletin is another on this subject and
deals with methods for analysis of chlorinated phenolics in pulp
industry wastewaters.
The first technical bulletin on this subject was issued as
Stream Improvement Technical Bulletin No. 347. This technical
bulletin reflects the improvements in the method made since then.
It discusses the modifications made to the original procedures
and why these were required.
The bulletin includes (a) the revised gas chromatographic
procedure for analysis of chlorophenols in water and (b) an im-
proved gas chromatographic/mass spectrometer procedure which
permits identification of six additional compounds of interest.
The laboratory investigation of these procedures and prepa-
ration of the technical bulletin was carried out by Lawrence E.
LaFleur, Organic Analytical Program Manager. He was assisted by
Mr. Kenneth Ramage. Both are located at the West Coast Regional
Center.
Your comments and questions on the contents of this bulletin
are solicited and should be directed to this office or to Mr.
LaFleur, NCASI West Coast Regional Center, P.O. Box 458,
Corvallis, OR 97339, telephone 503-754-2015.
ours very truly,
Russell 0. Blosser
Technical Director
ROB:mh
CN«on« Count* at (• Pip«r kvtuMry to, A, **} SMm ImprcMiranl toe 1
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TABLE OF CONTENTS
Page
I INTRODUCTION 1
II DISCUSSION OF NCASI METHOD CP-85.01 1
A. Scope and Application 1
B. Reagents 1
C. Sample Preservation 2
D. Procedure Modifications Due to Matrix Effects 2
E. Calibration 2
F. Quality Control 2
III DISCUSSION OF NCASI METHOD CP-86.01 3
A. Scope and Application 3
B. Acetylation Procedure 4
C. GC/MS Analysis Procedure 4
IV SUMMARY AND FUTURE STUDIES 5
V LITERATURE REFERENCES 5
APPENDICES:
APPENDIX A: NCASI Method CP-85.01 A-l
CHLORINATED PHENOLICS IN WATER BY
IN SITU ACETYLATION/GC-ECD DETERMINATION
APPENDIX B: NCASI Method CP-86.01 B-l
CHLORINATED PHENOLICS IN WATER BY
IN SITU ACETYLATION/GC/MS DETERMINATION
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NCASI METHODS FOR THE ANALYSIS OF CHLORINATED PHENOLICS
IN PULP INDUSTRY WASTEWATERS
I INTRODUCTION
As part of NCASI's ongoing methods development and evalua-
tion program, the procedures used for the analysis of chlorinated
phenolic compounds characteristic of bleached pulp mill effluents
have been continually improved and refined since the original
method evaluations were reported in Technical Bulletin No. 347
(1). The purpose of this report is to provide analysts with a
revised method which reflects the improvements which have been
incorporated into the earlier procedure, thereby bringing them up
to date with current practices. The following section highlights
some of the changes. Appendix A presents NCASI Method CP-85.01
in standard methodology format.
It also became apparent that a GC/MS confirmation method
would be desirable, particularly when NCASI Method CP-85.01 was
applied to new matrices. Section III of this report discusses
the modifications to the in situ acetylation which were required
to adapt the method for GC/MS analysis. The procedure, NCASI
Method CP-86.01, is presented in standard methodology format in
Appendix B.
II DISCUSSION OF NCASI METHOD CP-85.01
A. Scope and Application
NCASI Method CP-85.01 reflects an expansion in scope and
application both in terms of the number of analytes and the
types of matrices to which it has been applied. The increased
number and diversity of analytes was in part due to the availa-
bility of standards (initially by in-house synthesis, more
recently through commercial suppliers) but mostly to provide
data necessary to evaluate and monitor the environmental signifi-
cance of the wider array of sample matrices being analyzed.
Information needs pertaining to environmental samples which have
undergone anaerobic degradation prompted inclusion of certain
chlorinated phenols which aren't normally found in bleach pulp
mill effluents. The additional chlorinated guaiacols and
catechols and the chlorinated benzaldehydes resulted from a
desire to better characterize bleach pulp mill effluents. The
specific method modifications or adaptations required to accommo-
date the expanded scope are discussed below.
B. Reagents
The chlorinated benzaldehyde compounds (i.e. chlorovanill-
ins, chlorohydroxybenzaldehyde and chlorosyringaldehyde) were
found to form hemi-acetals when stored for prolonged periods in
alcohol solvents such as methanol. Thus, Method CP-85.01 calls
for preparation of stock solutions of these analytes in acetone
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and that working solutions be made up fresh just prior to use
and be subsequently discarded. This short exposure to tnethanol
has not presented any problems.
C. Sample Preservation
Sample and extract preservation studies showed that with
acidification to a pH of two with I^SO*, samples stored refriger-
ated for up to 30 days showed no significant changes in analyte
concentrations. The data documented storage up to that length of
time but did not indicate 30 days was an upper limit. Storage
beyond this time would have to be supported with additional
information. Similarly, refrigerated extracts were found to be
stable over a 30 day period.
D. Procedure Modifications Due To Matrix Effects
One problem encountered with some of the different matrices
resulted from the inherent buffering capacity of the sample.
The normal carbonate buffer added to the sample failed to raise
the pH adequately enough to insure ionization of some of the
weakly acidic analytes resulting in low recoveries. To resolve
this problem, the pH of the sample is adjusted to 11.6 with 5
percent NaOH following the addition of the carbonate buffer.
This provides both the desired final pH and buffering capacity.
Other matrix problems can be minimized by using a smaller
aliquot of the sample and adjusting to the final volume with
reagent water. This is required when the concentrations of
analytes exceed the linear range of the GC-ECD but also is an
option to minimize matrix effects. It should be recognized that
this directly influences detection limits.
The sample preservation requirements had to be modified to
include addition of sodium thiosulfate to remove residual
chlorine, particularly in bleach plant process stream samples.
E. Calibration
The single point calibration procedure described in Techni-
cal Bulletin No. 347 was abandoned in favor of a six point
calibration curve. Although the calibration procedure is
definitely more time consuming, it substantially improved the
accuracy. A daily calibration check was added to the quality
control plan to test the validity of the calibration curve.
F. Quality Control
A table summarizing NCASI quality control (QC) data has been
included to provide guidelines of what method performance might
be anticipated. Many of the replicate analyses in the QC data
set were at or near the detection limit, so the reported relative
percent differences reflect method performance over the entire
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working range of the procedure. Generally, relative percent
differences of less than 15 to 20 percent can be expected with 35
percent being a suggested upper control limit.
The replicate determination requires that the analyte be at
measurable levels in order to provide the data to estimate the
precision, so, for many compounds which are not commonly encount-
ered (i.e. 3,5-dichlorophenol, 3,4-dichlorophenol, 2,3,6-tri-
chlorophenol, etc.) there is little data available. Recovery
determinations do not suffer from this limitation and the
summary data provided in the method gives a much better estimate
due to the larger number of data points. In general, recoveries
of 90 to 100 percent can be expescted for chlorophenols, chloro-
guaiacols and chlorinated benzaldehyde type compounds with the
relative standard deviations of the recoveries of these compounds
ranging from 15 to 25 percent. Chlorocatechol recoveries are
more in the range of 70 to 80 percent with relative standard
deviations of 22 to 37 percent.
Both the replicate data and the recovery summaries show
that the chlorocatechols remain the most difficult group of
compounds to quantify. The chlorovanillins also seem to cause
problems, but this may be due to lesser experience since they
were the last group of analytes incorporated into NCASI Method
CP-85.01. The lower sensitivity of the monochloro- and dichloro-
compounds of all classes of compounds makes their detection and
quantification more difficult thus giving rise to generally
lower precision and recovery.
Ill DISCUSSION OF NCASI METHOD CP-86.01
A. Scope and Application
NCASI Method CP-86.01 was developed to provide a means of
qualitatively confirming compound identifications while semi-
quantifying the concentrations. The method as presented has not
been used as extensively as NCASI Method CP-85.01 and therefore
the performance characteristics are not as well documented. For
this reason, the scope of the method has been limited to semi-
quantitative. This does not imply that the concentration data
obtained by NCASI Method CP-86.01 is inaccurate, just that the
precision and accuracy of the method has not been well docu-
mented.
The lower sensitivity of the electron capture detector for
compounds with a single chlorine atom prevents their analysis by
NCASI Method CP-85.01. The higher selectivity of a GC/MS
analysis and adjustments made to make up for the inherently
lower sensitivity of the mass spectrometer operated in the full
scan mode allows the scope of NCASI Method CP-86.01 to be
extended to include mono-chloro compounds. The ability to
quantify compounds which are not chromatographically separated
through the use of extracted ion current techniques further
allows the scope of the method to be expanded. Thus, six addi-
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tional compounds can be detected and semi-quantifled by NCASI
Method CP-86.01.
B. Acetylation Procedure
The lower sensitivity of a GC/MS compared to an BCD required
that the sample volume be increased in order to achieve similar
detection limits. Thus, three 100 mL portions were acetylated
in situ, extracted with three portions of hexane and the hexane
extracts were combined and concentrated prior to analysis. It
was felt that this approach more closely approximated the
acetylation procedure used in NCASI Method CP-85.01 and would be
less likely to cause problems due to unforeseen difficulties. It
also provided a simple means for the analyst to increase or
decrease the sample size to accommodate individual sensitivity
requirements without raising questions about the applicability of
the in situ acetylation and/or extraction on larger sample
volumes.
The quantitation technique used in NCASI Method CP-85.01
does not require quantitative recovery of the analytes since the
internal standard is spiked into the sample prior to acetylation
and extraction. This effectively corrects for recovery.
However, in the case of the GC/MS procedure, it was considered
beneficial to improve the absolute recovery of the analytes to
further help improve sensitivity. This was accomplished by
combining three sequential hexane extracts from each acetylated
sample aliquot prior to concentration.
Since the quantitation technique still relies on the
calibration procedure mimicking the sample analysis procedure,
appropriate modifications in the procedures for the preparation
of the GC/MS calibration standards were incorporated into the
method.
C. GC/MS Analysis Procedure
A 30m DB-5 fused silica column was used for the analysis,
not because of improved chromatography, but as a compromise to
minimize overhead time required to change columns. All other
in-house GC/MS analyses routinely performed in our laboratory
utilize a DB-5 column and since relatively few chlorophenolic
conformational analyses are required and the DB-5 column provided
adequate separations, there seemed to be no reason not to use
it. Therefore, for at least those analytes listed in NCASI
Method CP-85.01 which are chromatographically separated, either
a DB-5 or a DB-1 column could be used for GC/MS analysis. A less
sophisticated gas chromatograph temperature program had to be
used due to the software limitations of the HP-5993 GC/MS data
system. Analysts should use their own judgement in making any
changes in the recommended temperature program. Any changes
deemed appropriate should be relatively straightforward and, with
appropriate documentation through quality assurance, should not
alter the applicability of the method.
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IV SUMMARY AND FUTURE STUDIES
NCASI Methods CP-85.01 and CP-86.01 as presented in Append-
ices A and B represent the culmination of NCASI laboratory
method evaluations and refinements. Although vigorous or formal-
ized ruggedness testing has not been conducted, analysts skilled
in trace environmental analyses should be able to conduct the
procedure and, with appropriate quality assurance documentation,
generate reliable data.
The Methods have essentially been subjected to single
laboratory validation studies. It is hoped that through distri-
bution of these procedures that other laboratories will become
familiar with the methods. The inevitable positive feedback can
be incorporated into improved protocols. This will set the stage
for critical interlaboratory validation studies. Upon completion
of those studies, the performance characteristics of the Methods
should be fully determined.
The results of such an intercalibration study were recently
described by Starck, et.al.(2). The procedure used was quite
similar to NCASI Method CP-85.0L. The authors reported that
recoveries of greater than 80 percent were generally achievable
for analyte concentrations above 20 ppb. Below this concentra-
tion, the recoveries ranged from 60 to 70 percent. As is consis-
tent with NCASI Method CP-85.01 performance characteristics, the
chlorocatechols were found to exhibit the highest variabilities
in the recoveries reported. However, this study relied heavily
on spiked water (presumably reagent water) data. The relative
standard deviation of the chlorocatechol results for the waste
water sample was 40 to 54 percent and the recoveries of these
analytes were 0 to 10 percent. Thus, there remain significant
matrix effects which have not been resolved by their methodology.
Future interlaboratory studies should cover a wider range
of analytes (the study mentioned above only discussed six
compounds), address the preparation and accuracy of calibration
standards and cover as wide a range of matrices and concentra-
tions as possible. The resulting data will then complement the
study described above and complete the documentation of the
methods performance characteristics.
V LITERATURE REFERENCES
(1) "Experience With the Analysis of Pulp Mill Effluents for
Chlorinated Phenols Using an Acetic Anhydride Derivatization
Procedure," NCASI Technical Bulletin No. 347 (June 1981).
(2) Starck, B., Bethge, P.O., Gergov, M., Talka, E., "Determina-
tion of Chlorinated Phenols in Pulp Mill Effluents - An
Intercalibration Study," Paperi ja Puu - Papper och Tra, 12,
745-749 (1985).
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APPENDIX A
NCASI
METHOD CP-85.01
CHLORINATED PHENOLICS IN WATER BY
IN SITU ACETYLATION/GC-ECD DETERMINATION
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NCASI
METHOD CP-85.01
CHLORINATED PHENOLICS IN WATER BY
IN SITU ACETYLATION/GC-ECD DETERMINATION
1.0 Scope and Application
1.1 Method CP-85.01 is used to determine the concentration
of chlorinated phenols, chlorinated guaiacols, chlorinated
catechols and chlorinated benzaldehydes (i.e. vanillins, and
syringaldehyde) in water samples. Specifically, Method CP-85.01
can be used to determine:
Chlorinated Phenols
3,5-dichlorophenol
3,4-dichlorophenol
2,6-dichlorophenol
2,4-dichlorophenol
2,3,6-trichlorophenol
2,4,6-trichlorophenol
2,4,5-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol
Chlorinated Guaiacols
4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
Chlorinated Catechols
3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol
Chlorinated Benzaldehydes
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
Miscellaneous Compounds
trichlorosyringol
1.2 This method has been used to analyze untreated and
biologically treated pulp mill effluents, landfill leachates and
receiving waters and bleach plant effluents.
1.3 The method has been found unsuitable for groundwater
samples which contain high levels of non-chlorinated phenols
(i.e. creosote contamination) or samples where pentachlorophenol
and/or 2,3,4,5-tetrachlorophenol are present and are suspected
to have undergone anaerobic degradation.
1.4 When Method CP-85.01 is used to analyze unfamiliar
samples, quality assurance duplicates and recovery samples
should be run and compound identifications should be supported
by qualitative GC/MS.
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2.0 Summary of Method
2.1 Method CP-85.01 provides in situ derivatization,
extraction and gas chroraatographic conditions for the detection
of ppb levels of chlorinated phenolics. Samples are neutralized,
spiked with the Internal Standard, then buffered with K^CO^ in
order to form the phenolate ions which are then converted in
situ (i.e. in the aqueous matrix) to their acetate derivatives
by the addition of acetic anhydride. The chlorophenolic acetates
thus formed are extracted with hexane. A 1 uL to 2 uL portion
of the hexane extract is injected into a gas chromatograph using
a Grob type splitless injection technique and is chromatographed
on a fused silica capillary column using electron capture
detection. The standards used to determine the calibration
curve are prepared by spiking the Internal Standard and the
appropriate levels of analytes into blank water and then analyz-
ing in the same manner as the sample.
2.2 The Internal Standard used in the method 3,4,5-tri-
chlorophenol has been identified as a persistent anaerobic
degradation product of 2,3,4,5-tetrachlorophenol and/or penta-
chlorophenol. Other workers analyzing samples containing these
compounds which have been subjected to anaerobic conditions have
substituted 2,6-dibromophenol as the Internal Standard.
2.3 The sensitivity of Method CP-85.01 usually depends on
the level of interferences rather than on instrumental limita-
tions. The lower detection (LDL) and lower quantitation limits
(LQL) listed in Table 1 represent sensitivities that generally
can be achieved in biologically treated effluent with some
degree of reliability and confidence. Actual detection limits
would have to be determined on each sample.
2.4 Additional compounds can be determined by CP-85.01 but
have not been validated on the above mentioned sample matrices.
Chromatographic data for these compounds is given in Table 2.
3.0 Interferences
3.1 When Method CP-85.01 was applied to groundwater samples
collected in the vicinity of a source of creosote, (i.e. wood
preservation plant) the high levels of non-chlorinated phenols
caused poor recoveries and the method was unsatisfactory.
3.2 The Internal Standard, 3,4,5-trichlorophenol, has been
shown by some researchers to be a persistent anaerobic degrada-
tion product of 2,3,4,5-tetrachlorophenol and pentachlorophenol.
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TABLE 1 CHROMATOGRAPHIC CONDITIONS, DETECTION
LIMITS AND QUANTITATION LIMITS FOR
METHOD CP-85.01 IN TREATED PULP MILL EFFLUENTS
Compound
Relative
Retention
Timea'b
L:DLC
(ug/L)
LQLd
(ug/D
2,6-dichlorophenol
2,4-dichlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,4,6-trichlorophenol
2,4,5-trichlorophenol
2,3,6-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol
4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
trichlorosyringol
0.526
0.564
0.592
0.661
0.738
0.864
0.818
164
646
1,
I,
0.956
1,
1,
1,
086
380
469
1.723
,109
,262
1.337
1.494
1.673
1.991
1.207
1.567
1.636
1.777
ND
3.0
ND
ND
1.2
1.2
ND
0.8
0.6
3.5
3.5
0.6
0.6
0.6
ND
ND
3.0
ND
1.5
1.0
ND
ND
ND
ND
ND
5.0
ND
ND
2.4
ND
ND
1.5
1.0
7.0
7.0
1.5
1.0
1.0
ND
ND
5.0
ND
4.0
2.5
ND
ND
ND
ND
ND
a
c
d
Not Determined
Retention times of acetate derivatives relative to
3,4,5-trichlorophenol acetate
15 m x 0.25 mm I.D. fused siilica DB-1, 0.25 micron film
thickness. Helium carrier (p. = 31 cm/sec at 125°C)
90 percent argon/10 percent, methane detector make-up gas (30
mL/min).
Oven programed from 45°C after a one mimite hold at 15°C/
min to 100°C and then at 2°C/min to 165° then 20°C/min to
230°C. Under these conditions the retention time of
3,4,5-trichlorophenol aceta.te is 17.080 minutes.
LDL Lower Detection Limit
LQL Lower Quantitation Limit
Method CP-85.01 would have to be modified appropriately when
applied to samples suspected of containing these compounds and
having undergone anaerobic degradation. Other workers have used
2,6-dibromophenol as an alternative Internal Standard.
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TABLE 2 ADDITIONAL CHROMATOGRAPHIC DATA
Relative
Retention
Compound Time
4-chlorophenol 0.415
2,5-dichlorophenol 0.564
2,3-dichlorophenol 0.612
5-chlorovanillin 1.160
2,6-dibromophenol 0.826
trichloro-3-methyl catechol 1.877
4-chlorocatechol 0.924
3,4-dichloroguaiacol 0.973
3,5-dichloro-4-hydroxybenzaldehyde 1.456
3.3 Blanks most frequently are contaminated with penta-
chlorophenol. Generally this has been traced to the KTCC^ and
has been removed by baking the reagent at 400°C+ overnight. All
reagents should be tested for contamination prior to use.
3.4 All glassware should be washed with hot detergent
water, air dried and then baked at 400°C for 6-8 hours. Volu-
metric pipets should be washed in an alcoholic - KOH bath and
then rinsed thoroughly with tap water before air drying.
4.0 Apparatus and Materials
4.1 Glassware:
125 mL separatory funnel
100 mL beaker
50 mL graduated cylinder
Volumetric pipets (TD)
2 dram vials with Teflon-lined screw caps
Centrifuge tubes with Teflon-lined screw caps
4.2 pH Meter: Calibrated using two point procedure
4.3 Gas Chromatograph: Analytical system complete with
gas chromatograph suitable for splitless capillary injection,
electron capture detector, electronic integrator and recording
device.
4.4 Chromatography Column: 15m x 0.25 mm I.D. fused
silica DB-1 (0.25 u film thickness).
4.5 Centrifuge
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5.0 Reagents
5.1 Hexane: Distilled in glass; Methanol: Distilled
reagent grade.
5.2 Acetic anydride: Redistilled reagent grade.
5.3 Reagent water: Organic free such as produced by a
Barnstead Model D2798 NANOpure-A water purification system.
5.4 Sodium Hydroxide: 5 percent w/w in reagent water.
5.5 Sulfuric Acid: Mix one part concentrated H2SO4 with
four parts reagent water.
5.6 Potassium Carbonate: Dissolve 150g ^003 (purified by
heating at 400°C for 6 to 8 hours in a shallow tray) in 250 mL
reagent water.
5.7 Internal Standard Stock Solution: Weigh (to the
nearest 0.1 mg) 25 +3 mg of 3,4,,5-trichlorophenol and dissolve
to volume with methanol in a 50 mL ground-glass-stoppered
volumetric flask. Transfer the stock solution into an amber
bottle with a Teflon-lined screw cap and store under refrigera-
tion (4°C).
5.8 Internal Standard Spiking Solution: Pipet 5.0 mL of
the stock solution into a 100 mL ground-glass-stoppered volu-
metric flask and dilute to volume with methanol. Transfer the
spiking solution into five ca 20 mL portions in separate Teflon-
lined screw capped vials, number 1-5 and store under refrigera-
tion (4°C).
5.9 Calibration standard stock solutions: Individual
stocks are prepared by dissolving the amounts of the analyte
indicated in either Table 3 or .4 (+3 mg weighed to the nearest
0.1 mg) in the indicated solvent in 50 mL ground-glass-stoppered
volumetric flasks. Combined secondary dilution stocks are
prepared by pipetting the volumes of the individual stock
solutions indicated in Table 3 and 4^ into separate 50 mL ground-
glass-stoppered volumetric flasks and diluting to volume with
the solvents indicated. The final working solution of the
calibration standard is prepared by pipetting 5.0 mL of each of
the secondary dilution stock into a 25 mL ground-glass-stoppered
volumetric flask and diluting to volume with methanol. All
stock solutions and secondary dilutions are transferred into
amber bottles with Teflon-lined screw caps and are stored under
refrigeration (4°C). The working solutions are discarded after
use.
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5.10 Calibration Curve Standards: The calibration curve
standards are prepared by spiking s-eparate 50.0 mL portions of
reagent water with 25 uL of the Internal Standard spiking
solution and 25, 50, 75, 100, 125, and 150 uL portions of the
final calibration working solution. The resulting solutions are
then acetylated and extracted in a manner exactly analogous to
the samples.
TABLE 3
METHANOL STOCK SOLUTIONS
Compound
mg in
50 mL Stock
2,6-dichlorophenol 4 0
2,4-dichlorophenol 40
3,5-dichlorophenol 40
3,4-dichlorophenol 40
2,4,6-trichlorophenol 40
2,4,5-trichlorophenol 40
2,3,6-trichlorophenol 40
2,3,4,6-tetrachlorophenol 40
pentachlorophenol 10
4,6-dichloroguaiacol 4 0
4,5-dichloroguaiacol 40
3,4,5-trichloroguaiacol 40
4,5,6-trichloroguaiacol 40
tetrachloroguaiacol 40
3,6-dichlorocatechol 40
3,4-dichlorocatechol 40
4,5-dichlorocatechol 40
3,4,6-trichlorocatechol 40
3,4,5-trichlorocatechol 40
tetrachlorocatechol 40
trichlorosyringol 40
mL in
Secondary
Dilution
2
2
2
2
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
Secondary
Solution
ng/uL
32.0
32.0
32.0
32.0
16.0
16.0
16.0
16.0
2.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
32.0
TABLE 4
ACETONE STOCK SOLUTIONS
Compound
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
mg in
50 mL Stock
40
40
40
mL in
Secondary
Dilution
2
2
2
Secondary
Solution
ng/uL
32.0
32.0
32.0
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6.0 Sample Collection, Handling and Preservation
6.1 Samples should be collected in glass containers and
all portions of automatic sampling equipment which come in
contact with the sample should be constructed of glass, Teflon
or stainless steel. Composite samples should be refrigerated
during the sampling period.
6.2 The samples must be iced or refrigerated from the time
of collection until acetylated.
6.3 A portion of the sample should be tested for free or
residual chlorine. Add 35 mg of sodium thiosulfate per ppm free
chlorine per liter. Adjust the sample pH to approximately two
using sulfuric acid. Record the volume of acid used on the
sample identification tag so the sample volume can be corrected
later.
6.4 All samples must be acetylated within 30 days and be
completely analyzed within 30 days after acetylation.
7.0 Procedures
7.1 Sample Preparation
7.1.1 In Situ Acetylation: Remove the sample from
the refrigerator and allow it to come to room temperature.
Shake the sample vigorously to insure it is homogeneous and
then measure out an appropriate aliquot. If less than 50
mL of sample is used, bring the final volume up to 50 mL
with reagent water. Neutralize the sample to pH 7.0 to 7.1
using 5 percent NaOH and 1:4 sulfuric acid. Add 1.3 mL of
the potassium carbonate solution and adjust the pH to 11.6
±0.1 with 5 percent NaOH if necessary.
Transfer the sample to a 125 mL separatory funnel and
spike it with 25 uL of the Internal Standard spiking
solution. Shake the sample to insure thorough mixing. Add
1.0 mL of acetic anhydride and shake the sample with
frequent venting for 30 seconds. Let the sample stand for
5 minutes then shake and vent.
Add 5 mL of hexane and shake vigorously for 1 to 2
minutes with frequent venting. Allow the phases to separate
and drain and discard the aqueous portion. If there is an
emulsion problem, drain the organic layer into a centrifuge
tube, cap and centrifuge for two to three minutes or until
the emulsion is broken. Transfer as much of the hexane as
possible into a vial with Teflon-lined screw cap, label and
refrigerate until analyzed.
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D17
7.2 The recommended gas chromatographic column and operat-
ing conditions for the instrument are: 15m x 0.25 mm I.D. fused
silica DB-1, 0.25 micron film thickness. Helium carrier gas
(u = 31 cm/sec at 125°C)/ 90 percent argon/10 percent methane
detector make-up gas (30 mL/min). The injection port temperature
is 210°C and the oven is programed from an initial temperature of
45°C after a 1 minute hold at !5°C/min to 100°C and then 2°C/min
to 165°C then 20°C/min to 230°C. The Ni63 detector is operated
at 300°C.
The injection port is configured for a Grob type splitless
injection with a 30 second purge activation delay.
7.3 Calibration
7.3.1 Calibration Curve: Establish gas chromato-
graphic operating parameters equivalent to those indicated
in Section 7.2. Using 1 \iL splitless injections of the
calibration curve standards, tabulate the ratio of the area
of the analyte divided by the area of the Internal Standard
data against the concentration of the analyte. Using these
data, calculate the linear regression and tabulate the
slope and intercept data.
This procedure should be repeated whenever the daily
calibration check is out of range, the instrument has not
been used or has been down, a new column has been installed,
etc.
7.3.2 Daily Calibration Check: The working calibra-
tion curve must be verified on each working day by the
measurement of one or more calibration standards. If
the concentration of any analyte based on the current
calibration curve varies by more than +20 percent, the test
must be repeated at a different concentration level. If
this value is also out of range, a new calibration curve
must be prepared.
7.4 Sample Analysis
7.4.1 Sample extracts are analyzed using the gas
chromatographic operating conditions indicated in Section
7.2. Peak integration parameters and area reject thresholds
should be set such that the sensitivities indicated in
Table 1 (Section 2.3) can be achieved.
7.4.2 Inject 1 uL of the sample extract using
the Grob type purged splitless injection technique. If the
peak areas of the identified analytes exceed the linear
range of the instrument, a separate smaller aliquot of the
sample should be acetylated, extracted and analyzed.
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D18
7.4.3 Calculate the concentration of the analytes
using the following equation:
(As) (Vo) (ms)
(AIS) x 50
Concentration = + bs
where: As = area of the analyte
AIS = a*"ea of the internal standard
Vo = volume of sample acetylated (in mL)
ms = slope from calibration curve for analyte
^s = intercept from calibration curve for
analyte.
8.0 Quality Control
8.1 Blanks: Before processing any samples or whenever a
new reagent is prepared, the analyst should demonstrate through
the analysis of a reagent water blank that utilizes all glassware
and reagents required for sample analyses that all materials are
interference free. The blank samples should be carried through
all stages of the sample preparation and measurement.
8.2 Frequency: Approximately 12 to 15 percent of routine
samples should be allocated for quality control. In addition to
this, representative samples from each new or untested source or
sample matrix should be treated as a quality control sample.
Laboratory replicates and fortification should be conducted on
each QC sample to document method performance as indicated by
precision and recovery.
8.3 Replicates: Replicates; consist of running two or more
separate aliquots of the sample through the entire analytical
procedure. The range and mean concentration of the replicates
are determined from the results. The relative percent difference
is calculated as follows:
Relative Percent Difference = 100
(range\
mean j
Table 5 summarizes the relative percent differences measured by
the NCASI laboratory and gives ari indication of the precision of
the method.
8.4 Recovery: Using the mean concentration determined by
the replicate analyses, determines a spiking level which will
give a minimum of three times the background. Spike an aliquot
of the sample with the determined amount of the calibration
standard working solution and proceed to analyze the sample in
the normal manner. Using the results of that analysis, calculate
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D19
the percent recovery as follows:
. _ Level Measured - Background
Percent Recovery = Level Spiked *
x 100
where the background is the mean of the replicate determina-
tions described above.
Table 5 summarizes the percent recoveries measured by the NCASI
laboratory and gives an indication of the accuracy of the method.
TABLE 5 SUMMARY OF THE NCASI LABORATORY QA/QC DATAa
Compound
2,6-dichlorophenol
2,4-dichlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,4,6-trichlorophenol
2,3,6-trichlorophenol
2,4,5-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol
4,6-dichloroguaiacol
4,5-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,6-trichlorocatechol
3,4,5-trichlorocatechol
tetrachlorocatechol
6-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
trichlorosyringol
Relative
Percent Difference
x(n)bMaximum
Percent
Recovery
c Rel.S.D,
2.1
7.6
2.8
10
4.7
5.8
10.5
7.8
13.2
8.2
5.9
7.1
6.3
11.4
12.6
10.3
9.5
11.5
11.7
13.4
18.9
5.5
(5)
(22)
(3)
(2)
(26)
(1)
(4)
(26)
(18)
(12)
(12)
(32)
(28)
(33)
(4)
(1)
(21)
(12)
(29)
(24)
(14)
(17)
(5)
(31)
8.3
27.2
8.3
20.0
17.5
13.3
31.3
30.0
27.7
31.9
28
27
,1
3
28.0
16.7
32.2
24.0
34.1
26.7
33.3
33.3
30.0
31.0
108
106
108
104
98
106
114
96
104
104
103
95
95
91
83
91
80
70
78
76
108
94
98
91
13.3
14.1
10.6
14.8
21.7
10.4
17.5
15.8
18.5
19.0
18.6
19,
10,
,6
,6
18.1
37.7
35.9
31.0
22.3
36.9
36.0
25.5
14.6
25.6
24.6
* QA/QC data up to 6/86 included in summary
b n = number of determinations
8.5 Where doubt exists over the identification of a peak
on the chromatograph, confirmatory techniques such as mass
spectrometry (e.g. NCASI Method CP-86.01) should be used.
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D20
APPENDIX B
NCASI
METHOD CP-86.01
CHLORINATED PHENOLICS IN WATER BY IN SITU
ACETYLATION/GC/MS DETERMINATION
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D21
NCASI
METHOD CP-86.01
CHLORINATED PHENOLICS IN WATER BY IN SITU
ACETYLATION/GC/MS DETERMINATION
1.0 Scope and Application
1.1 Method CP-86.01 is used to qualitatively confirm and
semi-quantitate the concentration of chlorinated phenols,
chlorinated guaiacols, chlorinated catechols, and chlorinated
benzaldehydes (i.e. vanillins and syringaldehydes) in water
samples. Specifically, Method CP-86.01 can be used to confirm or
determine:
Chlorinated Phenols
2-chlorophenol
4-chlorophenol
3,5-dichlorophenol
3,4-dichlorophenol
2,6-dichlorophenol
2,4-dichlorophenol
2,3,6-trichlorophenol
2,4,6-trichlorophenol
2,4,5-trichlorophenol
2,3,4,6-tetrachlorophenol
pentachlorophenol
Chlorinated Guaiacols
4-chloroguaiacol
4,5-dichloroguaiacol
4,6-dichloroguaiacol
3,4,5-trichloroguaiacol
4,5,6-trichloroguaiacol
tetrachloroguaiacol
Chlorinated Catechols
4-chlorocatechol
3,6-dichlorocatechol
3,4-dichlorocatechol
4,5-dichlorocatechol
3,4,5-trichlorocatechol
3,4,6-trichlorocatechol
tetrachlorocatechol
Chlorinated Benzaldehydes
6-chlorovanillin
5-chlorovanillin
5,6-dichlorovanillin
chlorosyringaldehyde
3,5-dichloro-4-hydroxy-
benzaldehyde
Miscellaneous Compounds
trichlorosyringol
1.2 This method has been used to analyze untreated and
biologically treated pulp mill effluents and bleach plant process
streams.
1.3 When CP-86.01 is used to analyze unfamiliar samples,
quality assurance duplicate and recovery samples should be
run. Method CP-86.01 is intended to complement Method CP-85.01,
Chlorinated Phenolics In Water By In Situ Acetylation/GC-ECD
Determination,
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D22
2.0 Summary of Method
2.1 Method CP-86.01 provides in situ derivitization,
extraction and gas chromatographic conditions for the detection
of ppb levels of chlorinated phenolics. Samples are neutralized,
spiked with the Internal Standard, then buffered with potassium
carbonate in order to form the phenolate ions which are then
converted in situ (i.e. in the aqueous matrix) to their acetate
derivatives by the addition of acetic anhydride. The chloro-
phenolic acetates thus formed are extracted with hexane. A 1
to 2 uL portion of the hexane extract is injected into a gas
chromatograph using a Grob type splitless injection technique and
is chromatographed on a fused silica capillary'column using mass
spectrometric determination. The standards used to determine the
calibration curve are prepared by spiking the Internal Standard
and the appropriate levels of analytes into blank water and then
derivatizing in the same manner as the sample.
2.2 The Internal Standard used in the method 3,4,5-tri-
chlorophenol has been identified as a persistent anaerobic
degradation product of 2,3,4,5-tetrachlorophenol and/or penta-
chlorophenol. Other workers analyzing samples containing these
compounds which have been subjected to anaerobic conditions and
are using a similar in situ acetylation GC-ECD procedure have
substituted 2,6-dibromophenol as the Internal Standard.
2.3 The sensitivity of Method CP-86.01 depends on both the
level of interferences in the matrix and on the sensitivity of
the GC/MS. Generally, low ppb detection limits can be achieved
in most samples. Actual detection limits would have to be
determined on each type of matrix.
3.0 Interferences
3.1 When a similar procedure (NCASI Method CP-85.01) was
applied to groundwater samples collected in the vicinity of a
source of creosote, (i.e. wood preservation plant) the high
levels of non-chlorinated phenols caused poor recoveries and the
method was found unsatisfactory. It is likely that Method
CP-86.01 would be subject to the same limitation, although no
tests have been run to confirm this.
3.2 The Internal Standard, 3,4,5-trichlorophenol, has been
shown by some researchers to be a persistent anaerobic degra-
dation product of 2,3,4,5-tetrachlorophenol and/or pentachloro-
phenol. Thus, Method CP-86.01 would have to be modified appro-
priately when applied to samples suspected of containing these
compounds and having undergone anaerobic degradation. Other
workers have used 2,6-dibromophenol as an alternative Internal
Standard in similar in situ acetylation GC-ECD procedures.
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D23
3.3 Blanks most frequently are contaminated with penta-
chlorophenol. Generally this has been traced to the potassium
carbonate and has been removed by baking the reagent at 400°C
overnight. All reagents should be tested for contamination prior
to use.
3.4 All glassware should be washed with hot detergent
water, rinsed, air dried and then baked at 400°C for 6-8 hours.
Volumetric pipets should be washed in an alcoholic KOH bath and
then rinsed thoroughly with tap water before air drying.
4.0 Apparatus and Equipment
4.1 Glassware
250 mL Separatory funnel with Teflon stopcock
250 mL beaker
100 mL graduated cylinder
Volumetric pipets (TD)
Centrifuge tubes: 35 mL with Teflon lined screw cap
Centrifuge tube: 15 mL graduated conical with ground
glass stopper
2 dram vials with Teflon-lined screw caps
Concentrator tube, Kuderna-Danish: 15 mL
Evaporative flask, Kuderna-Danish: 250 mL, attach to
concentrator tube with springs
Snyder column, Kuderna-Danish: three-ball macro
4.2 pH Meter: Calibrated using two point procedure
4.3 Centrifuge: Bench top model
4.4 Evaporation/concentration assembly: Pierce 19797
Uni-Vap Evaporator or equivalent.
4.5 Water bath: Constant temperature capable of tempera-
ture control (+ 2°C). The bath should be used in a hood.
4.6 Gas Chromatograph/Detector System
4.6.1 Column: 30 m x 0.25 mm bonded-phase fused
silica DB-5 capillary column (J&W Scientific DB-5 or
equivalent).
4.6.2 Mass Spectrometer: Capable of scanning from 35
to 450 amu every 1 sec or less, utilizing 70 volts (nomi-
nal) electron energy in the electron impact ionization mode.
A computer system must be interfaced to the mass spectro-
meter capable of allowing the continuous acquisition and
storage on machine-readable media of all mass spectra
obtained throughout the duration of the chromatographic
-------
D24
program. The computer must have software that can search
any GC/MS data file for ions of a specific mass and that can
plot such ion abundances versus time or scan number. This
type of plot is defined as an Extracted Ion Current Profile
(EICP). Software capabilities must also allow integrating
the abundance in any EICP between specified time or scan
number limits.
5.0 Reagents
5.1 Non-spectrograde hexarie distilled in glass (Burdick and
Jackson)
5.2 Acetic anhydride: Redistilled reagent grade
5.3 Reagent water: Organic free such as produced by a
Barnstead Model D2798 NANO-pure-A water purification system
5.4 Sodium hydroxide: 5 piercent w/w in reagent water
5.5 Sulfuric acid: Mix one part cone. ^504 with four
parts reagent water
5.6 Potassium Carbonate: Dissolve 150 g K2C03 (purified by
heating at 400°C for 6 to 8 hours in a shallow tray) in 250 mL
reagent water
5.7 Internal Standard Stock Solution: Weigh (to the
nearest 0.1 mg) 25 + 3 mg of 3,4 ,5-trichlorophenol and dissolve
to volume with methanol in a 50 mL volumetric flask. Transfer
the stock solution into an amber bottle with a Teflon-lined screw
cap and store under refrigeration.
5.8 Internal Standard Spiking Solution: Pipet 5.0 mL of
the stock solution into a 100 ml, ground-glass-stoppered volu-
metric flask and dilute to volume with methanol. Transfer the
spiking solution into five ca 20 mL portions in separate Teflon-
lined screw capped vials, number 1 to 5 and store under refriger-
ation (4°C).
5.9 Calibration Standard Stock Solutions: Prepare stock
solutions of individual compounds by weighing (to the nearest 0.1
mg) 25 + 1 mg of each compound of a known purity. Dissolve the
material in methanol (acetone must be used for the chlorinated
benzaldehydes) and bring to volume in a 25 mL ground-glass-
stoppered volumetric flask. Transfer the individual stock
solutions to 25 mL scintillation vials with Teflon-lined screw
caps and refrigerate at 4°C. Prepare the working solution by
pipeting 1.0 mL of each stock solution into a 50 mL ground-glass-
stoppered volumetric flask. Bring to volume with methanol. This
working solution is discarded after use.
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D25
5.10 Calibration Curve Standards: The calibration curve
standards are prepared by spiking separate 100 raL portions of
reagent water with 150 y.L of the Internal Standard spiking
solution and 50, 750, 1500 uL portions of the calibration
standard working solution. The resulting solutions are then
acetylated, extracted and concentrated in a manner analogous to
a 100 mL sample aliguot.
6.0 Sample Collection, Preservation and Storage
6.1 Collection: Grab samples must be collected in glass
containers having a Teflon-lined screw cap. Automatic sampling
equipment which comes in contact with the sample should be
constructed of glass, Teflon, or stainless steel. Composite
samples should be refrigerated during the sampling period.
6.2 Preservation: All samples must be preserved by
adjusting to pH two, with H2SC»4, and refrigerating. This should
be done as soon as possible after sample collection. Samples
must be shipped in iced containers as quickly as possible.
6.3 A portion of the sample should be tested for free or
residual chlorine. Add 35 mg of sodium thiosulfate per ppm free
chlorine per liter.
6.4 Storage: Samples may be stored in the refrigerator
(4°C) for up to 30 days. Acetylated extracts must be analyzed
within 30 days after acetylation.
7.0 Procedures
7.1 Sample Preparation:
7.1.1 In Situ Acetylation: Remove the sample from the
refrigerator and allow it to come to room temperature.
Shake the sample vigorously to insure it is homogeneous
and then measure out three 100 mL aliquots. Neutral-
ize the sample to pH 7.0 to 7.1 using 5 percent NaOH
and 1:4 sulfuric acid. Add 2.6 mL of the potassium carbon-
ate solution and adjust the pH to 11.6 + 0.1 with 5 percent
NaOH if necessary.
Transfer the sample to a 250 mL separatory funnel and
spike it with 50 uL of the Internal Standard spiking
solution. Shake the sample to insure thorough mixing.
Add 2.0 mL of acetic anhydride and shake the sample with
frequent venting for 30 seconds. Let the sample stand for 5
minutes then shake and vent.
Add 10 mL of hexane and shake vigorously for 1 to 2 minutes
with frequent venting. Allow the phases to separate and
drain off the aqueous portion into the beaker. If there is
-------
an emulsion problem, drain the organic layer into a centri-
fuge tube, cap and centrifuge for 2 to 3 minutes or until
the emulsion is broken. Transfer as much of the hexane as
possible into the Kuderna-Danish (K-D) assembly. Transfer
the aqueous portions back to the seperatory funnel and
extract two more times with 10 mL hexane, combining the
extracts in the K-D. Repeat this process with the remaining
two 100 mL sample aliquots, combining all hexane extracts
and rinses into the one K-E> assembly. Add 1 or 2 carbor-
undum boiling chips and secure the assembly in the water
bath. Watch the sample carefully and remove when the K-D
receiving tube is about 1/4 full. Do not allow the sample
to go to dryness. Transfer the concentrated extract to a 15
mL centrifuge tube using three 1 mL hexane rinses. Concen-
trate to a final volume of ca 0.2 mL. Cap arid store in the
refrigerator until analyzed. After analysis has been
completed, transfer the sample using three 1 mL hexane
rinses to a labeled 2-dram Teflon-lined screw cap vial and
refrigerate.
7.2 The recommended gas chromatographic column and operat-
ing conditions for the instrument are : 30 m x 0.2:5 mm id fused
silica DB-5, 0.25 micron film thickness. Helium carrier gas (36
cm/sec at 200°C). Injection port temperature 210°C. Column
temperature, isothermal at 45°C for one minute then temperature
programed at 6°C/min to 280°C holding for 25 minutes.
7.3 The recommended mass spectrometer operating conditions
are: mass scan range m/e 42 to 336 with a scan speed of 216.7
amu/sec.
7.4 Calibration
7.4.1 Prior to any analysis of standards or samples,
the mass spectrometer must be tuned in such a manner that a
mass spectrum of DFTPP meeting all criteria in Table 1 can
be obtained.
7.4.2 Calibration Curve: Establish GC/MS operating
parameters equivalent to those described in Sections
7.2 and 7.3. Analyze 1 uL splitless injection of the
calibration curve standards and integrate the extracted
ion current areas for each of the characteristic ions shown
in Table 2. Tabulate the ratio of the area of the analyte
quantitation ions divided by the area of the Internal
Standard. Using this data and the concentrations of the
analytes, assuming a 300 mL sample volume, calculate the
linear regressions and tabulate the calibration slope and
intercept data.
-------
D27
DFTPP KEY MASSES AND ABUNDANCE CRITERIA*'b
Ion Abundance Criteria
30 to 60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40 to 60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5 to 9% of mass 198
275 10 to 30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17 to 23% of mass 442
a J.W. Eichelberger, L.E. Harris, and W.L. Budde, "Reference
Compound To Calibrate Ion Abundance Measurement In Gas
Chromatography-Mass Spectrometry." Analytical Chemistry
£7,995 (1975).
b 50 ng DFTPP injected using a Grob type splitless injection
and the following gas chromatographic conditions:
Injection port temperature 210°C, oven programmed from
160°C after a one minute hold at. 6°C/minute to 210°C.
Mass spectrometer conditions are set to scan from 45 to
445 amu at 216.7 amu/sec.
7.4.3 Daily Calibration Check: The working calibration
curve must be verified on each working day by the analysis
of one or more calibration curve standards. If the recovery
of any analyte varies by more than +20 percent, the test
must be repeated at a different concentration level. If this
value is also out of range, a new calibration curve must be
prepared.
7.5 Sample Analysis
7.5.1 The sample extract is analyzed using the
conditions described is Sections 7.2 and 7.3. The extracted
ion current profile areas for each of the ions listed in
Table 2 are tabulated.
-------
1)28
TABLE 2 CHARACTERISTIC IONS AND RELATIVE RETENTION TIMES
Relative
Characteristic Ions Retention
Compound Primary Secondary Timea
2-chlorophenol 128 130, 170 0.598
4-chlorophenol 128 130, 170 0.637
2,6-dichlorophenol 162 164, 204 0.747
2,4-dichlorophenol 162 164, 204 0.771
3,5-dichlorophenol 162 164, 204 0.784
3,4-dichlorophenol 162 164, 204 0.835
4-chloroguaiacol 158 160, 200 0.863
2,4,6-trichlorophenol 196 198, 238 0.877
2,3,6-trichlorophenol 196 198, 238 0.923
2,4,5-trichlorophenol 196 198, 238 0.939
4,6-dichloroguaiacol 192 194, 234 0.987
3,4,5-trichlorophenol(IS) 196 1.00
3,5-dichloro-4-
nydroxybenzaldehyde 189 191, 232 1.001
4,5-dichloroguaiacol 192 194, 234 1.041
3,5-dichlorocatechol 178 180, 262 1.053
2,3,4,6-tetra-
chlorophenol 230 232, 272 1.066
5-chlorovanillin 186 188, 228 1.086
6-chlorovanillin 186 188, 228 1.094
3,4-dichlorocatechol 178 180, 232 1.108
4,5-dichlorocatechol 178 180, 232 1.130
3,4,5-trichloroguaiacol 226 228, 268 1.143
4,5,6-trichloroguaiacol 226 228, 268 1.180
3,4,6-trichlorocatechol 212 214, 296 1.184
5,6-dichlorovanillin 220 222, 262 1.220
pentachlorophenol 266 268, 308 1.231
chlorosyringaldehyde 216 218, 258 1.231
3,4,5-trichlorocatechol 212 214, 296 1.243
tetrachloroguaiacol 260 262, 302 1.258
trichlorosyringol 256 258, 298 1.272
tetrachlorocatechol 246 248, 330 1.338
a Retention times of acetate derivatives relative to
3,4,5-trichlorophenol acetate. Under the chromato-
graphic conditions in Section 7.2, the retention time
for 3,4,5-trichlorophenol acetate is 20.92 minutes.
7.5.2 Qualitative criteria: Obtain EICPs for the
primary ions and the two secondary ions listed in Table
2. The following criteria must be met in order to make a
qualitative identification. The characteristic ions of
each compound of interest must maximize within two scans of
each other and the retention time must fall within 20
-------
D 29
seconds of the authentic compound. The relative peak areas
of the characteristic ions must fall within 20 percent
of the relative intensities as determined in the reference
compound obtained from the previously analyzed calibra-
tion standards.
7.5.3 Quantitation: Calculate the concentration of
the analytes using the following equation:
Concentration = | j (ms) + bs
where: As = area of the analyte ion
AIS = area of the internal standard ion
ms = slope from calibration curve for
analyte ion
bs = intercept from calibration curve for
analyte ion
If the sample produces an interference for the primary
ion, use a secondary characteristic ion to quantitate.
8.0 Quality Control
8.1 Blanks: Before processing any samples or whenever a
new reagent is prepared, the analyst should demonstrate through
the analysis of a blank that utilizes all glassware and reagents
required for sample analyses that all materials are interference
free. The blank samples should be carried through all stages of
the sample preparation and measurement.
8.2 Frequency: A minimum of 5 percent of routine samples
should be allocated for quality control. In addition to this,
representative samples from each new or untested source or
sample matrix should be treated as a quality control sample.
Laboratory replicates and fortification should be conducted on
each QC sample to document method performance as indicated by
precision and recovery.
8.3 Replicates: Replicates consist of running two or more
separate aliquots of the sample through the entire analytical
procedure. The range and mean concentration of the replicates
are determined from the results and the relative percent differ-
ence is calculated as follows:
Rel. Percent Difference = 100 /range\
I mean I
8.4 Recovery: Using the mean concentration determined by
-------
D30
the replicate analyses, determine the spiking level which will
give a minimum of three times the background. Spike the sample
with the determined amount of the calibration standard working
solution and proceed to analyse the sample in the normal manner.
Calculate and record the percent recovery as follows:
Percent Recovery = Level Measured-Background x 100
Level Spiked
where the Background is the mean of the replicate
determinations described above.
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WEST COAST flEOIONAL CCMTC
D 31 po*»«a
CervalHs. OA «na
(909)794401
NATIONAL COUNCIL OF THE PAPER INDUSTRY FOR AIR AND STREAM IMPROVEMENT, INC.
May 8, 1987
MEMO TO: Frank Thomas
FROM: Larry LaFleur
SUBJECT: Revised Isotopic Dilution Quantitation Procedures for
Chlorinated Phenolics Analysis Procedures
Attached is a summary of the revised quantitation procedures we
have discussed in the past and agreed to incorporate into the
analysis of the Cooperative Study chlorinated phenolics analysis
procedures. Essentially, stable isotope internal standards have
been incorporated wherever possible. The standards were obtained
and details were worked out before we began the analysis of the
samples from the final three mills. Thus, as indicated in the
reports I have already sent out, NCASI Method CP-86.01 was used
for the first two mills and this revised quantification procedure
was used for the last three mills.
-------
D32
REVISED QUANTIFICATION PROCEDURE
FOR CHLORINATED PHENOLICS ANALYSIS
The compounds are quantified using multiple internal
standards, with the internal standard to be used designated as
the one closest in retention time to that of a given analyte.
When a labelled analog exists for an analyte, isotopic dilution
is the quantitation method used. The internal standards and the
corresponding analytes are listed below:
2H4 - 4 -chlor ophenol
^3-2 , 4-dichlorophenol
~2 , 4 , 5-trichlorophenol
3,4, 5-trichlorophenol
13Cg-pentachlorophenol
2 -chlorophenol
2 , 6-dichlorophenol
2 , 3-dichlorophenol
3 , 4-dichlorophenol
2 , 4 -dichlorophenol
2,4, 5-trichlorophenol
4 , 5-dichloroguaiacol
3,4, 5-trichloroquaiacol
4,5, 6-trichloroquaiacol
5-chlorovanillin
6-chlorovanillin
pentachlorophenol
5 , 6-dichlorovanillin
tetrachloroguaiacol
A four-point (including the origin) calibration curve is
established by analyzing three levels of analytes using a
constant amount of the internal standards in each. The ratios of
the EICP area of the analyte quantitation ion divided by the EICP
area of the appropriate internal standard quantitation ion are
plotted against analyte concentration. The slope and intercept
are calculated using a linear regression equation and these
values are used to calculate sample concentrations as follows:
Ax
Concentration = slope x — + intercept
where: Ax + EICP area of the analyte primary quantitation ion
o
Aj + EICP area of the internal standard primary
quantitation ion
-------
D33
For those compounds (2,4 dichlorophenol, 2,3,5-
trichlorophenol, and pentachlorophenol ) where a labeled analog is
present, quantitation is performed using the relative responses
of analyte to labeled analog to create a calibration curve as
previously mentioned for the internal standard quantitation. The
relative responses (RR) are calculated using the equation:
RR =
(Rjn-Rx) (Ry+1)
where :
Rx = the isotope ratio measured for the native analyte
= the isotope ratio of an analytical mixture of the
native analyte and labelled analog
The Rx and Ry values are calculated from the EICP data of
the specified quantitation ion obtained by analyzing separate
aliquots of the native analytes and the labelled analogs. This
need only be done once at the beginning of the project. The Rm
values are generated over the range of concentrations which will
be measured and are the ratios of the EICP areas of the analyte
quantitation ion divided by the EICP areas of the labelled analog
quantitation ion. The calibration curve is established by
plotting RR against analyte concentration. As before, the slope
and intercept are calculated and values are used to calculate
sample concentrations as follows:
Concentration = slope (RR) + intercept
where: RR = relative response factor defined above
RR =
A!
Ax = EICP area of the analyte quantitation ion
Aj = EICP area of the labelled analog
quantitation ion.
The following table presents the pertinent data for all
compounds used to establish the calibration curves.
-------
D 34
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-------
ATTACHMENT E
RESULTS FOR 2378-TCDD and 2378-TCDF
(Master Sample Lists)
-------
25-Feb-B
Hill A
Laboratory Data
SAMPLE
NUMBER
SAMPLE DESCRIPTION
LAE
TCDD 320/322 «EC REPORT
(ppt) RATIO 13C12TCDD DATE
LAE
TCDF 304/306 * REC REPORT TCDF/TCDD
(ppt) RATIO 13C12TCDF DATE RATIO
A. BACKGROUND SAMPLES
DE020801 Treated River Water
DE020802 Uater Treatient Precis. Sludee
DE020803 Vater Treatient Sandfliter Sludee
DE02QB04 Softwood Chips
DE0208C5 Hardwood Chips
ND(0.00514)
61.0 11-16-87
ND(0.0107)
51.9 11-16-87
ERR
ERR
ERR
ERR
ERR
B. PULPING PROCESS
DE020806 CoBbined Pulpine 4 Recaust WVs
C. CHEHICAL RECOVER? PLANT
DE020807 CoBbined Process Wastewater
DE02D80B Lite Hud
ERR
ERR
ERR
D. BLEACH PLANT
DE020901
DE020902
DE020902
DE020903
DE020904
DE020905
DE020906
DE020907
DE020908
DE020909
DE020910
DE0209H
DE020912
DE020913
DE020914
DE020809
DE020B10
Unbleached Softwood Pulp
Bleached Softwood Pulp
Bleached Softwood Pulp
AVERAGE
Unbleached Hardwood Pulp
HVPO Hardwood Pulp
Peroxide Hardwood Pulp
Softwood Bleach Line
S-l Washer. C Staze
S-2 Uasher, Eo Stage
S-3 Washer, H Stage
Hardwood Bleach Lines
K-6 Washer. C Stage
K-4 Uasher, Eo Stage (Hypo line)
K-5 Washer, H Stage (Hypo line)
K-2 Uasher, Eo Stage (Per line)
K-3 Washer. H Stage (Per line)
K-l Washer, H Stage (Per line)
Hypo Solution
Caustic Solution
WX0.738)
15.2
16.3
15.8
NDI0.309)
4.89
2.98
0.238
1.82
0.342
0.0212
ND(0.0326)
NDI0.0168)
0.0453
0.0403
0.0247
l»
0.76
0.79
ti
0.79
0.85
0.81
0.85
0.80
0.84
m
it
0.82
0.83
0.79
69.7
76.0
82.3
70.4
64.1
77. 1
72.0
68.1
65.6
78.9
51.7
56.4
91.0
52.5
60.1
9-25-87
3-19-87
4-21-87
9-25-87
4-21-87
4-21-87
4-28-87
3-19-87
5-22-87
4-28-87
5-22-87
6-19-87
5-22-87
6-19-87
5-12-87
ND(0.271)
333
333
WHO. 231)
47.3
50.1
3.806
32.6
5.778
0.305
0.247
0.114
0.318
0.170
0.174
0.78
it
0.78
0.67
0.88
0.82 ->
0.68
0.84
0.77
0.85
57.1 9-25-87
74.8 4-21-87
64.3 9-25-87
54.6 7-17-87
54.3 7-17-87
0.82 -> 37.8 4-28-87
0.88 72.5 3-19-87
0.82 75.3 5-22-87
50.2
39.9
61.4
59.4
53.5
57.0
6-15-87
6-15-87
7-17-87
6-15-87
7-17-87
6-15-87
ERR
21.06
ERR
9.67
16.81
15.99
17.91
16.89
14.39
UNDEFINED
UNDEFINED
7.02
4.22
7.04
ERR
ERR
DE020915 Conbined Process Wastewater
0.296 0.81
106 1-16-87
El
-------
Oi-Har-68
SAMPLE
NUHBER
DE020811
DE020812
DE020813
DE020814
DE020916
DE020917
DE020815
DE020816
DE020817
DE020822
DE020823
DE021001
DE021002
DE020818
DE020918
DE020919
DE020819
DE020820
DE020920
DE020920
DE020921
DE020922
DE020922
DEQ20922
DE020621
DE020821
DE020923
DE020824
DE020924
SAKPLE DESCRiPTSOH
E. PAPER HACH1NES
Cosbined Process Vastewaters
Process Additives
AlUB
Filler Clay
Coater Clay
Dve-1 (Helierco Blue HGV)
Dye-2 (Cartosol Brill. Paper Yellow)
Resin Size Eiulsion (Neuphon
High Brightness Filter (Hvcali
Sliiicide (Dearborn 6202)
Soda Ash
Sodiui Thiosulfate
Whitewater - Clean
Whitewater - Dirty
F. UTILITIES. yASTEWATER TREATMENT
Powerhouse Uastevater
BottoB Ash
Fly Ash
I1IITP Priiary Sludge
yVTP Secondary Sludge
k'UTP Coiposite Sludge
WTP Coiposite Sludge
AVERAGE
CoBbined Untreated Vastevater
Final Wastewater Effluent
Final Uastewater Effluent
Final Vastewater Effluent
AVERAGE
Landfill Leachate
Landfill Leachate
AVERAGE
G. OTHER
Sludge (not froi Kill A)
Thiosulfate I H2S04 Reagent Blank
Field Blank
LAE
TCDL 320/322 HREC REPORT
vpDti RATiO iaC12Tf,6b DATE
0.0205 0.81 52.4 6-19-87
NDiO.660) »* 77.9 9-21-87
23.5 0.76 96.2 9-21-67
709 0.82 77.8 9-21-87
37.4 0.72 86.9 3-19-87
35.8 0.80 80.3 4-21-87
36.6
0.136 0.79 71.1 6-18-87
0.111 0.72 89. B 1-16-87
0.150 0.86 44.5 2-12-87
0.111 0.85 63.2 2-12-87
0.124
0.0309 0.78 59.1 7-9-87
0,0196 0.86 52.7 9-11-87
0.0253
470 0.79 64.5 4-21-87
ND(0.0102) »« -> 35.3 9-21-87
Ui
" TCDF 304/306 I REC REPORT
«< *poti RATIO 13C12TCDF DATE
0.191 0.80 52.5 3-19-87
NDiO.345) ** 61.2 9-21-87
382 0.81 60.1 9-21-87
10S32 0.80 48.2 9-21-87
624 0.89 74.6 3-19-87
732 0,76 72.5 4-21-87
676
1.916 0,78 64.8 6-18-87
2.18 0.74 42.6 2-12-87
2.18
0.124 0,78 48.7 7-9-87
0.095 0,79 52.6 9-11-87
0.110
4186 0.72 47.4 4-21-87
WHO. 0293) H 42.7 9-21-87
LdOomorv Data
TCDF/TCDD
RATIO
ERR
Enn
ERR
ERR
ERR
ERR
ERR
ERF.
ERR
ERR
ERR
ERR
ERR
ERR
ERR
16.26
15.42
18.52
14.09
17.56
4.36
8.91
ERR
E2
-------
ifi-Feb-68
SAMPLE
NUMBER SANPLE DESCRIPTION
Kill B
Laboratory Data
TCDD
(ppt)
320/322
RATIO
(REC
13C12TCDD
LAB
REPORT «t
DATE *«
TCDF
(ppt)
304/306
RATIO
1 REC
13C12TCDF
LAB
REPORT
DATE
TCDF/TCDD
RATIO
A. BACKGROUND SAMPLES
86374601 Treated Intake
86374602 Filter Backwash
86374603 Softwood Chips
86374604 Hardwood Chips
66374605 Softwood Sawdust
86374671 Softwood Sawdust
B. PULPING PROCESS
86374606 Brownstock Filtrate (Int./Eit.)
86374607 Pulp Mi 11
86374609 Recovery. Evap. Recaust
86374672 Recovery, Evap, Recaust
C. CHEMICAL RECOVERY PLANT
NDIO.00693)
54.5 11-16-87
NDI0.00950) if
47.1 11-16-87
ERR
ERR
ERR
ERR
ERR
ERR
ERR
ERR
ERR
86374610 Lite Hud
ERR
D. BLEACH PLANT
86374611 Unbleached Pulp
86374612 Bleached Pulp
86374612 Bleached Pulp
66374661 Bleached Pulp
AVERAGE (612/661)
86374613 Chiorination State (C)
86374673 Chlorination Stage (C)
AVERAGE (613/673)
66374674 Chlorination Stare (Grab)
86374614 Dioxide Stage (D)
86374615 Caustic State (E)
86374615 Caustic State (E)
AVERAGE
86374616 First Hypo Stage (H)
66374617 Second Hypo Stage (H)
86374618 Hypo Solution
86374619 Caustic Solution
86374620 Chlorine Dioxide Solution
MH0.949)
0.0298
i«
0.80
41.4 9-25-87
1.54 0.68 -> 39.0 9-25-87
10.2
11.0
12.6
11.3
NDI0.0327)
0.0463
0.0232
0.83
0.77
0.69
H
0.84
54.6
60.2
67.0
42.1
57.6
4-21-87
8-19-87
4-21-87
3-19-87
11-16-87
54.3
64.4
63.9
60.9
0.0635
0.0722
0.0679
0.65
0.73 ->
0.77
0.88 ->
0.70
67.1
10.3
55.4
30.6
48.2
4-21-87
8-19-87
4-21-87
3-19-87
11-16-87
78.6 5-12-87
0.133 0.66
62.5 5-12-87
ERR
5.40
ERR
2.93
ERR
4.46
0.229
0.219
0.224
0.258
0.132
ND(0.009B)
0.61
0.81
0.63
0.78
H ->
59.8
69.2
50.9
51.4
39.9
6-19-87
7-7-87
5-22-87
6-19-87
3-19-87
1.254
0.834
1.044
1.129
0.913
ND(0.0054)
0.67
0.70
0.71
0.84
it ->
44.1
49.4
59.7
80.8
38.8
6-19-87
7-17-87
5-22-87
11-16-87
3-19-87
4.66
4.38
6.92
UNDEFINED
ERR
ERR
E3
-------
SAMPLE
NUHBER
86374621
86374623
66374624
86374625
86374626
86374627
86374628
86374629
86374641
86374642
86374643
86374644
86374644
86374646
86374645
86374645
16-Feb-68
TCDD
SAHPLE DESCRIPTION (ppt)
E. PAPER MACHINES
Paper Hachine ND(0.00514)
Sliiicide (CB 210)
Dye (Tel low)
Sliiicide (D3TA)
Dye (Violet)
HTI 6440
Perez 631
Santo Rez
F. UTILITIES. «ASTE«ATER TREATMENT
Priiary Sludge 18.9
Secondary Sludge (No/Poly) 88.9
Secondary Sludge (U/Poly)
Untreated Vastevaters NDL0129)
Untreated Vastevaters NDiO.00644)
AVERAGE 0
Leachate ND(0.00405)
Final Effluent 0.0157
Final Effluent 0.0145
AVERAGE 0.0151
G. OTHER
Hill B
Laboratory Data
LAB LAB
320/322 U£C REPORT »« TCDF 304/306 1 REC REPORT TCDF/TCDD
RATIO 13C12TCDD DATE «» (ppt) RATIO 13C12TCDF DATE RATIO
» -> 35.9 8-19-87 0.108 0.69 -> 36.9 8-19-87 ERR
0.79 102.1 9-21-87 101 0.80 90.1 9-21-87 5.34
0.80 78.2 4-21-87 808 0.72 84.8 4-21-87 9.09
ERR
» >2.4 6-18-87 0.092 0.68 49.8 6-18-87 UNDEFINED
«i -> 27.5 9-21-87 0.124 0.67 -> 27.9 9-21-87 UNDEFINED
0.108 UNDEFINED
H 13.7 9-11-87 0.0105 0.64 40.9 9-11-87 ERR
0.86 1)9.7 7-9-87 0.133 0.65 -> 30.5 7-9-87
0.66 159.0 11-16-87 0.110 0.72 57.8 9-30-87
0.122 6. OB
86374681 Field Blank
E4
-------
16-Feh-88
SAMPLE
NUKBEK
DE026001
DE026101
DE026102
DE026103
DE026104
SAMPLE DESCRIPTION
A. BACKGROUND SAHPLES
Treated Eiver Water
yater Soft. Sludge
Sandfilter Backvash
HardHood Chips
Raw yater CMP
TCDD 320/322 iREC
(ppt) RATIO 13C12TCDD
LAB
REPORT
DATE
TCDF
(put)
304/306
RATIO
(REC
13C12TCDF
LAB
REPORT
DATE
Hill C
Laboratory Data
TCDF/TCDD
RATIO
MHO. 00531) «
41.9 8-19-87
ND(0.00694) u
41.0 11-16-87
ERR
ERR
ERR
ERR
ERR
B. PULPING PROCESS
DE026107 Coibined Pulping CMP
DE026111 Recaust And Liie Kiln
C. BLEACH PLANT
DE026002 Unbleached Pulp
DE026003 Bleached Pulp
DE026004 C/D Filtrate
NDI0.564)
ND(0.620)
ND(0.00593)
u
ii
60.2 9-25-87
91.1 11-16-87
63.4 4-28-87
NDI0.162)
14.9
0.0929
ii
0.89
0.73
44.6
62.5
53.7
9-25-87
3-19-87
4-28-87
ERR
ERR
ERR
UNDEFINED
UNDEFINED
C/D-1
C/D-2
C/D-3
C/D-4
DE026005
DE026211
DE026212
C/D Filtrate (Grab-1)
C/D Filtrate (Grab-2)
C/D Filtrate (Grab-3)
C/D Filtrate (Grab-4)
E/0 Filtrate
E/0 Filtrate
AVERAGE (005/211)
E/Q Filtrate
NDI0.0106) »« 52.2 6-19-87
ND(0.0154) » 48.3 6-19-87
0
0.0573 0.87 -> 24.8 7-17-87
0.0543 0.83 -> 13.1 7-17-87
0.0558
UNDEFINED
ERR
E/0-1 E/0 Filtrate (Grab-1)
E/0-2 E/0 Filtrate (Grab-2)
E/0-3 E/0 Filtrate (Srab-3)
E/0-4 E/fl Filtrate (Grab-4)
DE026006 D Filtrate
DE026213 D Filtrate
AVERAGE (006/213)
DE026214 D Filtrate
D-l D Filtrate (Grab-1)
D-2 D Filtrate (Grab-2)
D-3 D Filtrate (Grab-3)
D-4 D Filtrate (Grab-4)
DE026114 Scrubber
DE026116
DE026117
CI02 Solution
Caustic Solution
NDfO.0112)
ND(0.00341)
0
»
49.1
80.3
3-19-87
5-12-87
NDI0.0056) H
0.0272 0.69
0.0136
52.1
68.3
3-19-87
5-12-87
UNDEFINED
UNDEFINED
ERR
WHO. 00912)
68.4 9-21-87
0.429 0.76
54.8 9-21-87
ERR
ERR
E5
-------
SAMPLE
NUMBER
DE026118
DE026123
DE026124
DE026201
DE026202
DE025203
DE026204
DE026205
DE026007
DE026008
DED26009
DE026010
DE026215
DE026011
DE026011
DE026012
DE026013
DE026014
DE026207
DED26216
DE026206
DE026206
09-Bai-Ba
LAE
7CDD 510/3:2 XREC REPORT »» TCL-F 304/306 * REC
SAHPLE DESCRIPTION Ippt) RATiQ 13C12ICDD DATE »* (opt; RATIG 13C12TCDF
D. PAPER MACHINES
CoRbined Process yater 0.0106 0.70 6C.1 6-19-37 0.197 0,7; 56.5
Dve (Hobav Pont. Brill. Blue A)
Dye (Pemsoi Ye II on BRA Extra-6)
Dve (Anthosin Red 21P-BASF)
Biocide (Betz RI-41)
Defoaier (Fleeted 3170;
Dye (Hobay Pont. Bond Yellow 303)
E. UTILITIES. yASTEyATER TREATMENT
Station 15 tfoodboiler
Coal Ash - Siuiced
Coal Ash - ESP
Mechanical Coal Ash
Uood Waste Ash Vater
liood Vaste Ash Water
CoBbined Devatered Sludje 3.37 0.80 77.7 4-21-67 42.6 0,76 53.3
Coibined Denatered Sludge 3.27 0.70 68.2 8-19-67 34.5 0.71 63.8
AVERAGE 3.32 36.6
Pri»arv Influent ND(G.D0276) » 51. i 6-16-87 0.0352 0.72 46.2
Secondary Effluent (0-24 hrs; NDI0.00281) « 62.6 7-9-87 0.0128 0,67 57.1
Landfill Leachate ND(0.00595j «« 50.8 9-11-87 ND(C.00669) *« -> 31.4
Thickened Secondary Sludge 11.2 0.81 -> 22.4 1-20-88 75.4 0.8 5E.5
Thickened Secondary Sludee
Secondary Effluent (36-72 hrs) NDI0.00339) »* 50.7 7-9-87 0.00846 0,79 54.0
Secondary Effluent (36-72 hrs) ND10.00424) «• 61.7 9-30-67 O.OiiO 0.65 42.1
AVERAGE 0 0.01124
F. OTHER
Mill C
Laboratory Data
LAE
REPORT TCDF'TCID
DATE RATIO
3-13-87 16.55
ERE
ERR
ERR
ERR
ERF,
ERR
ERR
ERF.
ERR
ERR
ERR
ERF,
4-21-67
8-19-67
11.61
6-18-67 UNDEFINED
7-9-87 UNDEFINED
9-11-87 ERR
1-20-88 6.73
ERR
7-3-87 UNDEFINED
11-16-87
UNDEFINED
DE026220 Siudje (not froi Mil! C)
DE026206 Reagent Blank
DE026209 Field Blank
317 0.82
63.2 9-21-87
3266 0,81
47.7 9-21-87
10.3
E6
-------
SAMPLE
NUMBER
16-Feb-88
5AKPLE DESCRIPTION
TCDD
(ppt)
320/322 JREC
RATIO 13C12TCDD
LAB
REPORT
DATE
Hill D
Laboratory Data
LAB
i» TCDF 304/306 * REC REPORT TCDF/TCDD
«« (pot) RATIO 13C12TCDF DATE RATIO
A. BACKGROUND SAMPLES
DF024401 Unchlorinated Hater
DF024402 Chlorinated North Entry
DF02U02 Chlorinated North Entry
AVERAGE
DF024403 Chlorinated South Entry
DF024404 SofUood Chips
ND(0. 00456)
ND(0.00773)
0
««
36.9
46.9
7-9-87
8-19-87
ND(0.0052D
NDI0.00469)
0
ii
28.5
51.1
7-9-87
8-19-87
ERR
ERR
UNDEFINED
ERR
ERR
B. PULPING PROCESS
DF024405 Brownstock Sewer
ERR
C. CHEMICAL RECOVERY PLANT
DF024406 Evap..Recov..Liie Kiln Sever
DF024407 Lite Hud
DF024408 Vet Lite
ERR
ERR
ERR
DF024409
DF024410
D. BLEACH PLANT
Coibined Bronnstock Pulp
Bleached Pulp - A
DF024411 Bleached Pulp - B
DF024411 Bleached Pulp - B
AVERAGE
ND(0.695) H
NDd.03) ««
3.89 0.80
3.99 0.75
3.94
47.4
54.6
75.8
67.6
9-25-87
4-21-87
4-21-87
8-19-87
ND10.203)
NDU.23)
7.68
7.90
7.79
H
it
0.69
0.81
35.2
41.4
66.4
28.3
9-25-87
4-21-87
4-21-87
8-19-87
ERR
ERR
1.98
DF024412 A Side Chi urination (C)
DF024605 A Side Chlorination (C)
DF024605 A Side Chlorination (C)
AVERAGE (412/605)
DF024701 A Side Chlorination (Grab-1)
DF024702 A Side Chlorination (Grab-2)
DF024703 A Side Chlorination (Grab-3)
DF024704 A Side Chlorination (Grab-4)
DF024705 A * B Side Caustic (Grab-1)
DF024706 A * B Side Caustic (Grab-2)
DF024707 A * B Side Caustic (Grab-3)
DF024708 A * B Side Caustic (Grab-4)
DF024413 Caustic Coibined (E)
DF024413 Caustic Coibined (E)
AVERAGE (413)
HD(0.0132)
0.0174
0.0955
0.0376
ii
0.77
0.79
80.3 4-28-87
90.8 4-28-87
40.3 7-7-87
0.257 0.76
0.257
45.3 6-19-87
0.123
0.0286
0.0542
0.0686
0.509
0.434
0.472
0.80
0.77
0.71
0.81 ->
0.74 ->
12.1 4-28-87
55.1 4-28-87
37.6 7-7-87
34.9
32.2
1.82
6-19-87
11-16-87
1.83
E7
-------
SAMPLE
NUMBER
16-Feb-88
Hill D
Laboratory Data
SAMPLE DESCRIPTION
TCDD
(ppt)
320/322
RATIO
SREC
13C12TCDD
LAB
REPORT it
DATE ««
TCDF
(ppt)
304/306
RATIO
SREC
13C12TCDF
LAB
REPORT
DATE
TCDF/TCDD
RATIO
D. BLEACH PLANT (cont.)
DF024414 A Side Hypo (H)
DF024709 A Side Hypo (Grab-1)
DF024710 A Side Hypo (Grab-2)
DF024711 A Side Hypo (Grab-3)
DF024712 A Side Hypo (Grab-4)
DF024415 B Side Chlorination (C)
DF024713 B Side Chlorination (Grab-1)
DF024714 B Side Chlorination (Grab-2)
DF024715 B Side Chlorination (Grab-3)
DF024716 B Side Chlorination (Grab-4)
DF024418 B Side Hypo (H)
0.0551 0.77
42.6 5-22-87
0.0857
0.71
50.7 5-22-87
1.56
0.119 0.70
102.6 4-28-87
0.394'
0.79
41.5 4-28-87
3.31
0.331 0.82
75.4 5-22-87
0.602
0.80
67.3 5-22-87
1.82
DF024717
DF024718
DF024719
DF024720
DF024416
DF024417
DF024501
DF024502
DF024503
DF024504
DF024505
DF024506
DF024507
B Side Hypo (Grab-1)
B Side Hypo (Grab-2)
B Side Hypo (Grab-3)
B Side Hypo (Grab-4)
Hypo Solution
Caustic Solution
E. PAPER MACHINES
Paper Machine
Acid Regeneration
Caustic Regeneration
Size Eiulsion
Methyl Violet
Ye! Ion 96
Biocide
ND(0.00590) »*
53.1 8-19-87
0.0146
0.65
56.7 8-19-87
ERR
ERR
ERR
ERR
ERR
ERR
ERR
ERR
ERR
E8
-------
SAMPLE
UMBER
;-F02451i
DFD24604
DF024512
DFG24512
DF024512
DF024513
DF024506
DF024606
DF024514
DF024515
DF02460?
DFC24516
DF024517
DF024518
DF024519
Q9-Har-88
T
3AHFLE DESCRIPTION 'p
F. UTILITIES, WSTEWATER TREATKEST
ilUTF Influent
y»TP Influent
AVERAGE i51 1/60*1
y«TP Effluent ND(0.
tflfTP Effluent ,'JDiO.
y«TP Effluent HD.'O.
AVERAGE
Centered Siud?e
['•ewatered Siud?e
Devatered Sludee
AVERAGE (513/6061
112 Clarifier Frinarv Siud?e
Secondary Siud?e Before Chlorination
Secondary Sludfe Before Chlorinstion
111 Boiler Scrubber
Sludje Laeoon ND(0.
Hi Boiier Bottoe Ash
Secondary Sludje After Chlorination
uuL
pt)
3.0283
00746i
00715)
ooaoB;
0
17.6
19.2
17.4
18.1
17.4
36.1
00317)
35.8
320,322 ttEC
RATIO 13C12TCDD
0.86 51.0
»* 50.1
n 55.6
«» 56.7
0.83 71.8
3.78 63.6
0.74 66.5
0.8t -/ 18.1
0.77 89.0
»« 42.2
0.80 33.6
LAB
REPORT
DATE
11-iB-B7
7-9-87
S-30-87
11-16-67
3-19-37
4-21-87
8-19-87
1-20-88
9-21-87
9-11-87
9-21-87
«* TCEF
** 'pot)
0.0634
0.0503
0.063*
NO (0.00688)
NIX 0.90663!
0
33.7
35.7
31.3
33.8
31.9
77.9
0.0156
73.2
Hii
Lob
LnB
;04/30t * REC REPORT
RATIO 13C127C&F DATE
0.31 -- ;5.« 6-13-57
0.76 ,'3,5 lj-16-3/
»« -> 34.6 7-9-S7
»» 49.1 S-30-37
0.38 57,5 3-19-67
0.31 55.6 4-21-37
0.71 47.8 6-19-8"?
0.79 77.2 1-20-88
0.68 62.4 9-21-57
0.67 *8.5 9-11-67
0.75 87.0 9-21-8'
i L1
oratory Data
TCDF'TCDD
RATIO
ERR
2.06
UNDEFINED
UNDEFINED
1.67
1.83
2.16
W
ERR
ERR
ESR
2.04
G. OTHER
&F024601 Bottle Blank
DF024602 Reagent Blank
DF024603 Sludee (not fron Kill D) 92.6 0.78 83.5 3-19-87 976 0.85 100.4 3-19-37 10.54
E9
-------
SAMPLE
NUMBER
lZ-Feb-88
SAMPLE DESCRIPTION
LAB
TCDD 320/322 MEC REPORT t*
(ppt) RATIO 13C12TCDD DATE »
TCDF 304/306 ( EEC
(ppt) RATIO 13C12TCDF
Mill f
Laboratory Data
LAB
REPORT
DATE
TCDF/TCDD
RATIO
A. BACKGROUND SAMPLES
RG186355 Upstreai River Water
RG1B63S6 Chlorinated Process Vater
RG186356 Chlorinated Process Vater
AVERAGE
ND(0.0226) H
ND(0.00632) «
0
39.1 3-19-B7
43.1 8-19-87
ND(0.0155) «
ND(0.00660) »»
0
36.2
33.3
3-19-87
8-19-87
ERR
UNDEFINED
UNDEFINED
UNDEFINED
RG186389 Chlorinated Process Hater
RG186357 Filter Backwash
SGI86357 Filter Backvash
B6186390 Filter Backvash
RG186358 Hardvood Chips
RG186359 Softwood Chips
RG186360 Groundvood Pulp
B. PULPING PROCESS
RG186361 MB Side General Severs
RG1S6362 Recaust.AfcB Pover Groups n/Evap
RG186363 Lite Hud
NDd.82)
HD(8.21)
it
n
64.9 3-19-87
33.1 11-16-87
8.61
49.6
0.81 ->
0.77
12.8
60.7
3-19-87
11-16-87
UNDEFINED
ERR
ERR
ERR
ERR
ERR
ERR
ERR
C. BLEACH PLANT
RG186364 Unbleached Pulp A Side
R6186391 Unbleached Pulp A Side
AVERAGE (364/391)
RG186365 Unbleached Pulp B Side
RG186366 Bleached Pulp A Side
RG186367 Bleached Pulp B Side
RG186367 Bleached Pulp B Side
AVERAGE
RG186368
RG186368
Combined Acid Sever
Coibined Acid Sever
AVERAGE (368)
RG1B6369 A Side C Seal Boi
RG186370 A Side E Seal Boi
RG166370 A Side E Seal Boi
AVERAGE (370)
RG186371 A Side D Seal Boi
KG186371 A Side D Seal Boi
AVERAGE (371)
RG186372
RG186373
BG186374
RG186375
RG186376
IG186377
K18637B
B Side C Seal Boi
B Side E Seal Boi
B Side D Seal Boi
Caustic Solution
Hypo Solution
Dioiide Solution
A Side Caustic
KD(0.
ND(0.
ND(0.
568)
441)
0
984)
25.6
55.7
46.7
51.2
0.270
0.277
0.274
0.0449
2.292
2.292
0.910
0.910
0.0669
3.597
1.92
it
ii
it
0.77
0.79
0.78
0.84
0.80
0.80
0.77
0.81
0.85
0.80
0.77
76.0
81.9
71.7
76
68.5
59.6
71.7
73.6
77.1
64.9
67.5
60.7
66.3
77.7
9-25-87
9-25-87
9-25-87
4-21-87
4-21-87
8-19-87
9-21-87
11-16-87
4-28-87
6-19-87
5-12-B7
4-28-87
6-19-87
5-12-87
t
0.
1.
2
2.
2.
0.
10.
10.
10.
4.
4.
4.
.32
946
133
.32
139
161
183
182
693
693
173
102
526
314
993
437
715
0.326
14.128
9.158
0.
0.
0.
0.
0.
0.
0.
0.
66
65
65
85
84
73
72
78
0.74 ->
0.
0.
82
88 ->
0.81
0.86
0.75
0.80
66.7
79.4
68.6
78.3
78.5
53.7
57.0
59.3
13.6
73.2
24.7
57.9
52.6
59.1
68.1
9-25-87
9-25-87
9-25-87
4-21-87
4-21-87
8-19-87
9-21-87
4-28-87
7-17-87
11-16-87
5-12-87
11-16-87
4-28-87
6-19-87
5-12-87
ERR
ERR
ERR
5.43
3.55
9.85
3.65
4.50
5.18
4.87
3.93
4.77
E10
ERR
ERR
ERR
ERR
-------
SAMPLE
NUMBER
86186379
RG186379
RG18636G
RG186392
RG166381
RG166362
RG166383
RG1B6384
RG186385
RG186402
RG186402
RG186386
RG186386
RG186387
RGL86387
RG186387A
RG186387B
RG186388
RG186388
RG186368A
RG186394
RG186405
E6186395
RG186396
RG186397
RG186404
R6186398
RG186399
RG186400
RG186401
I2-Feb-88
SAMPLE DESCRIPTION
D. PAPER HACHINE5
Nos 1,2,3,4 & 5 Machines
Nos 1,2.3.4 li 5 Hachines
AVERAGE
Otis Hill Return
Otis Rill Return
AVERAGE (380/392)
Titaniuf Dioiide
Sliiicide RX-36
Sliticide RI-31
Pontaiine Brilliant Paper
Pontaiine Fast Scarlet
E. UTILITIES. UASTEUATER TREATHENT
Priiary Influent
Priiary Influent
Priiary Influent
Priiary Influent
AVERAGE (402/386)
Coibined Devatered Sludge
Coibined Devatered Sludge
Coibined Devatered Sludge
Coibined Devatered Sludge
AVERAGE (3B7/387A/387B)
Final Effluent
Final Effluent
Final Effluent
Final Effluent
AVERAGE (388/388A)
Final Effluent (Grab)
Bottoi Ash
Fly Ash
Grav, Thick. Secondary Sludge
Grav. Thick. Secondary Sludge
Landfill Leachate
Coibined Bleach Plant Eff.
F. OTHER
Reagent Blank
Bottle Blank
Hill E
Laboratory Data
TCDD
(ppt)
0.0522
0.0526
0.0525
0.0908
0.106
0.0984
0.680
0.743
0.681
0.497
0.650
193
168
191
161
178
0.0881
0.0953
0.0804
0.0879
WHO. 276)
ND(0.461)
498
ND<0.00817)
320/322
RATIO
0.84
0.62
0.75
0.78
0.78
0.84 ->
0.76
0.79
0.81
0.79
0.84
0.79
0.77
0.70
0.65 ->
»
i«
0.77
H ->
SREC
13C12TCDD
77.4
49.0
63.7
67.4
68.1
15.8
79.3
41.0
82.4
64.5
78.9
87.9
71.5
65.9
37.4
53.4
66.5
101.1
39.6
LAB
REPORT
DATE
7-9-87
8-19-87
8-19-87
8-19-87
11-16-87
6-18-87
3-19-87
6-18-87
4-21-87
8-19-87
8-26-87
8-26-87
7-7-87
9-30-87
8-26-87
9-21-87
9-21-87
9-21-87
9-11-87
H TCDF
»« (ppt)
0.170
0.176
0.173
0.332
0.361
0.346
3.117
3.228
3.530
2.267
3.036
879
670
762
713
756
0.447
0.441
0.359
0.416
WHO. 183)
ND(0.310)
2147
0.0636
304/306
RATIO
0.72
0.75
0.74
0.73
0.76
0.75 ->
0.88 ->
4.76
0.76
0.75
0.78
0.70
0.76
0.74
0.78 ->
H
SREC
13C12TCDF
60.7
65.3
63.1
66.2
73.8
15.1
31.7
46.0
70.1
79.0
75.7
106.0
65.8
65.7
30.4
42.1
56.2
92.5
37.2
LAB
REPORT
DATE
7-9-87
8-19-87
8-19-87
8-19-87
11-16-87
6-18-87
3-19-87
6-18-87
4-21-87
8-19-87
8-26-87
8-26-87
7-7-87
9-30-87
8-26-87
9-21-87
9-21-87
9-21-87
9-11-87
TCDF/TCDD
RATIO
3.3
3.52
ERR
ERR
ERR
ERR
ERR
4.67
4.24
ERR
4.73
ERR
ERR
4.31
ERR
ERR
ERR
Ell
-------
ATTACHMENT F
MASS.FLOW RATES OF 2378-TCDD and 2378-TCDF
-------
ATTACHMENT F
NOTES
(1) ND - Not detected. Analytical detection level in parentheses.
(2) Ave - Concentration used for mass flow determinations is an
average of multiple analyses of the same sample or of
duplicate field samples.
(3) QA - Percent recoveries of internal standards less than 40%
are indicated. See Sections VI and VII for discussion
of the significance of these recoveries.
-------
Nil! A
8-Feb-8
Nil! A
Hass Balance [ND assuied 0.0 ]
Basis : 1 Day Saiple ID
Al. General Hill Inputs
1. Treated River Vater DE 020801
2. Hlf Chips DE 020805
3. SU Chips DE 020804
4. Landfill Leachate DE 020621
Bl. General Setter Inputs
1. Water Treatment Sludge DE 020802
2. Vater Treatient Bacbash DE 020803
3. Bleach Plant Total
4. Coibined Pulping DE 020806
5. Coibined Recovery DE 020807
6. Paver House DE 020818
7. Coibined Paper Machines DE 020811
Flo* Total
Cla. Bleach Plant Inputs
1. Ml Brounstock Pulp DE 020903
2. SV Brovnstock Pulp DE 020901
3. Treated River Vater DE 020801
4. Paperiachine Vhitewater DE 021001
Clb. Detailed Bleach Plant Filtrate Pious
1. SUC Stage Filtrate DE 020906
2. SU Eo Stage Filtrate DE 020907
3. SU H Stage Filtrate DE 020908
Softuood Line Subtotal
4. HWC Stage Filtrate DE 020909
5. HV(Hypo Line) Eo Filtrate DE 020910
6. HVIHypo Line) H Filtrate DE 020911
7. HIKPeroxide Line) Eo Filtrate DE 020912
8. HUtPeroiide Line) H Filtrate DE 020913
9. HiKPeroxide Line) H Filtrate DE 020914
Hardwood Line Subtotal
Bleach Plant Total
Dla. WTP Inputs
1. Influent To IOTP
2. Landfill Leachate
3. Fly Ash
Dlb. UUTP Sludge Inputs
I. Fly Ash
2. Priiary Sludge
3. Secondary Sludge
DE 020921
DE 020821
DE 020919
DE 020919
DE 02DB19
DE 020820
Flov
(HGD or Dry
Tons/Day)
20
595
105
0.1B
0.8
0.8
7.6
5.5
0.17
0.5
4.3
19.7
355
160
7
1.5
1.73
1.44
0.58
3.75
1.58
0.73
0.26
0.34
0.64
0.30
3.85
7.60
20.1
0.18
20
20
55
7.2
TCDD
(PPT)
0
0.0253
TOTAL
0.0205
TOTAL
0
0
0
TOTAL
0.238
1.62
0.342
0.0212
0
0
0.0453
0.0403
0.0247
TOTAL
0.136
0.0253
0
TOTAL
0
23.5
709
TOTAL
TCDD
(Grais)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
1.724E-05
1.724E-05
O.OOOEtOO
O.OOOE^OO
1.254E-02
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.336E-04
1.287E-02
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
1.558E-03
9.920E-03
7.508E-04
1.223E-02
1.268E-04
O.OOOEtOO
O.OOOEtOO
5.830E-05
9.762E-05
2.605E-05
3.107E-04
1.254E-02
1.035E-02
1.724E-05
O.OOOEtOO
1.036E-02
O.OOOEtOO
1.174E-03
4.635E-03
5.809E-03
TCDD
(Ibs) ND AVE
O.OOOEtOO HD(0.00514)
O.OOOEtOO
O.OOOEtOO
3.797E-08 X
3.797E-08
O.OOOEtOO
O.OOOEtOO
2.762E-05
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.349E-07
2.836E-05
O.OOOEtOO ND(0.309)
O.OOOEtOO MD(0.738)
O.OOOEtOO ND(0.00514)
O.OOOEtOO
O.OOOEtOO
3.433E-06
2.185E-05
1.654E-06
2.694E-05
2.793E-07
O.OOOEtOO ND(0.0326)
O.OOOEtOO ND(0.0168)
1.284E-07
2.150E-07
6.178E-08
6.845E-07
2.762E-05
2.279E-05
3.797E-08 X
O.OOOEtOO MH0.660I
2.283E-05
O.OOOEtOO ND(0.660)
2.585E-06
1.021E-05
1.279E-05
QA
27.9 J
27.9 »
17.6 J
17.6 t
Fl
-------
Hill A
08-Feb-88
Hill A
Hass Balance [ND assuied 0.0 J
Basis : 1 Day
A2. General Hill Exports
1. UUTP Effluent
2. UUTP Coiposite Sludge
3. HU Hypo Line Pulp
4. HV Peroxide Line Pulp
5. SU Line Pulp
6. Bottoi Ash
B2. General Hill Sever Exports
1. Influent To UUTP
C2a. Bleach Plant Exports
1. Bleached HV Hypo Pulp
2. Bleached HU Peroxide Pulp
3. Bleached SU Pulp
4. Coibined Process Uasteuater
(froeCib.)
C2b. Detailed Bleach Plant Exports
1. Cotbined Process Uastevater
D2a. UUTP Exports
1. Effluent
2. UUTP Coiposite Sludee
D2b. UUTP Sludge Exports
I. UUTP Conposite Sludge
Sanple ID
DE 020922
DE 020920
DE 020904
DE 020905
DE 020902
DE 020918
DE 020921
DE 020904
DE 020905
DE 020902
Flow
i«GD or Dry
Tons/Day)
23.2
82.2
160
160
144
2
20.1
160
160
144
7.6
TCDD
(PPT)
0.124
36.6
4.89
2.98
15.8
TOTAL
0.136
TIITAL
4.89
2.98
15.8
TCDD
(Grais)
1.089E-02
2.732E-03
7. 104E-04
4.329E-04
2.066E-03
O.OOOE+00
1.683E-02
1.035E-02
1.035E-02
7.104E-04
4.329E-04
2.066E-03
1.254E-02
TCDD
(Ibs)
2.398E-05
6.017E-06
1.565E-06
9.536E-07
4.550E-06
O.OQOE*QO
3.707E-05
2.279E-05
2.279E-05
1.565E-06
9.536E-07
4.550E-06
2.762E-05
Percent
Total ND AVE QA
64.7* X
16.2* X
4.2*
2.61
12.3* X
0.0*
100.0*
100.0*
100.0*
4.5*
2.7*
13.1* X
79.6*
DE 020922
DE 020920
DE 020920
TIITAL 1.575E-02 3.469E-05 100.0*
7.6 1.254E-02 2.762E-05 100.0*
TOTAL 1.254E-02 2.752E-05 100.0*
23.2 0.124 1.089E-02 2.398E-05 79.9*
82.2 36.6 2.732E-03 6.017E-06 20.1*
TdTAL 1.362E-02 3.000E-05 100.0*
82.2 36.6 2.732E-03 6.017E-06 100.0*
TCTAL 2.732E-03 6.017E-0
100.0*
F2
-------
Kill A
08-Feb-88
Hill A
Hass
Basis
Ai.
Bl.
Balance !ND assuied D.O 1
• : 1 Day
Saiple ID
Flow
IBGD or Dry
Tons/Day)
TCDF
(PPT)
TCDF
(Grais)
TCDF
(Ibs) ND AVE
QA
General Hill Inputs
1.
2.
3.
4.
Treated River Water
Hil Chips
SB Chips
Landfill Leachate
DE
DE
DE
DE
020801
020805
020804
020821
20
595
105
0.18
0
0.110
TOTAL
0.
0.
0.
7.
7.
OOOEtOO
OOOEtOO
OOOEtOO
494E-05
494E-05
0.
0.
0.
1.
1.
OOOEtOO WHO. 00107)
OOOEtOO
OOOEtOO
651E-Q7 I
651E-07
20.8 X
General Sever Inputs
I.
2.
3.
4.
5.
6.
7.
Cla.
1.
2.
3.
4.
Clb.
1.
2.
3.
4.
5.
6.
7.
8.
9.
Dia.
1.
2.
3.
Dlb.
1.
2.
3.
Water Treatient Sludge
Uater Treatient Backwash
Bleach Plant Total
Coibined Pulping
Combined Recovery
Power House
Coibined Paper Machines
Flow
Bleach Plant Inputs
HU Brounstock Pulp
SU Brovnstock Pulp
Treated River Vater
Paperiachine Whitewater
Detailed Bleach Plant Filtrate
SVC Stage Filtrate
SW Eo Stage Filtrate
SU H Stage Filtrate
Softvood Line Subtotal
HUC Stage Filtrate
HtKHypo Line) Eo Filtrate
HViHypo Line) H Filtrate
HWtPeroxide Line) Eo Filtrate
HlHPeroride Line) H Filtrate
HUCPeroxide Line) H Filtrate
Hardwood Line Subtotal
Bleach Plant
WUTP Inputs
Influent To WITP
Landfill Leachate
Fly Ash
Ifl/TP Sludge Inputs
Fly Ash
Priiary Sludge
Secondary Sludge
DE
DE
DE
DE
DE
DE
020802
020803
020806
020807
020818
020811
Total
DE
DE
DE
020903
020901
020801
DE0201001
0.8
0.6
7.6
5.5
0.17
0.5
4.3
19.7
355
160
7
1.5
0.191
TOTAL
0
0
0
TOTAL
0.
0.
2.
0.
0.
0.
3.
2.
0.
0.
0.
0.
0.
OOOEtOO
OOOEtQO
189E-01
OOOE^OO
OOOEtOO
OOOEtOO
109E-03
220E-01
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
0.
0.
4.
0.
0.
0.
6.
4.
0.
0.
0.
0.
0.
OOOEtOO
OOOEtOO
822E-04
OOOEtOO
OOOEtOO
OOOEtOO
847E-06
891E-04
OOOEtOO ND(0.231)
OOOEtOO ND(0.271)
OOOEtOO WHO, 00107)
OOOEtOO
OOOEtOO
20.81
Flows
DE
DE
DE
DE
DE
DE
DE
DE
DE
020906
020907
020906
020909
020910
020911
020912
020913
020914
Total
DE
DE
DE
DE
DE
DE
020921
020621
020919
020919
020819
020820
1.73
1.44
0.58
3.75
1.58
0.73
0.26
0.34
0.64
0.30
3.85
7.60
20.1
0.18
20
20
55
7.2
3.806
32.6
5.778
0.305
0.247
0.114
0.318
0.17
0.174
TOTAL
1.916
0.110
0
TOTAL
0
362
10932
TOTAL
2.
1.
1.
2.
1.
6.
1.
4.
492E-02
777E-01
268E-02
153E-01
824E-03
825E-04
122E-04
092E-04
5.
489E-05
37. 8X
3.914E-04
2.
4.
4.
1.
2.
9.
4.118E-04 9.
1.
3.
2.
1.
7.
976E-04
637E-03
189E-01
458E-01
494E-05
0. OOOEtOO
1.
0.
1.
7.
9.
458E-01
OOOEtOO
906E-02
147E-02
055E-02
4.
8.
4.
3.
1.
0.
794E-05
742E-04
018E-06
503E-06
471E-07
014E-07
071E-07
352E-07
012E-06
822E-04
211E-04
651E-07 I
OOOEtOO NDf 0.349)
23.9*
3.212E-04
0.
4.
1.
1.
OOOEtOO MHO. 349)
202E-05
574E-04
994E-04
23.9 X
F3
-------
mil A
08-Feb-88
Hill A
Mass Balance [ND assuied 0.0 ]
Basis : 1 Day
A2. General Hill Exports
1. UUTP Effluent
2. y»TP Coiposite Sludge
3. HU Hypo Line Pulp
4. HU Peroxide Line Pulp
5. SU Line Pulp
6. Bottoi Ash
62. General Hill Sever Exports
1. Influent To UUTP
C2a. Bleach Plant Exports
1. Bleached HU Hypo Pulp
2. Bleached HU Peroxide Pulp
3. Bleached SU Pulp
4. Coibined Process Vastenater
(froiClb.)
C2b. Detailed Bleach Plant Exports
1. Coibined Process Uastevater
(froiClb.)
D2a. UUTP Exports
1. Effluent
2. UUTP Coiposite Sludge
D2b. UUTP Sludge Exports
1. UUTP Coiposite Sludge
Saiple ID
DE 020922
DE 020920
DE 020904
DE 020905
DE 020902
DE 020918
DE 020921
DE 020904
DE 020905
DE 020902
DE 020922
DE 020920
FlON
(HGD or Dry
Tons/Day)
23.2
82.2
160
160
144
2
20.1
160
160
144
7.6
7.6
23.2
82.2
TCDF
(PPT)
2.18
678
47.3
50.1
333
TOTAL
1.916
TOTAL
47.3
50.1
333
TOTAL
TOTAL
2.18
678
TOTAL
TCDF
(Grais)
1.914E-01
5.060E-02
6.872E-03
7.279E-03
4.354E-02
O.OOOE+00
2.997E-01
1.458E-01
1.458E-01
6.872E-03
7.279E-Q3
4.354E-02
2.189E-01
2.766E-01
2.189E-01
2.189E-01
1.914E-01
5.060E-02
2.420E-01
TCDF
(Ibs)
4.217E-04
1.115E-04
1.514E-05
1.603E-05
9.590E-05
O.OOOE+00
6.602E-04
3.211E-04
3.211E-04
1.514E-05
1.603E-05
9.590E-05
4.822E-04
6.093E-04
4.822E-04
4.822E-04
4.217E-04
1.115E-04
5.331E-04
Percent
Total
63.91
16.9S
2.3*
2.41
14. 51
0.01
100. OS
100. OS
100. OS
2.5S
2.6S
15. 7S
79. IS
100. OS
100.0S
100.01
79. IS
20. 9S
100. OS
ND AVE QA
DE 020920
82.2
678 5.060E-02 1.115E-04
100.OX
F4
-------
Hill
08-Feb-88
Mill
Mass Balance
Basis : 1 Day
Al. General Hill Inputs
1. Treated Vater(River)
2. HV Chips
3. SV Chips
4. 5V Sawdust
il. General Sever Inputs
1. Combined Paper Machines
2. Caustic Sever
3. Coibined Pulping
4. Corrosive Sever
Flov
Cla. Bleach Plant Inputs
1. Brounstock Pulp
2. Process Uater
Clb. Detailed Bleach Plant Filtrate
1. C Stage Filtrate
2. E Stage Filtrate
3. H-l Stage Filtrate i
4. H-2 Stage Filtrate *
5. D Stage Filtrate *
> Recycled Flovs Flov
Dl. IfllTP Inputs
1. Influent To WVTP
Saiple ID
86374601
86374604
86374603
86374605
86374621
86374615
86374606
86374607
Total
86374611
86374601
Flovs
86374673/613
86374615
86374616
86374617
86374614
Total
86374644
Flov
(HGD or Dry
Tons/Day)
37.1
220
880
630
6.9
2.2
10.8
3.1
23
883
8.25
6.05
2.2
0.24
1.36
1.57
8.25
37.35
TCDD
(PPT)
0
TOTAL
0
0.224
TOTAL
0
0
TOTAL
0.0232
0.224
0.258
0.132
0.0298
TOTAL
0
TCDD
(Grais)
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.665E-03
O.OOOE+00
O.OOOE+00
1.865E-03
O.OOOE+00
O.OOOE+00
O.OOOE+00
5.313E-04
1.865E-03
2.344E-04
6.795E-04
1.771E-04
2.397E-03
O.OOOE+00
TCDD
(Ibs) ND AVE QA
O.OOOE+00 ND(0.00693) 25.2 *
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00 NDI0.00514) 35.9 X
4.108E-06 I
O.OOOE+00
O.OOOE+00
4.108E-06
O.OOOE+00 ND(0.949)
O.OOOE+00 ND(0. 00693) 25.2 X
O.OOOE+00
1.170E-06
4.108E-06 I
5.162E-07
1.497E-06
3.901E-07
5.279E-06
O.OOOE+00 ND(0. 00644) I
TOTAL
»86374614 Recycled To 86374673 [Acid Sever Assuied To Be Higher Mass)
86374616 And 86374617 Recycled To 86374615
F5
-------
Nil! B
08-Feb-88
Hill
Mass Balance
Basis : 1 Day
A2. General Hill Exports
1. UVTP Effluent
2. UUTP Priiary Sludge
3. UUTP Secondary Sludge
4. Bleached Pulp
5. Vater Treatment Backwash
6. Landfill Leachate
B2. General Hill Sever Exports
1. Influent To VUTP
C2a. Bleach Plant Exports
1. Bleached Pulp
«2. Acid Sever
*3. Caustic Sever
C2b. Detailed Bleach Plant Exports
U. Acid Sever
»2. Caustic Sever
Flov
D2. UVTP Exports
1. Effluent
2. UUTP Priiary Sludge
3. UVTP Secondary Sludge
Saiple ID
86374645
86374641
86374642
86374612/661
86374602
86374646
86374644
86374612/661
86374673/613
86374615
86374673/613
86374615
Total
86374645
86374641
86374642
Flov
(HGD or Dry
Tons/Day)
36.6
35
17
770
1.3
37.35
770
6.05
2.2
6.05
2.2
8.25
36.6
35
17
TCDD TCDD
(PPT) (Grais)
0.0151 2.092E-03
18.9 6.006E-04
88.9 1.372E-03
11.3 7.901E-03
O.OOOEtOO
0 O.OOOEtOO
TOTAL 1.197E-02
0 O.OOOEtOO
TOTAL O.OOQEtOO
11.3 7.901E-03
0.0232 5.313E-04
0.224 1.865E-03
TOTAL 1.030E-02
0.0232 5.313E-04
0.224 1.865E-03
TOTAL 2.397E-03
0.0151 2.092E-03
18.9 6.006E-04
88.9 1.372E-03
TOTAL 4.065E-03
TCDD
(lbs>
4.608E-06
1.323E-06
3.023E-06
1.740E-05
O.OOOEtOO
O.OOOE+00
2.636E-05
O.OOOEtOO
O.OOOE+00
1.740E-05
1.170E-06
4.108E-06
2.268E-05
1.170E-06
4.108E-06
5.279E-06
4.608E-06
1.323E-06
3.023E-06
8.953E-06
Percent
Total
17.51
5. OX
11.51
66.011
O.OJ
o.ox
too. o»
76. 7X
5.2*
18. U
100. OX
22. 2X
77.8X
100.04
51. 5X
14.8X
33. 8X
100. OX
AVE
QA
ND(0.00405)
ND(0.00644) X
X
X
086374614 Recycled To 86374673 [Acid Sever Assuied To Be Higher Mass]
86374616 And 86374617 Recycled To 86374615
-------
Hill
08-Feb-88
mn
Hass Balance
Al. General Hill Inputs
1. Treated Uater(River)
2. HU Chips
3. SV Chips
4. 5V Savdust
Bl. General Sever Inputs
Sanple ID
86374601
86374604
86374603
86374605
1. Coibined Paper Machines 86374621
2. Caustic Sewer
3. Coibined Pulping
4. Corrosive Sever
Cla. Bleach Plant Inputs
1. Brovnstock Pulp
2. Process Hater
Clb. Detailed Bleach Plant
1. C Stage Filtrate
2. E Stage Filtrate
3. H-l Stage Filtrate »
4. H-2 Stage Filtrate «
5. 5 Stage Filtrate »
« Recycled Flovs
Dl. UVTP inputs
1. Influent To WTP
86374615
86374606
86374607
Flov Total
86374611
86374601
Filtrate Pious
86374673/613
86374615
86374616
86374617
86374614
Flov Total
86374644
Flov
(HGD or Dry
Tons/Day)
37.1
220
880
630
6.9
2.2
10.8
3.1
23
883
8.25
6.05
2.2
0.24
1.36
1.57
8.25
37.35
TCDF
(PPT)
0
TOTAL
0.108
1.044
TOTAL
1.54
0
TOTAL
0.0679
1.044
1.129
0.913
0.133
TOTAL
0.108
TOTAL
TCDF
(Grais)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
2.821E-03
8.693E-03
O.OOOEtOO
O.OOOEtOO
1.151E-02
1.235E-03
O.OOOEtOO
1.235E-03
1.555E-03
B.693E-03
1.026E-03
4.700E-03
7.903E-04
1.025E-02
1.527E-02
1.527E-02
TCDF
(Ibs)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
6.213E-06
1.915E-05
O.OOOEtOO
O.OOOEtOO
2.536E-05
2.720E-06
O.OOOEtOO
2.720E-06
3.425E-06
1.915E-05
2.259E-06
1.035E-05
1.741E-06
2.257E-05
3.363E-05
3.363E-05
i 86374614 Recycled To 86374673
» 86374616 And 86374617 Recycled To 86374615
ND AVE QA
NDI0.00950)
13.9%
36.9*
ND(0.00950)
13.91
30.6*
22.2*
X 49.8 *, 27.9
F7
-------
Hill
08-Feb-88
Kill B
Hass Balance
A2. General Hill Exports
1. WTP Effluent
2. VUTP Priiary Sludge
3. WTP Secondary Sludfe
4. Bleached Pulp
5. Water Treatment Backwash
6. Landfill Leachate
62. General Hill Sewer Exports
1. Influent To WTP
C2a, Bleach Plant Exports
1. Bleached Pulp
«2. Acid Sewer
»3. Caustic Sewer
C2b. Detailed Bleach Plant Exports
tl. Acid Sever
«2. Caustic Sewer
Flow
D2. y«TP Exports
1. Effluent
2. VUTP Priiary Sludge
3. UUTP Secondary Sludge
Saiple ID
86374645
66374641
863746+2
86374612/661
86374602
86374646
86374644
86374612/661
86374673/613
86374615
86374673/613
86374615
Total
86374645
86374641
86374642
Flow
(HGD or Dry
Tons/Day)
36.6
35
17
770
1.3
37.35
770
6.05
2.2
6.05
2.2
8.25
36.6
35
17
TCDF
(PPT)
0.122
101
808
60.3
0.010J
TOTAL
0.1W
TOTAL
60.!)
0.067SI
l.OM
TOTAL
0.067SI
1.044
TOTAL
0.122
101
80£
TOTAL
TCDF
(Grais)
1.690E-02
3.210E-03
1.247E-02
4.258E-02
O.OOOEHX)
O.OOOE+00
7.516E-02
1.527E-02
1.527E-02
4.258E-02
1.555E-03
8.693E-03
5.2B3E-02
1.555E-03
8.693E-03
1.025E-02
1.690E-02
3.210E-03
1.247E-02
3.25BE-02
TCDF
(Ibs)
3.723E-05
7.070E-06
2.747E-05
9.379E-05
O.OOOEHX)
O.OOOE+00
1.656E-04
3.363E-05
3.363E-05
9.379E-05
3.425E-06
1.915E-05
1.164E-04
3.425E-06
1.915E-05
2.257E-05
3.723E-05
7.070E-06
2.747E-05
7.177E-05
Percent
Total
22.5*
4.3X
16. 6*
56.6*
O.W
0.0X
100. OX
100. M
100, OX
80. 6X
2.9X
16.5X
100. OK
15.2X
84.8*
100. OX
51. 9t
9.911
38.3*
100.0$
ND AVE QA
30.5 X
X 67.IX. 10.31. 55.41
X 49.8 X, 27.9 X
X 67.IX, 10.3X, 55.4*
30.61
X
30.6X
30.5X
« 86374614 Recycled To 86374673
i 86374616 And 86374617 Recycled To 86374615
-------
Nil! C
8-Feb-88
Nil! C
Mass Balance
Basis : I Day Saiple ID
Al. General Hill Inputs
1. Treated Kater(Hiver) DE 026001
2. HU Chips DE 026103
3. Landfill Leachate DE 026014
Bl. General Sewer Inputs
1. Coibined Paper Machines DE 026118
2. Misc. Boiler/Scrubber DE 026205
3. Sluiced Coal Bottoi Ash DE 026007
4. ffisc. Pulp Hi 11/Recovery DE 026111
5. disc. Pulping DE 026107
»6. Bleach Plant/Scrubber Vents DE 026114
7. No. 2 Softening Sludge DE 026101
Flo* Total
Cla. Bleach Plant Inputs
1. Brownstock Pulp DE 026002
2. Process Vater DE 026001
Clb. Detailed Bleach Plant Filtrate Flovs
1. C Stage Filtrate DE 026004
2. Eo Stage Filtrate DE 026005/211
3. D Stage Filtrate*! DE 026006/213
Dla. Ifl/TP Inputs
1. Influent To WTP
2. Landfill Leachate
Dlb. UUTP Sludge Inputs
1. Secondary Sludge
DE 026012
DE 026014
DE 026207
Flow
(HGD or Dry
Tons/Day)
30
2200
8.2
5
1
1.6
3.5
0.3
19.6
1011
13
2.95
4.9
0
31.5
TCDD
(PPT)
0
0
TOTAL
0.0106
0
TOTAL
0
0
TOTAL
0
0
0
0
0
TOTAL
TCDD
(Grais)
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.290E-04
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
3.290E-04
O.OOQEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOE+00
O.OOOE*00
TCDD
Obs)
O.OOOE*00
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.247E-07
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
7.247E-07
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
O.OOOEtOO
ND AVE QA
WHO. 00531)
NDIO. 00595)
ND(0. 00912)
MH0.564)
ND(0. 00531)
NDI0.00593)
ND(0.0106) !
NDI0.00341) I
NDI0.00278)
ND(0.00595)
22
11.2 2.237E-04 4.928E-07
« Mainly Saiple DE 026004(DE 026005/DE 026006 Possible)
** Interiittant Flov INonally Zero)
DE 026005 Partially Recycled To DE 026004
F9
-------
Mill C
08-Feb-88
Hill C
Hass Balance
Basis : 1 Day Saiple ID
A2. General Hill Exports
1. tl«TP Effluent (36-72hr) DE 026206
2. Coibined Denatered Sludge DE 026011
3. Bleached Pulp DE 026003
4. Coal Ash DE 026007
5. Coal Ash - ESP DE 026008
6. Coal Mechanical Ash DE 026009
B2. General Kill Sever Exports
1. Influent To WVTP DE 026012
C2a. Bleach Plant Exports
1. Bleached Pulp DE 026003
2. B.P. Effluent/Scrubber Vents DE 026114
3. C/D Filtrate DE 026004
4. Eo Stage Filtrate DE 026005
5. D Stage Filtrate" DE 026006/213
*» intenittant Fio«(Norially Zero)
D2. WTP Exports
1. Effluent (36-72hr) DE 026206
2. Coibined Denatered Sludge DE 026011
D2b. VUTP Sludge Exports
1. UVTP Coiposite Sludge DE 026011
E2. Other
1. WWTP Effluent (0-24 hrs) DE 026013
Recycle to Hill
Flo*
(HGD or D;-y
Tons/Day,1
29. !i
21li
930
31.ii
93(1
3.J.
2.9!>
4.E
(i
29. E
216
216
TCDD
(PPT)
0
3.32
0
TOTAL
0
TOTAL
0
0
0
0
0
0
3.32
TOTAL
3.32
TOTAL
TCDD
(Grais)
O.OOOE+00
6.511E-04
O.OOOE+00
6.511E-04
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+Ofl
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
6.511E-04
6.511E-04
6.511E-04
6.511E-04
TCDD
(Ibs)
O.OOOE+00
1.434E-06
O.OOOE+00
1.434E-06
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.434E-06
1.434E-06
1.434E-06
1.434E-06
Percent
Total ND AVE
0.0* HD(0. 00339)
100. OX
O.OX ND(0.62)
0.0*
0.0V
0.0*
100.0*
ND(0.00278)
0.0* NDI0.62)
O.QK ND(0.00912)
0.0* ND(0. 00593)
0.0* ND(0.0106)
0.0* ND( 0.00341)
0.0* NDI0.00339)
100.0*
100.0*
100.0*
100.0*
X
I
I
X
X
0 O.OOOE+00 O.OOOE+00
HD(0.00281)
F10
-------
Mill C
09-Feb-88
Hill C
Hass Balance
Basis : 1 Day
Al. General Hill Inputs
1. Treated Uater(River)
2. HU Chips
3. Landfill Leachate
Bl. General Sever Inputs
1. Coebined Paper Machines
2. Misc. Boiler/Scrubber
3. Sluiced Coal Bottoi Ash
4. Hisc. Pulp Hill/Recovery
5. Hisc. Pulping
« 6. Bleach Plant/Scrubber Vents
7. No. 2 Softening Sludge
Flo*
Cla. Bleach Plant Inputs
1. Brovnstock Pulp
2. Process Water
Clb. Detailed Bleach Plant Filtrate Flow
1. C Stage Filtrate
2. Eo Stage Filtrate
3. 0 Stage Filtrateti
Saiple ID
DE 026001
DE 026103
DE 026014
DE 026118
DE 026205
DE 026007
DE 026111
DE 026107
DE 026114
DE 026101
Total
DE 026002
DE 026001
! FlOKS
DE 026004
DE 026005/211
DE 026006/213
Flov
(HGD or Dry
Tons/Day)
30
2200
8.2
5
Inc 1.026015
1
1.6
3.5
0.3
19.6
1011
13
2.95
4.9
0
TCDF
(PPT)
0
0
TOTAL
0.197
0.429
TOTAL
0
0
TOTAL
0.0929
0.0558
0.0136
TCDF
(Grans)
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
6.114E-03
O.OOOE+OQ
O.OOOE+00
O.OOOE+00
5.683E-03
O.OOOE+00
1.180E-02
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.037E-03
1.035E-03
O.OOOE+00
TCDF
(Ibs)
O.OOOE+00
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.347E-05
O.OOOE+00
O.OOOE+00
O.OOOE+00
1.252E-05
O.OOOE+00
2.599E-05
O.OOOE+00
O.OOOE+00
O.OOOE+00
2.285E-06
2.280E-06
O.OOOE+00
ND AVE QA
ND(0.00694) 15.21
ND(0. 00869)
NDI0.162)
ND(0.00694) 15.21
X 25U3K
X
Dla. yUTP Inputs
1. Influent To UUTP
2. Landfill Leachate
DE 026012 31.5 0.0362 4.316E-03 9.507E-06
DE 026014 0 O.OOOE+00 O.OOOE+00 WHO.
TOTAL 4.316E-03 9.507E-06
Dlb. VUTP Sludge Inputs
1. Secondary Sludge
DE 026207
22
75.4 1.506E-03 3.318E-06
Mainly Saiple DE 026004(DE 0260D5/DE 026006 Possible)
Interiittant Flow (Mortally Zero)
DE 026005 Partially Recycled To DE 026004
Fll
-------
Hill C
09-Feb-88
Hill C
Mass Balance
Basis : 1 Day
A2. General Hill Exports
1. WTP Effluent (36-72hr)
2. Coibined De»atered Sludge
3. Bleached Pulp
4. Coal Ash
5. Coal Ash - ESP
6. Coal Hechanical Ash
B2. General Hill Sever Exports
1. Influent To BwTP
C2a. Bleach Plant Exports
1. Bleached Pulp
2. B.P. Effluent/Scrubber Vents DE 026114
3. C/D Filtrate
4. Eo Stage Filtrate
5. D Stage Filtrate"
» Intenittent Flov (Nonally Zero)
D2. WTP Exports
1. Effluent (36-72hr) DE 026206
2. Coibined Denatered Sludge DE 026011
Saiple ID
DE 026206
DE 026D11
DE 026003
DE 026007
DE 026008
DE 026009
DE 026012
DE 026003
DE 026114
DE 026004
DE 026005
DE 026006/213
!ero)
Flow
(MGD or Dry
Tons/Day)
29.5
216
930
31.5
930
3.5
2.95
4.9
0
TCDF
(PPI)
0.01124
36.6
14.9
TOTAL
0.0362
TOTAL
14.9
0.429
0.0929
0.0573
0.0136
TOTAL
TCDF
(Grais)
1.255E-03
7.571E-03
1.258E-02
2.141E-02
4.316E-03
4.316E-03
1.258E-02
5.683E-03
1.037E-03
1.063E-03
O.OOOEKX)
2.037E-02
TCDF
(Ibs)
2.764E-06
1.668E-05
2.771E-05
4.715E-05
9.507E-06
9.507E-06
2.771E-05
1.252E-05
2.285E-06
2.341E-06
O.OOOEHX)
4.486E-05
Percent
Total
5.9*
35. 4*
58.81
0.0*
0.0*
0.0*
100. OS
100.0*
100.01
61.61
27.9*
5.1*
5.2*
0.0*
100.0*
ND AYE
X
X
I
X
29.5 3.01124 1.255E-03 2.764E-06 14.2*
216 38.6 7.571E-03 1.668E-05 85.8*
TOTAL 8.826E-03 1.944E-05 100.0*
I 25*.13*
D2b. UtfTP Sludge Exports
1. WTP Coiposite Sludge
DE 026011
E2. Other
1. WTP Effluent (0-24 hrs) DE 0260L3
Recycle to Hill
216 38.6 7.571E-03 1.668E-05 100.0*
TOTAL 7.571E-03 1.668E-05 100.0*
2 0.0128 9.690E-05 2.134E-07
100.0*
F12
-------
Kill D
09-Feb-88
Hill D
Hass Balance
Basis : 1 Day
Al. General Hill Inputs
I. Treated UaterlNorth)
2. Treated Mater(South)
3. SU Chips
Bl. General Sever Inputs
1. Coibined Paper Machines
2. Misc. Pulping
3. disc. Evap./Recovery/Kiln
4. Boiler
5. A Side Acid Sever
6. B Side Acid Sever
7. Conbined Caustic Sever
Cla. Bleach Plant Inputs
1. Coibined Brovnstock Pulp
2. Process Uater
1. C Stage Filtrate A Side
2. Coibined E Stage Filtrate
3. H Stafe Filtrate A Side
4. C State Filtrate B Side
5. H Stage Filtrate B Side
Dla. UUTP Inputs
1. Influent To MITP
Dlb. UUTP Sludge Inputs
1. Priiary Sludge
2. Secondary Sludge
Saiple ID
DF 02*402
DF 024403
DF 024404
DF 024501
DF 024405
in DF 024406
DF 024516
DF 024412/605
DF 024415
DF 024413
Flov Total
> DF 024409
DF 024403
trate Flovs
DF 024412/605
:e DF 024413
DF 024414
DF 024415
DF 024418
Flov Total
DF 024604
DF 024514
DF 024515
Flov
(HGD or Dry
Tons/Day)
10.2
11.7
1712
9.6
3.5
0.25
0.06
1.42
0.95
2.72
18.5
419
5.02
1.42
2.72
1.42
0.95
0.92
7.43
18.85
54
8
TCDD
(PPT)
0
TOTAL
0
0.0376
0.119
0.257
TOTAL
0
TOTAL
0.0376
0.257
0.0551
0.119
0.331
TOTAL
0.0283
TOTAL
17.4
36.1
TCDD
(Grais)
O.OOOEtOO
O.OOOE+00
O.OOOE'OO
O.OOOE+00
O.OOOEHX)
O.OOOE+00
O.OOOEKX)
O.OOOE+00
2.021E-04
4.279E-04
2.646E-03
3.276E-03
O.OOOEtOO
O.OOOE'OO
O.OOOEfOO
2.021E-04
2.646E-03
2.96IE-04
4.279E-04
1.153E-03
4.725E-03
2.019E-03
2.019E-03
8.532E-04
2.622E-04
TCDD
(Ibs) ND AVE QA
O.OOOEKK) ND(0. 00456)
O.OOOE+00
O.OOOE*00
O.OOOE+00
O.OOOfrOO MHO. 0059)
O.OOOE+00
O.OOOEtOO
O.OOOE+00
4.451E-07 X
9.425E-07
5.828E-06
7.216E-06
O.OOOE+00 ND(0.695)
O.OOOE+00
O.OOOEfOO
4.451E-07 I
5.82BE-06
6.523E-07
9.425E-07
2.539E-06
1.041E-05
4.447E-06 X 28.4*
4.447E-06
1.879E-06
5.776E-07
3. Secondary Sludge
After Chlorination
DF 024519
35.8 2.601E-04 5.728E-07
F 13
-------
Hill D
09-Feb-88
Hill D
Flov
Saaple ID (HGD or Dry
Tons/Day)
A2. General Hill Exports
1. WvTP Effluent
2. Coibined Devatered Sludge
3. Bleached Pulp - A Side
4. Bleached Pulp - B Side
B2. General Sever Exports
I. IftiTP Influent
C2a. Bleach Plant Exports - General
1. Bleached Pulp A Side
2. Bleached Pulp B Side
3. A Side Acid Sever
4. B Side Acid Sever
5. Contained Caustic Sever
C2b. Detailed Bleach Plant Exports
1. Bleached Pulp A Side
2. Bleached Pulp B Side
DF 024512
DF 024513/606
DF 024410
DF 024411
DF 024604
Severs
DF 024410
DF 024411
DF 024412/605
DF 024415
DF 024413
DF 024410
DF 024411
3. Bleach Plant Flows Total (Clb.)
D2a. VVTP Exports
1. Effluent
2. Coibined Devatered Sludge
D2b. UVTP Sludge Exports
1. Contained Devatered Sludge
D2c. Sludge Lagoon
1. Sludge Lagoon Effluent
DF 024512
DF 024513/606
DF 024513/606
DF 024517
18.49
62
250
120
18.85
250
120
1.42
0.95
2.72
250
120
7.43
18.49
62
62
0.603
TCDD
(PPT)
0
18.1
0
3.94
TOTAL
0.0283
TOTAL
0
3.94
0.0376
0.119
0.257
TOTAL
0
3.94
TOTAL
0
18.1
TOTAL
18.1
TOTAL
0
TOTAL
TCDD
(Grais)
O.OOOEtOO
1.019E-03
O.OOOEtOO
4.293E-04
1.448E-03
2.019E-03
2.019E-03
O.OOOEtOO
4.293E-04
2.021E-04
4.279E-04
2.646E-03
3.705E-03
O.OOOEtOO
4.293E-04
4.725E-03
5.154E-03
O.OOOEtOO
1.019E-03
1.019E-03
1.019E-03
1.019E-03
O.OOOEtOO
O.OOOE+00
TCDD
Ubs)
O.OOOEtOO
2.244E-06
O.OOOEtOO
9.456E-07
3.190E-06
4.447E-06
4.447E-06
O.OOOEtOO
9.456E-07
4.451E-07
9.425E-07
5.828E-06
8.161E-06
O.OOOEtOO
9.456E-07
1.041E-05
1.135E-05
O.OOOEtOO
2.244E-06
2.244E-06
2.244E-06
2.244E-06
O.OOOEtOO
O.OOOEtOO
Percent
Total ND AVE
0.0* MD(0.00716)
70.4*
0.0* NDU.03)
29.6*
100.0*
0.0* NDU.03)
11.6*
5.5*
11.5*
71.4*
100.0*
0.0* NDU.03)
8.3*
91.7*
100.0*
0.0* NDI0.00716)
100.0*
100.0*
100.0*
100.0*
ERR ND(0, 00317)
ERR
It
X
X
X
X
X
X
X
X
F14
-------
Hill D
09-Feb-8B
Hill D
Mass Balance
Basis : 1 Day
Al. Genera! Hill Inputs
1. Treated Vater(North)
2. Treated Hater(South)
3. SW Chips
Flow
Saiple ID (HGD or Dry
Tons/i)ay)
DF 024402 10.2
DF 024403 11.7
DF 024404 1712
TCDF
(PPT)
0
TOTAL
TCDF
(Grais)
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0.
0.
0.
0.
TCDF
(Ibs)
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
Bl. General Sever Inputs
1.
2.
3.
4.
5.
6.
-7
t ,
Cla.
1.
2.
Clb.
1.
2.
3.
4.
5.
Dla.
1.
Dlb.
1.
2.
CoBbined Paper Machines
Hisc. Pulping
Hisc. Evap, /Recovery/Kiln
Boiler
A Side Acid Sever
E Side fccid Sever
Combined Caustic Sever
Bleach Plant Inputs
Combined Browns lock
Process Hater
Flo*
Pulp
Detailed Bleach Plant Filtrate
C Stage Filtrate A
Side
Coibined E Stage Filtrate
H Stage Filtrate A
C Stage Filtrate B
H Stage Filtrate B
UUTP Inputs
Influent To «HTP
UUTP Sludge Inputs
Priiary Sludge
Secondary Sludge
Side
Side
Side
Flo*
DF
DF
DF
DF
i'F
DF
DF
024501
024405
024406
024516
02*1 12' 605
C24415
024413
Total
DF
DF
024409
024403
9.6
3
0.
u.
£ ,
0.
2.
16
.5
25
06
ti
95
72
.5
419
5.
02
0.0146
0.0636
0.394
0.472
TOTAL
0
TOTAL
5,
0.
0.
u.
;..
1.
4.
7.
0.
0.
0,
305E-04
OOOEtOO
OODEtOC
OOOE'OO
667E-04
417E-03
859E-03
175E-03
OOOEtOO
OOOEtOO
OOOEtOO
1.
0.
0.
r.
V,
8,
3.
1.
1.
0.
0.
0.
169E-06
GOOE'Gi.
OOCEtCO
iiiiOEtOO
121E-07
121E-06
070E-05
580E-05
OOOEtOO
OOOEtOO
OOOEtOO
Flovs
DF
DF
DF
DF
DF
024412/605
024413
024414
024415
024416
Total
DF
DF
DF
024511/604
024514
024515
1.
2.
1.
0.
0.
7.
18.
42
72
42
95
92
43
85
54
6
0.0686
0.472
0.0857
0.394
0.602
TOTAL
0.0634
TOTAL
31.9
77.9
3.
4.
4.
1.
2.
9.
4.
4.
1.
5.
687E-04
859E-03
606E-04
417E-03
096E-03
202E-03
523E-03
523E-03
564E-03
659E-04
8.
1.
1.
3.
4.
2.
9.
9.
3.
1.
121E-07
070E-05
015E-06
121E-06
617E-06
027E-05
963E-06
963E-06
445E-06
246E-06
ND AVE 6A
ND(0.00469) X 291
X 12.1%, 55.111,37.611
X 34.9»
ND(0.203)
X 12.11.55.14.37.6*
X 34.91
X 35.41
3. Secondary Sludge
After Chlorination
DF 024519
8 73.2 5.317E-04 1.171E-06
F 15
-------
Kill D
09-Feb-88
Kill D
Hass Balance
Basis : 1 Day
Flov
Saiple ID (HGD or Dry
Tons/Day)
TCDF
(PPT)
TCDF
(Grais)
TCDF
(Ibs)
Percent
Total ND AVE QA
A2. General Kill Exports
t.
2.
3.
4.
vl/TP Effluent
Coibined Devatered Sludge
Bleached Pulp - A Side
Bleached Pulp - B Side
DF
DF
DF
DF
02*512
024513/606
024410
024411
18.49
62
250
120
0
33.6
0
7.79
TOTAL
0.
1.
0.
8.
OOOE*00
903E-03
OOOEtOO
488E-04
2.752E-03
0.
4.
0.
1.
6.
OOOE+00
191E-06
OOOEtOO
870E-06
061E-06
0.
69.
0.
0* KD(0.00663) I 35*
2* X
0* NDU.23)
30.84 X 66.4.28.31
100.
Of
B2. General Sewer Exports
1.
C2a.
1.
2.
3.
4.
5.
C2b.
1.
2.
3.
D2a.
I.
2.
D2b.
1.
D2c.
1,
VUTP Influent
Bleach Plant Exports - General
Bleached Pulp A Side
Bleached Pulp B Side
A Side Acid Sever
B Side Acid Sever
Coibined Caustic Sever
Detailed Bleach Plant Exports
Bleached Pulp A Side
Bleached Pulp B Side
DF
024511/604
18.85
0.0634
TOTAL
4.
4.
523E-03
523E-03
9.
9.
963E-06
963E-06
100.0* I 35.4*
100.
0*
Severs
DF
DF
DF
DF
DF
DF
DF
024410
024411
024412/605
024415
024413
024410
024411
Bleach Plant Flovs Total (Clb.)
Flo*
VUTP Exports
Effluent
Coibined Devatered Sludge
VUTP Sludge Exports
Coibined Devatered Sludge
Sludge Lagoon
i Sludge Lagoon Effluent
Total
DF
DF
DF
DF
024512
024513/606
024513/606
024517
250
120
1.42
0.95
2.72
250
120
7.43
377.43
18.49
62
62
0.603
0
7.79
C.0686
0.394
0.472
TOTAL
0
7.79
TOTAL
0
33.6
TOTAL
33.8
TOTAL
0.0156
TOTAL
O.OOOEfOO
6.
3.
1.
4.
7.
0.
8.
9.
1.
0.
1.
1.
1.
1.
3.
3.
488E-04
687E-04
417E-03
859E-03
494E-03
OOOE+00
488E-04
202E-03
005E-02
OOOE+00
903E-03
903E-03
903E-03
903E-03
560E-05
560E-05
0.
1.
8.
3.
1.
1.
0.
1.
2.
2.
0.
4.
4.
4.
4.
7,
7.
OOOEfOO
870E-06
121E-07
121E-06
070E-05
651E-05
OOOEtOO
B70E-06
027E-05
214E-Q5
OOOEtOO
191E-06
.191E-06
191E-06
191E-06
,8421-08
.B42E-08
0.
11.
4.
18.
64.
100.
0.
8.
91.
0* NDd.23) 41.4*
3* X 66.4.26.3*
9* X 12.1.55.1,37.6*
91
8* X 34.9*
0*
01 NDd.23) 41.4*
4* X 66.4,28.3*
6*
100. OS
0.
100.
0* WHO. 00663) 35*
0* X
100.0*
100.0* X
100.
OS
100.0*
100.0*
F16
-------
Hi!! E
l6-Feb-8
Hill E
Hass Balance I ND = 0.0 Assuied 1
Basis : 1 Day
Ai.
81.
Cl.
C2.
Dl.
Saiple ID
Flow
(HGD or Dry
Tons/Pay)
TCDD
(PPT)
TCDD
(Graes)
TCDB
(!bs) ND AVE QA
General Hill inputs
1.
2.
3.
4.
5.
Treated water(River)
HV Chips
SU Chips
Groundvood Pulp
Landfill Leachate *
« Intenittant Flov(SOepi)
RG1-86356
RG1-863B8
RG1-86359
RG1-86360
RG1-86398
34.6
1218
1620
200
0
0
TOTAL
0.
0.
0.
0.
OOOEtOO
OOOEtOO
OOOEtOO
OOOE+00
0. OOOEtOO
0.
OOOEtOQ
0.
0.
0.
0.
0.
0.
OOOEtOO ND(. 00632) I
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO ND(0. 00817) 39.6J
OOOEtOO
General Sever Inputs
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
Coibined Paper Machines
Hisc, Pulping
Hisc. Power Groups
Otis Hill Return
Uater Treatnent Backwash
A Side E Staee Filtrate
A Side D Stage Filtrate
B Side E Stage Filtrate
B Side D Staee Filtrate
Bottoi Ash *
Fly Ash «
* Included in 3. Flow
RG1-86379
RG1 -86361
RG1 -86362
RG1 -86380/92
RG1 -86357
RG1 -86370
RG1-66371
RG1-86373
RG1 -86374
RG1-86395
RG1-86396
Total
18.9
4.2
2.6
2.5
1.8
1
1.6
0.75
33.35
0.0525
0.0984
0
2.292
0.91
3.597
1.92
0
0
TOTAL
3.
0.
0.
9.
0.
1.
3.
2.
5.
0.
0.
756E-03
OOOEtOO
OOOEtOO
311E-04
OOOEtOO
562E-02
444E-03
178E-02
450E-03
OOOEtOO
OOOEtOO
5.098E-02
8.
0.
0.
2.
0.
3.
7.
4.
1.
272E-06 I
OOOEtOO
OOOEtOO
051E-06 I
OOOEtOO NDd.82)
440E-05
587E-06
798E-05
201E-05
O.OOOEtOO ND( 0.276)
0.
1.
OOOEtOO NDI0.461)
123E-04
Bleach Plant Inputs
I.
2.
3.
4.
5.
HU B Side Brovnstock Pulp
SV B Side Brownstock Pulp
SU A Side Brovnstock Pulp
Process Uater
Paper Machine Whitewater
RG1-86365
SG1-86364/91
RG1-86364/91
RG1-86356
RG1-86379
289
197
525
9
With Above
0
0
0
0
0.0525
TOTAL
0.
0.
0.
0.
0.
OOOEtOO
OOOEtOO
OOOEtOO
OOOEtOO
OOOE'OO
0.
0.
0.
0.
0.
OOOEtOO NDI0.964I
OOOEtOO ND(0.441)
OOOEtOO ND(0.441)
OOOEtOO ND(. 00632) X
X
OOOEtOO
Acid Sever Inputs
I.
2.
A Side C Filtrate
B Side C Filtrate
Flow
RG1-86369
8G1 -86372
Total
3
1.1
4.1
0.0449
0.0669
TOTAL
5.
2.
7.
098E-04
785E-04
884E-04
1.
6.
1.
123E-06
135E-07
737E-06
UVTP Inputs
1.
2.
3.
*
Influent To WTP
Coibined Acid Sewer
Landfill Leachate
RG1 -86386/02
RG1-86368
RG1 -86398
Intenittant Flow(SOgpi) Flow Total
37
4.03
41.03
0.650
0.274
0
TOTAL
9.
4.
0.
103E-02
179E-03
OOOEtOO
9.521E-02
2.005E-04 X 79.31, 411. 15.8*
9.
0.
2.
206E-06 X
OOOEtOO ND(0.00817) 39.6S
097E-04
Dlb. VUTP Slud?e Inputs
I. Gravity Thick. Sec. Sludfe RG1-86397
33.9 498 1.533E-02 3.376E-05
F17
-------
Hill E
09-Feb-BB
Kill E
Mass Balance I ND = 0.0 Assuied 1
Basis : i Day
A2. General Hill Exports
1. VWTP Effluent
2. Coibined Devatered Sludge
3. SU Bleached Pulp - A Side
4. HI/ Bleached Pulp - B Side
5. SU Bleached Pulp - B Side
62. General Sever Exports
1. UUTP Influent
2. Coibined Acid Sever
C2. Bleach Plant Exports
1. SU Bleached Pulp A Side
2. HW Bleached Pulp B Side
3. SV Bleached Pulp B Side
4. A Side C Filtrate
5. A Side E Stage Filtrate
6. A Side D Stage Filtrate
7. B Side C Filtrate
8. B Side E Stage Filtrate
9. B Side D Stage Filtrate
02. MTP Exports
1. Effluent
2. Coibined Devatered Sludge
Saiple ID
RGI-86388/88A
RG1-86387/A/B
RG1-86366
RG1-86367
RG1 -86366
RG1 -86386/402
RG1 -86368
RG1 -86366
RG1-B6367
RG1-86366
RG1-86369
RGi-86370
RGl-86371
RG1-86372
RGi-86373
RG1 -86374
RG1-86388/88A
RG1-B6387/A/B
Flow
(HGD or Dry
Tons/Day)
41
90
483
272
181
37
4.03
483
272
181
3
1.8
1
1.1
1.6
0.75
41
90
TCDD
(PPT)
0,0879
178
25.6
51.2
25.6
TOTAL
0.650
0.274
TOTAL
25.6
51.2
25.6
0.0449
2.292
0.91
0.0669
3.597
1.92
TOTAL
0.0879
178
TOTAL
TCDD
(Grais)
1.364E-02
1.455E-02
1.123E-02
1.265E-02
4.207E-03
5.206E-02
9.103E-02
4.179E-03
9.521E-02
1.123E-02
1.265E-02
4.207E-03
5.098E-04
1.562E-02
3.444E-03
2.785E-04
2.178E-02
5.450E-03
7.516E-02
1.364E-02
1.455E-02
2.819E-02
TCDD
(Ibsl
3.005E-05
3.204E-05
2.473E-05
2.785E-05
9.267E-06
1.147E-04
2.005E-04
9.206E-06
2.097E-04
2.473E-05
2.785E-05
9.267E-06
1.123E-06
3.440E-05
7.587E-06
6.135E-07
4.798E-05
1.201E-05
1.656E-04
3.005E-05
3.204E-05
6.209E-05
Percent
Total
26.2*
27.9*
21.61
24.3*
8.1*
100.0*
95.6*
4.4*
100.0*
14.9*
16.8*
5.6*
0.7*
20.8*
4.6*
0.4*
29.0*
7.3*
100.0*
48.4*
51.6*
100.0*
ND AVE QA
X 71.5U7.4l
X
X
X 79.3.41.15.8*
X
X 71.5*.37.41
X
F18
-------
Hill E
16-Feb-88
Hill E
Mass Balance [ ND - 0.0 Assuied 1
Basis : 1 Day
Hi. General Hill Inputs
1. Treated Vatert River)
2. m Chips
3. SU Chips
Bl.
Cl.
C2.
Dl.
4.
5.
Groundvood Pulp
Landfill Leachate f
« Interiittant Flov(50gpi)
Saiple ID
RG1 -86356
RG1-86358
RG1-86359
RGi-86360
RG1-86398
Flov
(HGD or Dry
Tons/Day)
34.6
121B
1620
200
0.072
TCOF
(PPT)
0
0.0636
TOTAL
TCDF
(Grais)
0. OOOEtOO
0. OOOEtOO
0. OOOEtOO
0.
I.
1.
OOOEtOO
733E-05
733E-05
0.
0.
0.
0.
3.
3.
TCDF
(Ibs) ND AVE QA
OOOEtOO ND(0. 00660) 33.3*
OOOEtOO
OOOEtOO
OOOEtOO
818E-08
818E-08
General Sever Inputs
1.
2.
3.
4.
5.
6.
7.
8.
9.
20.
11.
Coibined Paper Machines
disc. Pulping
Nisc. Pover Groups
Otis Hill Return
Vater Treatient Backvash
A Side E Stage Filtrate
A Side D Stage Filtrate
B Side E Stage Filtrate
B Side 0 Stage Filtrate
Bottoi Ash >
Fly Ash *
* Included in 3. Flow
RG1 -86379
RGi-86361
RG1-86362
RG1-863BO/92
RG1-86357
RG1 -86370
RG1-86371
RG1-86373
RGt-8637*
BG1 -86395
RG 1-86396
Total
18.9
4.2
2.6
2.5
1.8
I
1.6
0.75
33.35
0.173
0.346
8.61
10.314
4.715
14.128
9.158
0
0
TOTAL
1.
0.
0.
3.
7.
1.
8.
2.
2.
238E-02
OOOEtOO
OOOEtOO
274E-03
027E-02
785E-02
556E-02
600E-02
153E-01
2.
0.
0.
7.
1.
3.
1.
5.
4.
726E-05 X
OOOEtOO
OOOEtOO
212E-06 11
12.8*
548E-04 X 13.6*
931E-05 X 24.7*
885E-04
726E-05
ND(0.183)
HD10.310)
743E-04
Bleach Plant inputs
1.
2.
3.
4.
5.
HU B Side Brovnstock Pulp
SU B Side Brounstock Pulp
SV A Side Brovnstock Pulp
Process Hater
Paper Machine Whitewater
RG1-86365
RG1-B6364/91
RG1-86364/91
RG1-86356
RG1 -86379
289
197
525
9
With Above
2.32
1.133
1.133
0
0.173
TOTAL
6.
2.
5.
0.
0.
1.
088E-04
027E-04
401E-04
OOOEtOO
OOOEtOO
352E-03
1.
4.
1.
0.
0.
2.
341E-06
464E-07
190E-06 1
OOOEtOO ND(0. 00660) X 33.3)1
OOOEtOO X
977E-06
Acid Sever inputs
1.
2.
A Side C Filtrate
B Side C Filtrate
Flow
RG1-86369
RG1-86372
Total
3
1.1
4.1
0.173
0.326
TOTAL
1.
1.
964E-03
357E-03
3.322E-03
4.
2.
7.
327E-06
990E-06
317E-06
UVTF Inputs
1.
2.
3.
i
Influent To WTP
Coibined Acid Sever
Landfill Leachate
RG1-86386/02
RG1-86368
RG 1-86398
Interiittant Flov(SOgpi) Flov Total
37
4.03
0.072
41.102
3.036
2.693
0.0636
TOTAL
4.
4.
1.
4.
252E-01
108E-02
733E-05
663E-01
9.
365E-04 I 31.7*.
9.048E-05
3.818E-08
1.
027E-03
Dlb. UUTP Sludge Inputs
t. Gravity Thick. Sec. Sludge 8G1-86397
33.9 2147 6.609E-02 1.456E-04
F19
-------
Hill £
09-Feb-88
Hill E
Nass Balance ( ND - 0.0 Assuied 1
Basis : 1 Day
A2, General Mill Exports
1. VUTP Effluent
2. Coibined Devatered Sludge
3. SU Bleached Pulp - A Side
4. HY Bleached Pulp - B Side
5. SU Bleached Pulp - B Side
B2. General Sever Exports
1. UVTP Influent
2. Coibined Acid Sever
C2. Bleach Plant Exports
1. SU Bleached Pulp A Side
2. HU Bleached Pulp B Side
3. SU Bleached Pulp 6 Side
4. A Side C Filtrate
5. A Side E Sta?e Filtrate
6. A Side D Stage Filtrate
7. B Side C Filtrate
6. B Side E Stage Filtrate
9. B Side D Stage Filtrate
D2. VUTP Exports
t. Effluent
2. Coibined Devatered Sludge
Saiple ID
RG1-86388/88A
RG1-86387/A/B
RG1-86366
RGi-86367
RG1-86366
RG1-86386/02
RG1-86368
RGl-86366
RGI-86367
RGl-86366
RG1-86369
RGi-86370
RG1 -86371
RG1-86372
RG1-86373
RG1 -86374
RG1-86388/88A
RG1-86387/A/B
Flow
(HGD or Dry
Tons/Day)
41
90
483
272
181
37
4.03
483
272
181
3
1.8
1
1.1
1.6
0.75
41
90
TCDF
(PPT)
0.416
756
139
182
139
TOTAL
3.036
2.693
TOTAL
139
182
139
0.173
10.314
4.715
0.326
14,128
9.158
TOTAL
0.416
756
TOTAL
TCDF
(Grais)
6.456E-02
6.178E-02
6.096E-02
4.495E-02
2.284E-02
2.322E-01
4.252E-01
4.108E-02
4.663E-01
6.096E-02
4.495E-02
2.284E-02
1.964E-03
7.027E-02
1.785E-02
1. 3571-03
8.556E-02
2.600E-02
3.317E-01
6.456E-02
6.178E-02
1.263E-01
TtDF
(Ibs)
1.422E-04
1.361E-04
1.343E-04
9.901E-05
5.032E-05
5.116E-04
9.365E-04
9.048E-05
1.027E-03
1.343E-04
9.901E-05
5.032E-05
4.327E-06
1.548E-04
3.931E-05
2.990E-06
1.885E-04
5.726E-05
7.307E-04
1.422E-04
1.361E-04
2.783E-04
Percent
Total
27.8*
26.61
26. 2*
19. 4)1
9.81
100. OS
91.21
8.8*
100.0*
18. 4*
13.5*
6.9*
0.6*
21.2*
5.4*
o.n
25.81
7.8*
100.0*
51.1%
48.9*
100.0*
NO AVE QA
! 65.8.30.4*
X
I
I 31.7*,46*,15.1*
I 13.6*
X 24.7*
X 65.8,30.4*
X
F 20
-------
ATTACHMENT G
ANALYTICAL RESULTS FOR CHLORINATED PHENOLICS,
TOTAL SUSPENDED SOLIDS, AND BIOCHEMICAL OXYGKN DEMAND
-------
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G 5
-------
Table 6-6
Oilorophenol Analyses SuiMry
IHTAKE!!
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichlorophenol
3,4-Dichlorcphenol
2,5-Dichlorophenol
2,4/2,5-Dichloraphenol
2,3-Oichlorophenol
2,4,5-Trichlorcphenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
M> - Mot detected
MILL A
PPb
ND
ND
ND
ND
ND
ND
ND
ND
M>
ND
10
ND
ND
ND
ND
ND
HILL A
Fit* (HGD)
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
20
Ibs/day
B
ppb
ND
KD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
B
PPb
Ibs/dav
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
37.1
Ibs/day
c
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
30
Ibs/day
D
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
D
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
11.7
Ibs/day
£
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
E
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
34.6
Ibs/day
Suirf
All Hills
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Sl» of
All Hills
Ibs/day
SIM of diloropbenols 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sm oi diloroquaiacols 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sui oi chlorovanillins 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sw oi all analytes 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
G 6
-------
Table 6-7
Chlorophenol Analyses Sumarv
HHTP INFLUENTS
HILL
Analvte
2-Chlorophenol
2,6-Didilorophenol
2,4-Dichlofophenol
3,4-OichloroPhenol
2,5-Oichlorophenol
2,4/2,5-Dichloraphenol
2,3-Didilorophenol
2,4.5-Trichlorophenol
Pentadilorophenol
4,5-Oichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-ChlorovanilIin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected in range of
NA - Not analyzed
HILL
FlOM
A
PPb
NA
ND
2.6
ND
NA
—
ND
ND
0.4
4.0
4.0
0.9
12.5
NA
3.8
0.8
B
Ibs/day ppb
0.00
0.00
0.44
0.00
0.00
0.00
0.00
0.00
0.07
0.67
0.67
0.15
2.10
0.00
0.64
0.13
ND
ND
9.8
M>
ND
—
ND
M)
ND
4.8
8.9
3.3
6.3
2.2
6.5
1.7
Ibs/day
0.00
0.00
3.05
0.00
0.00
0.00
0.00
0.00
0.00
1.50
2.77
1.03
1.96
0.69
2.03
0.53
C
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
13.8
5.2
ND
0.4
ND
13.3
2.1
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.63
1.37
0.00
0.11
0.00
3.50
0.55
D
PPb
ND
ND
—
ND
—
6.3
ND
ND
ND
24.3
9.0
7.4
4.8
4.0
21.0
11.3
Ibs/dav
0.00
0.00
0.00
0.00
0.00
0.99
0.00
0.00
0.00
3.82
1.42
1.16
0.76
0.63
3.30
1.78
E
PPb
ND
ND
—
ND
—
11.7
ND
ND
ND
24.0
30.6
5.3
50.1
»
13.5
12.4
Ibs/day
0.00
0.00
0.00
0.00
0.00
3.61
0.00
0.00
0.00
7.41
9.45
1.64
15.47
0.00
4.17
3.83
Suiof
All Hills
Ibs/day
0.00
0.00
3.49
0.00
0.00
4.60
0.00
0.00
0.07
17.03
15.68
3.98
20.39
1.31
13.63
6.82
1 to3ug/L (ppb).
A
(H6D)
PPb
20.1
Ibs/day |
B
•Pb
37.35
Ibs/day
C
PPb
31.5
Ibs/day
D
PPb
18.85
Ibs/day
E
PPb
37
Ibs/day
SUt of
All Hills
Ibs/day
Sum of dilorophenols
Sun of chloroquaiacols
Sw of chlorovanillins
Sui of all analytes
3.00 0.50 9.80 3.05 0.00 0.00 6.30 0.99 11.70 3.61 8.16
21.40 3.59 23.30 7.26 19.40 5.10 45.50 7.16 110.00 33.96 57.07
4.60 0.77 10.40 3.24 15.40 4.05 36.30 5.71 25.90 8.00 21.77
29.00 4.86 43.50 13.56 34.80 9.15 88.10 13.86 147.60 45.57 87.00
G7
-------
Table 6-6
Chlcrophenol Analyses Sunary
*TP EFai£NTS
MILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Dichlorophenol
2,3-Oichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-DichlorovaniUin
ND - Not detected in range of
NA - Not analyzed
MILL
Flo*
A
ppb
ND
ND
2.1
ND
ND
—
ND
ND
2.0
2.7
5.0
3.3
1.9
ND
ND
ND
Ibs/day
0.00
0.00
0.41
0.00
0.00
0.00
0.00
0.00
0.39
0.52
0.97
0.64
0.37
0.00
0.00
0.00
8
ppb
ND
ND
0.2
ND
ND
—
ND
ND
ND
ND
2.3
1.7
2.8
1.9
4.2
3.2
C - (36-72 MS)
Ibs/day
0.00
0.00
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.70
0.52
0.86
0.58
1.26
0.98
ppb
ND
ND
—
ND
—
ND
ND
0.7
ND
ND
ND
ND
ND
ND
ND
M>
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.17
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
D
PPb
ND
ND
—
ND
—
5.9
ND
ND
NO
3.1
10.0
7.2
4.5
W
4.8
1.0
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.91
0.00
0.00
0.00
0.48
1.54
1.11
0.69
0.00
0.74
0.15
E
ppO
ND
ND
—
ND
—
ND
ND
ND
ND
ND
5.6
ND
ND
ND
ND
ND
ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.92
0.00
0.00
0.00
0.00
0.00
3UI Crf
All Hills
Ibs/day
0.00
0.0(i
0.47
0.00
0.00
0.91
0.00
0.17
0.39
1.00
5.13
2.27
1.92
0.58
2.02
1.13
1 to 3ug/L (ppb).
A
(HGD)
PI*
23.2
Ibs/day
B
ppb
C - (36-72 US)
36.6
Ibs/day
ppb
29.5
Ibs/day
D
ppb
18.49
Ibs/day
E
Pf*
41
Ibs/day
QIM ni
am or
All Hills
Ibs/day
Sw of chlorophenols 4.10 0.79 0.20 0.06 0.70 0.17 5.90 0.91 0.00 0.00 1.94
Su« of chloroquaiacols 12.90 2.50 6.80 2.06 0.00 0.00 24.80 3.83 5.60 1.92 10.32
Sua oi chlorovanillins 0.00 0.00 9.30 2.84 0.00 0.00 5.80 0.89 0.00 0.00 3.74
SIM of all analytes 17.00 3.29 16.30 4.98 0.70 0.17 36.50 5.63 5.60 1.92 15.99
G8
-------
Table 6-9
Oilorophenol Analyses Smurv
BLEACH PLANT
CSTA6ES
HILL A - a
Analvte ppb Ibs/day
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oidilorophenol
3,4-Dichlorophenol
2,5-Dicfilorophenol
2,4/2,5-Didilorcphenol
2,3-Oichlorophenol
2,4,5-Trichlorcphenol
Pentachlorophenol
4,S-Oichloro9uaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetradiloroquaicol
5-Chlomanillin
6-Qilorwanillin
5,6-Oichlorovanillin
W
ND
3.1
M>
ND
—
ND
(D
ND
*
2.6
M>
3.1
ND
ND
ND
0.00
0.00
0.04
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.00
0.04
0.00
0.00
0.00
A-NN
PPb Ibs/day
ND
ND
5.3
»
ND
—
ND
ND
ND
3.2
3.5
0.9
0.9
ND
M>
M)
0.00
0.00
0.07
0.00
0.00
0.00
0.00
0.00
0.00
0.04
0.05
0.01
0.01
0.00
0.00
0.00
8
PPb Jbs/day
ND
ND
9.7
ID
ND
—
M)
ND
0.7
4.8
14.3
7.3
14.1
ND
5.6
6.1
0.00
0.00
0.49
0.00
0.00
0.00
0.00
0.00
0.04
0.24
0.72
0.37
0.71
0.00
0.26
0.31
C
ppb Ibs/day
ND
W)
—
ND
—
ND
M)
ND
ND
54.1
20.9
6.8
4.5
5.2
56.5
14.4
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.33
0.51
0.17
0.11
0.13
1.39
0.35
D - A SIDE
ppb Ibs/day
M)
M)
—
ND
—
11.2
M)
ND
H>
14.3
3.3
3.1
ND
ND
15.3
4.8
0.00
0.00
0.00
0.00
0.00
0.13
0.00
0.00
0.00
0.17
0.04
0.04
0.00
0.00
0.18
0.06
D - B SIDE
ppb Ibs/day
ND
M)
—
ND
—
13.9
M>
M)
ND
12.9
6.6
9.9
3.7
5.1
15.6
6.7
0.00
0.00
0.00
0.00
0.00
0.11
0.00
0.00
0.00
0.10
0.05
0.08
0.03
0.04
0.12
0.05
E - A SIDE
PPb Ibs/day
ND
ND
—
ND
—
15.3
ND
ND
ND
3.7
8.4
ND
5.9
M>
4.4
0.7
0.00
0.00
0.00
0.00
0.00
0.38
0.00
0.00
0.00
0.09
0.21
0.00
0.15
0.00
0.11
0.02
£ - B SIDE
ppb Ibs/day
ND
ND
—
»
—
7.5
ND
ND
ND
3.6
7.9
ND
6.5
N>
3.5
ND
0.00
0.00
0.00
0.00
0.00
0.07
0.00
0.00
0.00
0.03
0.07
0.00
0.06
0.00
0.03
0.00
Sui oi
Ail Hills
0.00
0.00
0.60
0.00
0.00
0.69
0.00
0.00
0.04
2.01
1.70
0.66
1.12
0.17
2.12
0.79
» - Not detected
HILL A - SH
A-W
D - A SIDE D - B SIDE E - A SIDE E - B SIDE
Flow (NED) 1.73
1.58
6.05
2.95
1.42
0.95
3
1.1 All Hills
ppb Ibs/day ppb Ibs/day ppb Ibs/day ppb Ibs/day ppb Ibs/day ppb Ibs/day ppb Ibs/day ppb Ibs/day Ibs/day
So of diloraphenols 3.10 0.04 5.30 0.07 10.40 0.53 0.00 0.00 11.20 0.13 13.90 0.11 15.30 0.38 7.50 0.07 1.33
St» of chloroquaiacols 5.90 0.09 8.50 0.11 40.50 2.04 86.30 2.12 20.70 0.25 33.10 0.26 18.00 0.45 18.00 0.17 5.49
SUB of dilorwanillins 0.00 0.00 0.00 0.00 11.70 0.59 76.10 1.87 20.10 0.24 27.40 0.22 5.10 0.13 3.50 0.03 3.06
StM of all analytes 9.00 0.13 13.80 0.18 62.60 3.16 162.40 4.00 52.00 0.62 74.40 0.59 38.40 0.96 29.00 0.27 9.90
G9
-------
Tiblt 6-10
Chlorophenol Analyses SuMary
BLEACH PLANT
E STAGS
HILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichloraphenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Dichlorophenol
2,3-Didilorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Didiloroguaiacol
3,4,5-Tricnloroguaicol
4,5,6-Trichloroguaicol
Tetrachloraquaicol
5-Qilorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected
HILL
Flow
A-SN
Ppb Ibs/day
ND 0.00
ND 0.00
16.1 0.19
ND 0.00
ND 0.00
- 0.00
ND 0.00
ND 0.00
ND 0.00
5.1 0.06
84.0 1.01
54.3 0.65
175 2.10
2.3 0.03
6.4 0.08
38.6 0.46
A-»
(HGD) 1.44
PPb Ibs/day
A-HM
ppfa Ibs/day
ND 0.00
ND 0.00
26.6 0.16
ND 0.00
ND 0.00
- 0.00
ND 0.00
ND 0.00
ND 0.00
166 1.01
123 0.75
36.5 0.22
19.8 0.12
16.2 0.10
113 0.69
13.2 0.08
A-HH
0.73
PPb Ibs/day
B
PPb
ND
ND
43.60
ND
ND
—
ND
ND
6.1
196
351
146
170
24.4
163
97.0
B
PPb
Ibs/day
0.00
0,00
0,80
0,00
0,00
0,00
0,00
0,00
0,11
160
644
2.68
112
0,45
2.99
1.78
2.2
Ibs/day
C
PPb
ND
ND
—
ND
—
7.9
ND
ND
7.5
395
86.6
39.6
30.5
15.2
209
40.2
C
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.32
0.00
0.00
0.31
16.15
3.54
1.62
1.25
0.62
B.55
1.64
4.9
Ibs/day
D
PPb
ND
ND
—
ND
—
117
ND
ND
7.1
521
314
220
81.5
37.8
371
146
D
PPb
Ibs/day
0.00
0.00
0.00
0.00
0.00
2.66
0.00
0.00
0.16
11.83
7.13
4.99
1.85
0.86
8.42
3.31
2.72
Ibs/day
E - A SIDE
PPb Ibs/day
1.0 0.02
ND 0.00
- 0.00
ND 0.00
- 0.00
76.0 1.14
ND 0.00
ND 0.00
6.8 0.10
286 4.30
422 6.34
60.4 0.91
358 5.38
31.4 0.47
241 3.62
128 1.92
E - A SIDE
1.8
PPb Ibs/day
E - B SIDE
ppb Ibs/day
ND 0.00
ND 0.00
- 0.00
ND 0.00
- 0.00
33.8 0.45
ND 0.00
ND 0.00
ND 0.00
106 1.42
184 2.46
34.8 0.46
199 2.66
16.4 0.22
79.8 1.07
70.5 0.94
E - B SIDE
1.6
PPb Ibs/day
All Hills
Ibs/day
0.02
0.00
1.16
0.00
0.00
4.57
0.00
0.00
0.68
38.36
27.67
11.54
16.48
2.74
25.41
10.15
Sm of
All Hills
Ibs/day
Sw of dilorophenols
Sw of chloroquaiacols
Sun oi chlorovanillins
Sut of all analytes
16.10 0.19 26.60 0.16 49.70 0.91 15.40 0.63 124.10 2.82 83.80 1.26 33.80 0.45 6.42
318.40 3.83 345.30 2.10 863.00 15.84 551.70 22.56 1136.50 25.80 1126.40 16.92 523.80 6.99 94.04
47.30 0.57 142.40 0.87 284.40 5.22 264.40 10.81 554.80 12.59 400.40 6.01 166.70 2.23 38.30
381.80 4.59 514.30 3.13 1197.10 21.98 831.50 34.00 1815.40 41.21 1610.60 24.19 724.30 9.67 138.77
G 10
-------
Tablt 6-11
Chlorophenol Analyses Sunary
BLEACH PLANT
OSTAEES
Aiulyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichloropbenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2,4/2,5-Didtlorophenol
2,3-Dichlorophenol
2,4,5-Trichloropbenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloro9uaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected
Mill B
PPb
NO
ND
ND
ND
ND
—
ND
ND
ND
1.4
6.6
0.9
4.B
ND
ND
ND
HILL B
RON (HGD)
Pf*
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.09
0.01
0.06
0.00
0.00
0.00
1.57
Ibs/day
C
PI*
ND
ND
—
ND
—
ND
ND
ND
ND
4.6
2.1
ND
ND
ND
2.8
0.7
C
PI*
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0
Ibs/day
E-A
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
1.7
4.2
ND
ND
ND
1.6
ND
E-A
PI*
SIDE
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.04
0.00
0.00
0.00
0.01
0.00
SIDE
1
Ibs/day
E-S
PPb
ND
ND
—
ND
—
ND
ND
ND
ND
KD
ND
ND
ND
ND
ND
ND
E-E
PPb
ISIDE
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
IS10E
0.75
Ibs/day
Sturi
All Hills
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.12
0.01
0.06
0.00
0.01
0.00
Suaof
All Hills
Ibs/day
St» of chlorophenols 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sw of chloroquaiacols 13.70 0.18 6.70 0.00 5.90 0.05 0.00 0.00 0.23
Sl» of dilorovanillins 0.00 0.00 3.50 0.00 1.60 0.01 0.00 0.00 0.01
Sm of all aulytes 13.70 0.18 10.20 0.00 7.50 0.06 0.00 0.00 0.24
Gil
-------
Table 6-12
Chlorophenol Analyses Sundry
BLEAm PLANT
H STAGES
Analvte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Dichlorophenol
3,4-Dichlorophenol
2,5-Oichlorophenol
2, 4/2, 5-Dichloraphenol
2,3-DichlorophenoI
2,4,5-Tridilorophenol
Pentachlonphenol
4,5-Dichloroguaiacol
3,4,5-Trichloroquaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Oichlorovanillin
ND - Not detected
HILL B
ppb
ND
ND
3.7
ND
ND
—
ND
NO
4.0
15.9
31.5
68.5
81.4
15.0
19.6
64.8
HILL B
Flow (HED)
Ppb
(H-l)
Ibs/day
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.03
0.06
0.14
0.16
0.03
0.04
0.13
(H-l)
0.24
Ibs/day
B (H-2)
Pf*
ND
ND
ND
ND
ND
—
ND
ND
1.3
S.6
11.3
11.8
21.0
4.6
£.9
14.7
B
ppb
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.06
0.13
0.13
0.24
0.05
0.10
0.17
(tt-2)
1.36
Ibs/day
D - A SIDE D
ppb
M)
ND
—
ND
—
ND
ND
ND
ND
22.5
5.7
9.7
1.0
2.4
23.6
4.9
Ibs/day
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.26
0.06
0.11
0.01
0.03
0.27
0.06
D - A SIDE D
PPb
1.42
Ibs/day
-BSIDE
PPb
ND
ND
—
ND
—
4.9
ND
ND
ND
19.3
10.7
22.7
6.1
2.8
22.7
.12.4
Ibs/day
0,00
0.00
0,00
0.00
0,00
0,06
0..00
0,00
0,00
0.22
0,12
0.26
0,07
0.03
0.26
0.14
All Hills
Ibs/day
0.00
0.00
0.01
0.00
0.00
0.06
0.00
0.00
0.03
0.57
0.38
0.64
0.48
0.14
0.67
0.49
- B SIDE
PPb
0.92
Ibs/day
CllB ffrf
aw VT
All Hills
Ibs/day
Sw of dilorophenols 7.70 0.02 1.90 0.02 0.00 0.00 4.90 0.06 0.09
Sui
-------
Tiblt 6-13
Chloroptenol Analyses SuMiry
UWFILL
Analyte
2-Chlorophenol
2,6-Dichlorophenol
2,4-Oichlorophenol
3,4-Dichlorcphenol
2,5-Dichlorophenol
2,4/2,5-Dichlorophenol
2,3-Oichlorophenol
2,4,5-Trichlorophenol
Pentachlorophenol
4,5-Dichloroguaiacol
3,4,5-Trichloroguaicol
4,5,6-Trichloroguaicol
Tetrachloroguaicol
5-Chlorovanillin
6-Chlorovanillin
5,6-Dichlorovanillin
ND - Not detected
HILL B
PPb
ND
ND
ND
M)
ND
ND
ND
ND
ND
ND
ND
ND
M>
M)
ND
ND
Ibs/day
0.00
O'.OO
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
HILL B (H-U
Sw of chlorophenols
Su oi chloroquaiacols
SIM erf chlorovanillins
Su« of all analytes
Flow (HBO)
W*
0.00
0.00
0.00
0.00
Ibs/day
0.00
0.00
0.00
0.00
G13
-------
TABLE G-14
BOD5 and TSS RESULTS SUMMARY
MILL A
Sample TSS 5 Day
I.D. ppm BOD ppm
OE 020818 6 0
(Powerhouse Wastewater)
DE 020801 10 0
(Treated river water)
DE 020921 654 175
(combined untreated wastewater)
DE 020821 94 400
(Moonlight Leachate)
DE 020807 16 119
(Recovery #9)
DE 020915 66 212
(Bleach Plant #5)
DE 020806 1402 291
(Kraft Mill #6)
DE 020811 1132 214
(Paper Mill #2)
DE 020922 104 29
(Secondary Clarifier)
G 14
-------
TABLE G-15
BOD5 and TSS RESULTS SUMMARY
MILL B
SAMPLE SAMPLE TSS BOD
CODE DESCRIPTION (ppm) (ppm)
A-l Treated Water 11 0.5
B-la Brown Stock Filtrate Tank 64 115
B-lb Brown Stock Filtrate Tank 51 253
o'flow outside Kraft Mill
B-2a Corrosive sewer-recovery 144 337
evaporator, recaust, refiners
B-3 Kraft sewer - Kraft pulping
and Alkaline Bleach 70 226
D-3a C12 Seal Tank o'flow 40 253
D-4a E-l Seal Tank o'flow 36 240
E-l Tissue Machine sewer 204 16
F-3a Combined Acid sewer 49 142
F-3b Combined Process sewer 193 158
F-4 Secondary Effluent 40 5
F-5 Landfill Leachate 312 71
G15
-------
TABLE G-16
BOD5 and TSS RESULTS SUMMARY
MILL C
Sampl e
ID
DE026
OE026
06026
OE026
DE026
DE026
OE026
06026
D6026
OE026
OE026
06026
OE026
06026
D6026
OE026
OE026
001
105
106
108
109
110
112
113
119
120
121
122
012
013
014
205
206
Sample Description
Treated River Hater
Untreated Groundwater
Untreated River Water
Station 7
Station 8
Station 28
Station 9
Station 13
Station 1
Station 3
Station 4
Station 5
Primary Influent (Sta 20)
Secondary Effluent (C-24)
Sludge Landfill leachate
Wood Boiler and Boilerhouse (Sta 15)
Secondary Effluent (36-72)
TSS
(mg/1 )
10
6
21
397
1134
25
99
2016
1684
330
768
616
540
16
66
1084
36
BOO
(mg/1 )
2
301
11
10
9
G L6
-------
TABLE G-17
Sample
ID
Bl
B2
Cl
C2
C3
D4
D5
D6
D7
D9
El
Fl
F2
F7
8005 and TSS RESULTS SUMMARY
MILL D
Sample Description
Brownstock decker sewer
Dreg wash sewer
Evaporator sewer
Recovery boiler sewer
Lime kiln sewer
Chlorination stage - A-side
Caustic stage - A-side
Hypo stage - A-side
Chlorination stage - B-side
Hypo stage - B-side
Ground wood mill/paper machines
WWTP influent
WWTP effluent
Sludge lagoon effluent
TSS B005
(mg/L) (mg/L)
26 180
1250
<1 120
4.5
253
10.5
12.7
12
17.5
13
1490 305
875 232
14.5 13.2
102a
NOTE: (a) COD value presented.
G 17
-------
TABLE G-18
BOD5 and TSS RESULTS SUMMARY
MILL E
Stnplt 1
A-l
A2
B1.2
CIS
m i *>< <
Di , I VVV*
02
El
B3
17
BOD ag/1
1
1
220
375
120
200
340
16
1,400+
TSS M/l
2
*
230
600
1,100
350
680
89
160
Upstream River Water
(Chlorinated Process Water
A Side General Sewer
A Side.Caustic
B Side General Sever
Otis Mill Return
Primary Influent
Final Effluent
landfill Leachate
* A2 - All •••pi* ustd for •*•*. Ho TSS,
G 18
------- |