A SURVEY OF PCS IN WASTEWATER
FROM PAPER RECYCLING OPERATIONS
United States
Environmental
Protection Agency
Region I
NEW ENGLAND REGIONAL LABORATORY
60 WESTVIEW AVE. LEXINGTON MASSACHUSETTS 02173
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A SURVEY OF PCB IN WASTEWATER
FROM PAPER RECYCLING OPERATIONS
by
John J. Zambrano
and
Kevin J. Walter
of the
New York State
Department of Environmental Conservation
Presented at the
North East Regional Meeting of the
National Council of the Paper Industry
For Air and Stream Improvement, Inc.
November 1, 2, 1978
Boston, Massachusetts
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TABLE OF CONTENTS
Page No.
i. List of Tables and Figures 1.
I. Introduction 1
II. Purpose and Scope 3
III. PCB’s and Recycled Paper 5
IV. Sampling and Analytical Methods 9
V. Mill Production and Wastewater Treatment 13
VI. Results 15
VII. Discussion and Conclusions 19
References 23
Appendix PCB Concentrations, Individual Analyses A-i
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LIST OF TABLES AND FIGURES
Table Follows
Number Title Page
1 Profile of Mills Reviewed for Survey 3
2 Survey Mills Recycled Paper Consumption 13
3 Survey Mills Wastewater Treatment 14
Characteristics
4 Summary of Analyses 15
5 Median PCB Concentrations of Individual 16
Mills
6 PCB Mass Discharges 17
7 PCB’s Discharged per Ton of Recycled 18
Paper Used.
Figure
Number
1 PCB Concentrations Cumulative Frequency 16
Di tribution
1
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I. Introduction
Polychiorinated biphenyls (PCB’s) emerged in the 1970’s as a
significant water contaminant and serious hazard to human and
animal health. The presence of this chemical is widespread, but
it appears that New York State might very well be the leader in
contamination by these persistent chlorinated hydrocarbons (ref. 1).
Reports of high levels of PCB contamination of fish caught in New
York State waters became more and more common in the mid 1970’s.
Levels frequently exceeded the FDA limit of 5 ppb.
The initial concern of the Department was the control or
elimination of the direct sources of PCB wastewaters. In September
1976 the Department and General Electric Company, the state’s
major user of PCB’s for capacitor production, reached a settlement
concerning their wastewater discharge (ref. 2). The Company was
permitted a 1 gr/day discharge based on an achievable concentra-
tion of 1 ppb.
In the aftermath of the General Electric case, the Department
became concerned with potential discharge of wastewater with
indirect contamination by PCB’s. Those of us associated with the
paper industry had been aware for some time of the contamination
of recycled paper from at least two uses of this chemical in years
I
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prior to 1971. What was not known, however, was the levels of
this contaminant in paper mill wastewater discharges and specific-
ally in the large number of New York State mills using recycled
paper. New York State has long led the country in total number
of paper mills even though total State tonnage is well below that
of many states. For these reasons it was believed necessary to
institute PCB monitoring in wastewater discharges from mills
using recycled paper.
2
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II. Purpose and Scope
The purpose of the monitoring survey was to determine the
individual levels of PCB’s discharged from New York State paper
mills. The information would be used to determine if specific
receiving water quality problems might be attributed to these
discharges and whether treatment or controls or additional moni-
toring would be necessary or practical at the levels measured.
New York State has approximately 61 operating paper mills.
Of these, approximately 40 or 66 h use some amount of recycled
papers. The requirement for PCB self-monitoring was to be imple-
mented through the state’s N/SPDES permit program. As a practical
matter, therefore, the survey was restricted to mills with N/SPDES
permits. Mills discharging to municipal systems would not be
surveyed.
The number of mills using recycled paper and discharging
directly is approximately 29. A further reduction in the survey
population resulted from the elimination of.mills that could trace
recycled paper to a source of virgin fiber without possible PCB
contamination. This left approximately 18 mills for permit modi-
fication and self-monitoring of PCB’s. Table 1 presents a summary
of the above analysis of the New York Mills. As indicated, the
3
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TABLE 1
NEW YORK STATE PAPER MILLS
PROFILE OF MILLS REVIEWED FOR SURVEY
Parameter
Number
Total
Paper
Mills
61
Mills
Using
Recycled
Paper
40
Mills Using Recycled
Paper and Discharging
Directly (Not in Muni-
cipal System)
29
Mills Using Recycled
Paper With Possible
PCB Contamination and
Discharging Di ect1y
18
Percent
of Total
lOO7 66%
48%
3070
Percent
of Mills
Using
Recycled Paper
100%
7370
4570
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survey included approximately 4570 of mills usi ng aI l forms of
recycled paper.
The survey was to be conducted. over a one year period with
samples collected and analyzed once per manth. This frequency
and number of samples were judged satisfactory to determine a
statistically reliable level and cover a sufficient period, to
be representative of processing variations and sources of recycled
paper. The sampling and analysis, although expensive, would not
be prohibitive for the paper mills involved.
4
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III. PCB’s and Recycled: Paper
PCB’s were first manufactured in 1929. Due to their extreme
chemical and biological stability, and very low electrical con-
ductivity, PCB’s were used in many industrial products with varied
applications.
The most recently publicized, and historically largest use
of PCB has been as a dielectric fluid in transformers and capa-
citors. Beginning in 1957, however, a new use was developed for
PCB in carbonless copy paper. In 1971 this use of PCB was dis-
continued due to the growing health concerns about the presence
of PCB in food. In the period between 1957 and 1971, a total of
over 44 million pounds of Aroclor 1242 was used in carbonless copy
paper manufactured under license of the National Cash Register
Company (NCR). This carbonless paper was often called NCR paper,
perhaps after the name of the company rather than an abbreviation
for “No Carbon Required.” This amount of Aroclor 1242, a certain
mixture of PCB’s manufactured by Monsanto Chemical Company,
accounted for approximately 6.37 of Monsanto’s total domestic PCB
sales during 1957-1971. Carbonless paper contained an average of
3.4% Aroclor 1242 by weight.
5
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The purpose of Aroclor 1242 in carbonless paper was to act as
a solvent for color reactants which were encapsulated into micro-
scopic gelatin-gum bubbles on the surface of the paper. When
pressure was applied by a pen or pencil, the bubbles would rupture
allowing the release of PCB carried dyes. In 1971, the use of a
substitute solvent was begun, therefore, only carbonless paper
manufactured between 1957 and 1971 is suspect of containing PCB.
A second potential source of PCB in recycled papers is due
to the use of PCB’s in certain inks between approximately 1968
and 1971. The uses of these inks included ultraviolet light sens-
itive inks and “flexographic” inks for printing on flexible pack-
aging materials. It has been estimated (reference 3) that the use
of such inks in 1970 was about 20 million pounds containing
approximately 20,000 pounds of PCB, mostly Aroclor 1254. Based
on available trends and the short period of time involved, it was
further estimated that the total use of PCB’s in printing inks
was about 50,000 pounds. This amount can therefore be classified
as minor since it corresponds to 0.1 percent of the total PCB use
in carbonless paper.
Miscellaneous reported uses of PCB in paper include use as a
fire retardant and/or plasticizer in adhesives, surface coatings,
paints, sealants, etc. (ref. 3.4)
6
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Many types of paper currently being recycled today were
possibly originally made with PCB contaminated paper products.
Paper pulp made from this type of recycled paper may therefore be
called indirectly contaminated. An example of the indirect con-
tamination problem is foodboard. During 1971, the Food and Drug
Administration traced PCB contamination in cereal to foodboard
packaging materials. Foodboard PCB concentrations of several
hundred parts per million were recorded. In order to control this
problem, and meet the FDA 10 ppm PCB limit for foodboard, the
industry switched to non-PCB contaminated recycled paper sources.
Recycling today of old foodboard, however, may or may not there-
fore be a source of PCB’s.
As mentioned previously, 40 of the 61 New York paper mills
use some type and percentage of recycled paper. Virgin chemical
and groundwood pulp has been considered PCB free. Since newspaper
is virtually 100% groundwood pulp, recycled newsprint (over issue
and super news) is also considered to be non-contaminated. Number
one news, however, may possibly be contaminated from miscellaneous
types of papers which may be present up to 5% by weight. Addi-
tionally, those mills whose only recycled paper use was directly
tracable to virgin fiber were considered non-contaminated.
Examples of this type of pulp would be Kraft mill broke, envelope
clippings, off-quality Kraft-fine paper, etc. The types of pulp
7
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used in the 18 mills in the sampling program included a large
percentage of the 47 standard categories of recycled paper. Of
particular interest, however, were those types of recycled paper
most likely to have PCB contamination. These types include #1
mixed, super mixed, #1 sorted white ledger, and #1 sorted colored
ledger.
8
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IV. Sampling and Analytical Methods
Samples were collected for the survey beginning in October,
1976 and ending in September, 1978. Sampling methods employed by
the 18 mills varied from mill to mill. N/SPDES permit instructions
to the mills specified that 24 hour flow proportioned composite
samples be taken of the treated effluent once per month, however
six mills took a single grab for their sample. For two of the
mills, mill I and mill M, a grab sample is considered representa-
tive of a daily discharge due to several days detention in their
wastewater treatment systems. Of the 12 mills taking 24 hour
composite samples, 9 used flow proportioned automatic sampling
equipment, and 3 mills manually composited hourly grab samples
for a 12 or 24 hour sampling period. A listing of the type of
sample for each mill is shown in Table 3.
Samples were collected in both glass and plastic containers
during the sampling period. All mills except mill M transmitted
samples to the laboratory in glass containers. However, many of
the mills were provided with new glass sample containers by their
laboratories. Samples from mills A, B, N, P and Q were hand
delivered to the laboratory, the remainder were transported by
USP or other common carrier. All samples were taken of the final
9
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‘1 -
effluent immediately prior to discharge to the receiving waters,
except mill C which sampled raw wastewater as it left the mill
prior to wastewater treatment.
In all except one case where in-company analytical facilities
were used, the survey mills selected private laboratories to con-
duct PCB testing. A total of eight laboratories were utilized.
One laboratory tested samples for seven mills, and another tested
three mil]!s samples. The remaining six laboratories tested for
one or two survey mills each. All of the laboratories utilized
gas chromatography (CC) with the electron capture detection method.
Extraction, sample cleanup, concentration, and chromatogram inte-
gration techniques varied considerably between laboratories.
Although it was judged impossible to determine what relative
effect these differences had on the data reported, It Is worth-
while to discuss some of the differences in analytical method.
Extraction procedures used generally paralleled the EPA triple
liquid-liquid extraction in hexane and 15% methylene chloride.
One extraction or two extractions were performed by some of the
laboratories rather than a triple extraction. In some cases
alternate solvents were used such as pure hexane, hexane acetone,
or petroleum ether. All laboratories except one used a single
pass through a fluorosil column for cleanup. Most laboratories
l0
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used the kuderna-danish method to concentrate the samples, however
to differing final volumes. It is also known that varying initial
volumes of sample were used.
Although 1.0 ppb detectability was specified by New York
State, much of the data submitted was performed to a detectability
of 0.1 ppb, or as low as 0.01 ppb. In this regard the method of
quantification or integration is of interest. The techniques used
ranged from computer verification and integration of chromatogram
peaks to the measurement of the magnitude of one or more repre-
sentative peaks. Some laboratories manually integrated chromato-
grams. Due to the environmentally altered nature of the various
aroclors, the identification and quantification techniques can
only be compared between laboratories by split standard sample
,
analyses. This was beyond the scope of the survey. -
PCB concentrations were reported in accordance with NYS
instructions as total PCB by most survey mills, rather than as
various aroclors. In order to calculate total PCB’s though, each
lab compared the sample to standard aroclorchromatograms.
Virtually every laboratory followed different procedures in this
regard. One laboratory compared only to 1242, another used 1016,
1221, 1242, and 1254, while still another used 1242, 1248, 1254
and 1260, and one of the laboratories used only 1242 and 1254.
11
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In all survey mills except one, the most commonly found aroclors
1242 and 1254 were utilized as standards at a miminum.
All laboratories were questioned about the accuracy of their
results in the 0.05 - 1.0 ppb range. Based on previous analyses
of EPA and State standards, the laboratories reported error to
be± 57. to±4O h, the higher error at the lowest concentrations.
Importantly, it is noted that all analytical results sub-
mitted were gross, not net, values. Therefore any background PCB
concentrations in mill intake waters were reflected in the final
discharge concentrations. N& allowance was made for intake
waters, even in the few cases where mills analyzed for it.
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V. Mill Production and Wastewater Treatment
A summary of the types of mills, pulp and paper production
and the amount of recycled paper is presented in Table 2. Included
in the survey were eight (8) boardmills, seven (7) tissue mills,
one (1) fine paper mill, one (1) molded products mill and one (1)
deinked market pulp mill. One of the board mills, Mill C, and the
molded products mill produce groundwood pulp for a portion of
their pulp requirements. The fine paper mill and one of the
tissue mills process deinked pulp for a portion of their pulp.
Total paper production of the surveyed mills is 2100 tons!
day (TPD) of which 1225 tons or 58% is recycled paper. The pro-
duction of 2100 TPD at the surveyed mills, over the period of the
study was an average of 88% of peak capacity.
Detailed paper production and recycled paper use was not
available for the 11 New York State mills using recycled paper
and discharging to municipal systems. It is estimated, however,
that their total paper production is about 1000 TPD and the
recycled paper use is about 600 TPD. Total New York State recycled
paper use is, therefore, approximately 1800 tons/day and this
survey would represent 68% of the state’s recycled paper use
tonnage.
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TABLE 2
SURVEY MILLS
RECYCLED PAPER CONSUMPTION
Recycled Consumption
Total Pulp! Recycled Paper of Recycled
Paper Pro- Paper Production Paper
Mill Mill Type duced (TPD) Used (TPD)l ( Days/year) ( Ton/year )
A Board(Felt) 450 33 68 2,240
B Tissue 9 10 300 3,000
C CW Pulp!
Board 40/65 27 300 8,100
D Board 70 74 300 22,200
E Board 100 106 350 37,100
F Tissue 30 2 350 700
G Tissue 20 4 300 1,200
H Board 160 170 350 59,500
I Board 90 94 300 28,200
J Board 96 103 300 30,900
K GW Pulp!
Molded Products 43/50 8 300 2,400
L Tissue 70 1]. 300 3,300
N Deinked Pulp!
Fine Paper 75/400 88 350 30,800
N Deinked Pulp!
Tissue 50/125 117 350 40,950
0 Deinked Pulp 125 147 350 51,450
P Tissue 45 24 350 8,400
Q Tissue 85 90 350 31,500
R Board 110 117 350 40950
Totals, Survey Mills 165/2100 1,225 402,890
Totals, All New York
State Mills Using
Recycled Paper /3100 1,800 600,000
‘Recycled paper consumption obtained from paper production using known
shrinkage or assumed shrinkage of 67g.
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The 1800 TPD of recycled paper is approximately 25% of all,
i.e. virgin and recycled paper, production in New York State and
compares closely with the 1976 nationwide rate of 23% or 13.9
million tons/year of recycled paper (ref. 5)
Yearly recycled paper use of the survey mills totaled 403,000
tons. Estimated use of all the mills in New York State is 600,000
tons per year.
Table 3 lists the types of treatment and average wastewater
flows. The types of treatment ranged from no treatment with high
solids losses to biological treatment with chemically aided
secondary clarification.
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TABLE 3
SURVEY MILLS
WASTEWATER TREATMENT CHARACTERISTICS
Mill
Mill Type
Wastewater’
Tree tment
Average
Was tewa ter
Flow (MGD )
Type of
PCB Samolin2
Board (Fe it)
Tissue
Q 7 Pulp/
Board
Board
Board
Tissue
Tissue
Board
Board
Board
GW Pulp/
Molded
Products
Tissue
Dejnked Puip/
Fine Paper
Dejnked Pulp!
Tissue
Dejnked Pulp
Tissue
Tissue
AS
None
See Note 2
AS
None
2 Stage DAF
2 Stage DAF
ASB
ASB
ASB
AS
Cla r if
2 Stage DAF
Clarif
None except in
mill saveall
TF-ASB
3.9
0.4
2.2
0.4
0.5
1.1
0.4
0.5
0.7
0.9
iTreatment System Abbreviations:
DAF = Dissolved Air Flotation
CLARIF = Chemically Aided Sedimentation
ASB = Aerated Stabilization Basin with Secondary Clarification
AS = Conventional Activated Sludge with Secondary Sedimentation
TF = Trickling Filter with Secondary Sedimentation
RBS = Rotating Biological Surfaces with Secondary Sedimentation
2 Mill C has ASB treatment but PCB sampling was conducted on the untreated
was tewater
A
B
C
D
E
F
G
H
I
J
K
L
N
N
0
P
Q
24 hourly grabs
1 grab
24 hour composite
24 hourly grabs
12 hourly grabs
1 grab
1 grab
24 hour composite
1 grab
24 hour
24 hour
1 grab
RBS
Cia r if
1.8
1.1
6.4 1 grab
R Board
Total
composite
composite
compos ite
composite
compos ite
composite
compos ite
24
24
24
hour
hour
hour
1.5
0.2
1.2
0.6
4.7
28.5
24 hour
24 hour
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VI. Results
PCB analyses received from the 18 survey mills are tabulated
in Appendix A. A total of 220 analyses were reported. A summary
of the analyses is presented in Table 4. The summary includes
205 of the 220 analyses received. The remaining 15 were conducted
with detectabilities above 1 ppb and, therefore, were not adequate
for our purpose.
As indicated in Table 4, 50 of the analyses were reported as
positive (not as less than) results. The remainder were reported
as less than the indicated value. The range of concentrations was
<0.01 to 18 ppb.
Because of the high percentage of tests reported as less than
the indicated value, computations of average values and frequency
distributions are hampered. The 1 ppb concentration was considered
a key level and hence a large number of analyses are reported as
less than 1.0 ppb. The most meaningful computation, therefore,
is the percentage of tests less than 1. ppb PCB. As shown in
Table 4, this value is 817 for the results from all mills. The
median concentration, 507 cumulative frequency, therefore, would
be less than 1.0 ppb.
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TABLE 4
SUNMARY OF ANALYSES 1
‘Number Number of Analyses with Values
of Positive Range < 1.0 ppb
Mill Analyses Analyses ( ppb) Number 7 of Total
A 18 3 <0.01- 0.38 18 100
B 13 2 <0.5-3. 12 92
C 12 6 <0.06- 5.0 9 75
D 12 5 <0.06- 2.6 11 92
E 10 10 0.7-5.7 1 10
F 14 6 <0.06-12.0 12 86
G 5 1 <1.0 -13.0 4 80
H 11 - 3 <1.0 -14.0 8 73
I 10 1 < 1.0 -10.5 9 90
J 10 1 < 0.1 - 1.0 9 90
K 13 0 < 0.1 - 0.3 13 100
L 11 3 < 0.01-18.0 10 91
M 12 4 < 0.05- 0.26 12 92
N 11 6 <0.1-4.5 5 45
0 12 2 < 1.0 - 0.89 12 100
P 13 4 < 1.0 - 1.5 10 77
Q 4 2 <1.0-2.7 3 75
R 14 0 < 0.01-<1.O 14 100
Total i2 205 59 < 0.01-18.0 167 81
Total 22 178 59 < 0.01-18.0 152 85
‘Table includes analyses with detectability of 1.0 ppb or lower.
Total number of all analyses is 220.
2 Total 1 includes all mills. Total 2 eliminates mills B, C, E, Q
whose results are for untreated wastewater.
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As mentioned above, 3 mills in the survey group had no treat-
ment and one mill inappropriately sampled raw waste. Table 4
indicates that elimination of the analyses from these mills results
in 85% of the remaining analyses being less than 1.0 ppb.
Figure 1 is a cumulative frequency distribution of the results
from all 18 mills. The section of the curve below I ppb repre-
sents the 167 test results shown in Table 4.
In order to characterize each milits average concentration,
median values were utilized. Median concentrations eliminated
the biasing of results by very high concentrations and more impor-
tantly reduced the error in using analyses reported as less than
the indicated value.
For the purpose of computing median concentration, analyses
reported as less than the indicated number were considered as
equal to the number. Therefore, median values represent a maximum
possible median. The true median will be lower. A summary of
the calculated median concentrations for each mill is presented in
Table 5. With the exception of Mill E, all mills had a median
concentration of less than 1 ppb. The average of all the Mill
median concentrations is 0.76 ppb.
Elimination of the data of the mills without treatment,
results in an average concentration of .61 ppb with all mills
below 1.0 ppb median concentration.
16
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FIG. I
PCB CONCENTRATION
CUMULATIVE FREQUENCY DISTRIBUTION
l o
15.0
io,o
0.
0.
8,0 Number of Analyses 205
Number <. I.Oppb 167
6.0
C) 81%
2: - I S I I I
I 2 5 tO 25 30 40 50 60 70 80 90 95 98 99
% Equal to or less Than Value Indicated
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TABLE 5
MEDIAN PCB CONCENTRATIONS OF INDIVIDUAL MILLS 1
Median Concentration Median Concentration
(ppb) Mills with Decta- (ppb) Mills with Decta-
Mill bility < 1.0 or lower bility <0.25 or lower
A 0.10 0.10
B 1.0
C 0.4 0.4
D 0.05 0.05
E 2.6 2.6
F 1.0
G 1.0
H 1.0
I 1.0
J 1.0
K 0.2 0.2
L 0.1 0.1
M 0.05 0.05
N 1.0
0 1.0
P 1.0
Q 1.0
R 0.1 0.1
Average i2 0.76 0.45
Average 22 0.61 0.10
1 Nedian is defined as the 5ODh cumulative frequency value, however,
analyses reported as less than indicated numbers were considered as
equal to the indicated number. Therefore the median values represent
-maximum possible medians. True medians values will be lower.
2 Average I includes all mills. Average 2 eliminates mills B, C, E, Q
whose results are for untreated wastewater.
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A number of mills reported all results with detectabilities
of <0.25 or lower. Calculations with these mills would reduce
the error in the computation of median and may result in a closer
approximation of a true average median concentration for paper
mills. As indicated in Table 5, these eight mills had an average
median concentration of 0.45 ppb which is significantly lower than
the 0.76 ppb concentration using all mills.
When the analyses of the two mills without treatment in this
group are eliminated, the average median concentration is sub-
stantially reduced to 0.10 ppb.
The concentration of PCBtS in wastewater effluents is signif-
icant from the considerations of dectability, background water
levels and the practicality of treatment. The mass of PCB’s dis-
charged, however, is significant for receiving water and overall
ecological effects. Table 6 presents computations for the daily
and yearly mass discharge of PCB’s. As shown, the total discharge
from all mills is 43 gram per day and 14 kilograms (30 Ibs) per
year. It should be noted that these values are calculated using
median rather than arithmetic average concentrations from each
mill and that the median values are approximations as explained
previously. Therefore these mass discharges represent maximum
possible values.
17
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TABLE 6
PCB MASS DISCHARGES
Median
Flow Cone. 1 PCB DISCHARGE
Mill ( MGD) ( ppb) gr/day gr/yr
A 3.9 0.1 1.5 102
B 0.4 1.0 1.5 450
C 2.2 0.4 3.3 990
D 0.4 0.05 0.07 21
E 0.5 2.6 4.9 1,715
F 1.1 1.0 4.2 1,470
C 0.4 1.0 1.5 450
H 0.5 1.0 1.9 665
I 0.7 1.0 2.6 780
J 0.9 1.0 3.4 1,020
K 1.8 0.2 1.4 420
L 1.1 0.1 0.4 120
M 6.4 0.05 1.2 420
N 1.5 1.0 5.6 1,960
0 0.2 1.0 0.7 245
P 1.2 1.0 4.5 1,575
Q 0.6 1.0 2.3 805
R 4.7 0.1 1.8 630
Total 28.5 42.8 13,838
(30 ibs/yr)
Average 1.6 0.4(note 2) 2.3 769
Range 0.4-6.4 0.07-5.6 21-1960
iMedian is defined as the 50% cumulative frequency value, however,
analysis reported as less than indicated numbers were considered as
equal to the indicated number. Therefore the median values represent
maximum possible medians. True medians values will be lower.
2 Weighted agerage
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PCB’s discharged per ton of recycled paper used are pre-
sented in Table 7. When all mills are grouped, the average value
is 190 mg/ton with a range of 1 to 2100. Eliminating the analyses
from mills without treatment results in an average of 219 mg/ton
and a range of 1 - 2100. The group of 8 mills with a dectability
of<.25 ppb or lower, has an average of 57 mg/ton. Eliminating
the analyses from the two mills without treatment results in an
average of 48 mg/ton and a range of 1 - 175 mg/ton. A weighted
average of all mills results in a unit weight of 34 mg of PCB’S
per ton of recycled paper.
The analyses used in this report are total PCB’s. Seven
survey mills, however, reported a portion of their analyses as
specific aroclors. Of these mills, aroclor 1242, which was the
aroclor used in carbonless copy paper, was found in the effluent
of 4 mills. Aroclors 1248, 1254 and 1221 were also found in some
mill’s effluent.
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TABLE 7
PCB’s DISCHARGED PER TON
OF RECYCLED PAPER USED
Mills A B C D E F C H I
(mg/ton) 45 150 122 1 46 2100 375 11 27
Mills J K L M N 0 P Q R
(mg/ton) 33 175 36 14 48 5 187 25 15
Number Range Avg.
Group of Mills ( mg/ton) ( mg/ton )
1) All Mills 18 1 - 2100 190
2) Mills with Treatment 14 1 - 2100 219
3) Mill with Dectability 8 1 - 175 57
of<.25 or lower
4) Mills with Dectability 6 1 - 175 48
of<.25 or lower and
with Treatment
5) Weighted Average of 18 1 - 2100 34
All Mills
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VII. Discussion and Conclusions
A cumulative frequency distribution of results from all
millsshows about 85°h of the analyses are 1 ppb or less. Above
1 ppb the distribution increases rapidly to a high of 18 ppb.
Inspection of these high values indicates that with the exception
of Mills E and N, they are distributed somewhat uniformly among
the mills. Their occurrence is not readily understood considering
the large number of values below 1 ppb. They may be a result of indi-
vidual highly contaminated purchases of paper or possibly a result f
testing errors. Because they are relatively infrequent and
distributed among most of the mills we have not considered them
highly significant. A PCB concentration of less than 1 ppb is
considered an accurate characterization of all mill’s average
discharge, with the exception of Mill E.
Mill E reported all of its analyses as posit5ve numbers.
The median concentration was 2.6ppb and the arithmetic average was
2.8 ppb. This concentration is significantly greater than any of
the other mills. As indicated previously, Mill E does not have
treatment and has little if any internal recovery of water and
fiber. The absence of treatment may be the reason for the
relatively high PCB levels. Treatment facilities for Mill E are
presently under construction and will be completed this spring.
Additional testing at that time would be appropriate.
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Analyses from mills B, C and Q are representative of no
treatment, however, they were not as high as the concentration
from Mill E.
As mentioned previously, the analysis of mills with decta-
bilities of <.25 ppb or lower results in a significantly lower
average concentration when compared to all mills If we consider
these mills to be representative of mills using recycled paper.
we can conclude that an average concentration of PCB’s in recycled
paper wastewater is less than 0.45 ppb and perhaps as low as 0.1
ppb when the effect of treatment is considered.
Mill intake water may potentially contain background levels
of PCB’s. As indicated previously the data presented in this
report is the gross discharge and could reflect the presence of
PCB’s in the intake water. The location with greatest potential
for a significant background level of PCB’s is the section of the
Hudson River from Hudson Falls to Troy. Of the PCB concentrations
measured by New York State in this section of the river during the
middle of the study period in 1977 and 1978, approximately 247 of
the analyses were reported as
-------
Conclusions from this survey are summarized as follows:
1. The average PCB concentration of every mill with primary
or secondary treatment is less than 1 ppb.
2. The weighted average of discharges from all mills, using
individual median concentrations is 0.4 ppb or less.
3. Data from the group of mills using analytical techniques
with increased minimum detectability indicates that the
average concentration of PCB’s in recycled paper mill waste-
water may be as low as 0.1 ppb for mills with treatment.
4. The absence of treatment at one mill (E) may be respon-
sible for its relatively high average PCB concentration of
2.6 ppb.
5. The NYS Department of Environmental Conservation had
previously concluded that the practical limit of carbon
treatment for PCB’s was 1 ppb. Based on the survey results
PCB wastewater treatment is not practical for mills with
primary or secondary treatment.
6. The total discharge of PCB’s from all survey mills is a
maximum of 30 lbs/year. The total discharge from all recycle
paper mills in New York State is estimated at a maximum of
45 lbs/year.
21
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7. The NYS Department of Environmental Conservation does
not have a water quality standard for PCB’s; however a
standard of 1 part per trillion has been proposed (ref. 6).
This receiving water standard if adopted, may necessitate a
reevaluation of the need for PCB monitoring and discharge
limitations.
8. The Environmental Protection Agency may propose PCB
effluent limitations for the paper industry. If standards
are adopted, they will have to be dealt with by recycled
paper mills nationally.
22
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REFERENC ES
1) New York State Department of Environmental Conservation,
Summary of Hudson River PCB Study Results , Technical Paper
#51, April, 1978.
2) New York State Department of Environmental Conservation,
Hudson River PCB Study Descripti-on and Detailed Work Plan ,
Bureau of Water Research, July, 1977.
3) Environmental Protection Agency, PCB’s Involvement in the
Pulp and Paper Industry , EPA Contract No. 68-01-3259, Office
of Toxic Substances, Washington, D.C., February 25, 1977.
4) Curry, Nolan A., “PCB Movement in the Environment,” presented
at the ninth mid-Atlantic Industrial Waste Conference,
Bucknell University, Lewisburg, Pennsylvania, August 8, 9,
1977.
5) lannazzi, F.D. and Firth, L.M., “Wastepaper Recovery,
Comparison of U.S. Rates with those of Selected Foreign
Countries,” TAPPI , Volume 61, No. 6, June, 1978.
6) New York State Department of Environmental Conservation,
“Proposed Classifications and Standards of Quality and
Purity,” Title 6, Official Compilation of Codes, Rules and
Regulations, Parts 700, 701, 702, and 704 , November, 1978.
23
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APPENDIX A
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APPENDIX A
Mill
PCB CONCENTRATIONS, pb)
INDIVIDUAL ANALYSES
B
Q P. ii
Mill
K
L
<0.2
3.6
<0.06
<0.06
2.0
12.0
13.0
3.0
<1.0
<0.1
<1.0
1.5
2.6
2.2
0.0
<1.0
<1.0
< 1.0
0.38
<1.0
0.7
<0.06
3.4
<1.0
<1.0
<1.0
<0.1
<0.1
<1.0
<0.06
<0.06
5.7
<1.0
<1.0
14.0
<20.0
0.1
<1.0
<0.06
<0.06
3.2
1.0
<1.0
2.0
<20.0
<0.3
<1.0
<0.06
0.05
3.0
2.0
<2.0
<1.0
<0.01
<1.0
0.4
<0.06
4.6
<1.0
<3.0
10.5
<0.01
0.2
<0.06
0.2
0.7
<1.0
<1.0
<1.0
<0.1
<20.0
5.0
0.1
1.8
1.0
<1.0
<1.0
<0.01
<20.0
3.0
<0.06
1.4
1.0
<1.0
<1.0
<.0.01
<1.0
<0.06
<0.06
1.0
<1.0
<1.0
0.13
<0.5
0.43
0.19
<1.0
<1.0
<1.0
<0.01
<1.0
<1.0
<1.0
<0.25
<1.0
<1.0
<0.25
<1.0
<0.25
<0.25
<0.25
<1.0
<0.1
<0.1
<0.05
1.1
<1.0
1.5
1.0
<0.1
<.0.1
<0.25
<0.05
0.18
4.2
<1.0
0.5
2.7
<1.0
<20.0
<0.25
18.0
<0.05
2.0
0.56
<1.0
<1.0
<0.05
<20.0
<0.25
0.1
<1.0
3.4
0.89
<1.0
<1.0
<0.1
<0.5
<0.25
<.0.1
0.26
4.5
<1.0
<1.0
<2.0
<0.1
<1.0
<0.3
<0.1
0.14
<1.0
<1.0
<1.0
<0.1
<1.0
<0.3
<0.1
<0.05
2.2
<1.0
<20.0
<0.1
<1.0
<0.2
<0.01
<0.05
<20.0
<20.0
<1.0
<0.1
<1.0
<0.1
<0.05
<0.05<20.0
<20.0
<1.0
<0.01
<1.0
<0.1
0.59
0.24
<0.5
<1.0
1.0
<0.01
1.0
<0.1
<0.25
<0.05
<1.0
<1.0
1.0
<0.05
<1.0
<0.1
<0.2
<0.05
<1.0
<0.1
<1.0
< 1.0
<.1.0
<1.0
< 1.0
< 1.0
< 1.0
<0.25
<0.25
<0.08
N
N
0
P
A-i.
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