United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-087 July 1981
Project Summary
Origin and Chemical
Composition of
Androscoggin River Foam
Bruce K. Wallin and Brian T. Bisson
A sampling and analysis program on
the Androscoggin River and at Inter-
national Paper Company's Andros-
coggin Mill in Jay, Maine was under-
taken to determine the origin and
chemical composition of Androscoggin
River foam. The report documents an
extremely complex chemical compo-
sition of river foam. A mass balance of
downstream river foam accounts for
approximately 50 percent of both
organic and inorganic matter. River
samples downstream of both indus-
trial and municipal point sources
foamed, but locations upstream of any
point sources foamed as well. It could
not be determined from the data
generated in this study whether any of
the industrial or municipal point sources
acted alone, or in combination with
one another and/or ambient conditions
to cause the foaming condition.
The Project Report was submitted in
fulfillment of Contract No. 68-03-
2605, Work Directives Nos. 2, Part II,
and 7 by the E.C. Jordan Co., under
the sponsorship of the U.S. Environ-
mental Protection Agency. The report
covers the period May 4, 1978 to
September 10, 1980, and work was
completed as of June 25, 1980.
This Project {Summary was devel-
oped by EPA's Industrial Environmen-
tal Research Laboratory, Cincinnati,
OH, to announce key findings of the
research project that is fully docu-
mented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
Background
For some time the rivers of northern
New England have been known to be
prone to foaming. Foaming on rivers in
other areas of the country is less well
documented, though there are examples
of estuarine foam problems such as
Peridido Bay in Florida.
Foam is defined as a dispersion of gas
bubbles in a liquid. In order for foam to
occur, a critical concentration of a
surface active substance must be pres-
ent. Surface active substances or sur-
factants are described as molecules
having both hydrophilic and hydrophobic
groups. The hydrophilic group has a
tendency to unite with water, and the
hydrophobic group is not capable of
uniting with water. This property causes
surfactants to concentrate at the gas/
liquid interface, thus satisfying both
portions of the molecules, and under
proper conditions foam is formed.
For many years the State of Maine
Department of Environmental Protection
(DEP) has received public comments
voicing concern about accumulations of
foam on the Androscoggin River. Gen-
erally, the public has perceived foam as
an aesthetic problem introduced to the
river by the several pulp, paper, and
paperboard mills located on the river.
However, sources of surfactants include
publicly owned treatment works (POTW)
and nonpoint sources, as well as the
pulp, paper, and paperboard industry.
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Foaming has been an historical prob-
lem within pulp, paper, and paperboard
mills. Resin and fatty acids were identi-
fied years ago in their effluent. Resin
and fatty acids are structurally surface
active. The concentration it takes to
make them surface active (and cause
foam) is variable with different com-
pounds and classes of compounds, but
the fact remains that resin and fatty
acids are surface active.
Publicly owned treatment works
(POTW) may also be a source of surfac-
tants. If a POTW treats purely municipal
wastes (no industrial contributions),
there are two general categories of
surfactant contributors - manmade de-
tergents, the sulfonates and neutrals
and surfactants that result from bio-
logical treatment itself. The metabolic
breakdown of the biological treatment
process results in the release of fatty
acids, and human fecal matter contains
fatty acids that are the result of incom-
plete absorption of the human digestive
tract.
Nonpoint sources may also contribute
to foaming potential in the river. Agri-
cultural lands may contribute fatty acids
from fecal matter on pasture lands.
Rural forest lands may also contribute
fatty acids from decaying biological
materials. Protein, which is a product of
any biological process, is somewhat
surface active, but it would not be
expected to be found naturally in any
appreciable quantities in a stream or
river.
The Androscoggin River headwaters
are in northwest Maine, where it flows
eastward from Umbagog Lake through
Errol and Berlin, New Hampshire, then
back into Maine through the towns of
Rumford, Jay, Lewiston, and Brunswick,
before discharging to the Atlantic Ocean
at Merrymeeting Bay. Three bleached
kraft mills and one groundwood mill are
located along the Androscoggin's 200-
mile length: Brown Company in Berlin,
New Hampshire; Boise Cascade Corpo-
ration in Rumford, Maine; International
Paper Company in Jay, Maine; and
Pejepscot Paper Company in Topsham,
Maine. Each of the three bleached kraft
mills produces pulp at a rate of approxi-
mately 1,000 tons per day (tpd), the
groundwood mill at a rate of 150 tons
per day, and each is served by a sec-
ondary wastewater treatment facility.
Study Objectives
Several organizations worked together
on the evaluation of Androscoggin River
foam. An explanation of how the project
unfolded puts the roles of the participants
in perspective. First, the public voiced
concerns to the State of Maine DEP over
foam accumulations on the Androscoggin
River. DEP requested assistance from
the EPA when the problem was found to
be beyond the state's funding and
technological capabilities. Since the
E.G. Jordan Co. was under contract with
EPA, it was retained to study the prob-
lem. The DEP was to provide support by
performing an ambient sampling and
analysis program on the Androscoggin
River. Battelle Laboratories was con-
tracted by EPA to assist in the study by
elucidation of the Androscoggin River
foam. It was felt that the ultimate
success of the project depended on a
detailed chemical breakdown of the
most complex foam, the terminal foam.
Daniel W. Armstrong, Ph.D., was sub-
contracted by E.C. Jordan Co. after
some of Battelle's early analyses had
begun to uncover the extreme complexity
of the foam chemistry. Dr. Amrstrong is
a chemist who specializes in surface
active material and, therefore, his role
in the project was to help with some of
the problems of surfactant chemistry.
At the outset of this study, the ob-
jectives were defined as follows:
1. Definition of the chemical constit-
uents causing both naturally oc-
curring foams and foams associated
with pulp, paper, and paperboard
mill discharges;
2. Development, through laboratory
and pilot plant studies, of foam
removal and treatment technolo-
gies capable of yielding non-foam
generating mill effluents; and
3. Assessment of the effectiveness
of the developed removal and
treatment technologies for mini-
mizing and/or eliminating surfac-
tants in mill's final effluent.
Due to the lack of available literature
and in-place technology to solve the
foam problem, these objectives outlined
an ambitious program. During the initial
phases of this study, the objectives were
redefined as follows:
1. Determine the chemical composi-
tion of Androscoggin River foam;
2. Determine the origin of the foam
constituents; and
3. Recommend further studies to
reduce or eliminate the foaming
condition.
A four-phase sampling and analysis
program was undertaken to study the
river foaming problem.
1. Phase I: The purpose of Phase
was to determine if resin and fatt
acids were present in a pulp
paper, and paperboard mill's ef
fluent. The International Pape
Company's Androscoggin Mill ii
Jay, Maine was selected as thi
pulp and paper mill for sampling
Analysis was performed by ga
chromatography/mass spectrom
etry (GC/MS) utilizing analytica
procedures developed by the EPA
Between Phases I and II a com
parison of gas chromatograph
(GC) and GC/MS analytical result
was made. It was found that G(
analyses provided accurate, reli
able results for a much lower cos
than GC/MS analysis could pro
vide. This was important to th<
study because had GC/MS beer
required, the higher cost wouk
have severely limited the numbe
of analyses that could be performed
This conclusion was borne out by;
GC versus GC/MS comparison ir
another EPA study.
2. Phase II: This phase began a proces
which was intended to ultimatel
lead to meeting study objective :
by developing "treatment technol
ogies capable of yielding non
foam mill effluents." Battelle am
DEP results had not demonstratei
the pulp, paper, and paperboan
industry was solely responsible fo
the foaming condition on the And
roscoggin River. However, it wa
known that pulp, paper, and paper
board mill effluents foamed, so thi
first step was to sample in a pulp
paper, and paperboard mill tofini
the sources of the surfactants
This would help by determinini
what to treat and where to treat ii
the rationale being that it would b<
more economical to treat a singli
process stream than to treat all o
the process streams together
Under Phase II, sampling am
analysis was continued at Inter
national Paper Company's And
roscoggin Mill by analyzing 24
hour composite samples from si:
locations.
3. Phase III: This phase continued thi
work of Phase II studying threi
sample locations at Internationa
Paper Corporation's Androscoggii
Mill in more detail. The object wa
to observe the day to day variabilit
in the mill processes and to chec
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the affect of various parameters
on foaming tendency of water
samples collected in the mill.
Parameters were varied that were
known to effect foaming tendency,
including pH, addition of water
softener (hexametaphosphate),
addition of sodium, and addition of
surfactant (Joy dishwashing de-
tergent). The pH has a dramatic
effect on the foaming tendency of
surfactants. Water softeners have
a higher affinity for metallic ions
than surfactants. If left in solution,
metallic ions form a complex with
certain surfactants rendering them
insoluble. Therefore, the addition
of water softeners allows any sur-
factants that are present to more
readily create foam. Sodium in-
creases the ionic strength of a
solution. Therefore, sodium lowers
the critical concentration of a
surfactant required to create foam.
When surfactants are present in
solution below their critical con-
centration (for creating foam),
foam will not form. However, foam
may be created by adding more
surfactant, such as Joy dishwash-
ing detergent. The foam then con-
centrates surfactants from both
the Joy and the solution's original
surfactants.
During Phase II, the bleach plant
effluent samples unexpectedly
foamed. Two groups of surfactants
were found to be responsible:
methylene blue active substances
(MBAS) and polyaromatic pulping
products. Therefore, during Phase
III, analyses were performed for
these surfactants as well as for
resin and fatty acids.
4. Phase IV: It was anticipated that
this phase would entail performing
a pilot scale foam generation sys-
tem study. However, the parallel
ongoing analysis by Battelle of the
terminal river foam had not dem-
onstrated that the pulp, paper, and
paperboard industry was solely
responsible for the river foam.
Therefore, it was inappropriate to
do a pilot plant study at Interna-
tional Paper Company's Andros-
coggin Mill. Instead, the Phase III
program was continued on a larger
scale by including the sampling
and analysis of the major industrial
and municipal point sources on
the Androscoggin River in Maine.
Foaming is a complex phenomenon.
Its composition may include anions,
cations, resin acids, fatty acids, and
numerous other elements. All of the
compounds that form foam on the
Androscoggin River have not been
identified, nor is there an EPA-approved
test to determine the foaming potential
of wastewater. However, the redefined
objectives of this study have been
partially met, and we are much closer to
an understanding of foam, and to devel-
oping an eventual solution to the prob-
lem.
The general accomplishments of this
study are as follows. A literature review
entitled "Foam and Its Elimination" was
completed in April 1979, and is ap-
pended. In addition, Battelle Columbus
Laboratories of Ohio analyzed collapsed
river foam samples in orderto chemically
characterize the materials present. A
large percentage of the materials can be
accounted for by summation of individual
analyses, as shown in Battelle's report,
also appended. However, of these mate-
rials that are extractable, only a few
percent are accounted for by summation
of the individual compounds identified
by gas chromatography/mass spectrom-
etry (GC/MS). It is probable that a large
portion of the extracted material de-
composed in the GC injector even after
derivatization.
The State of Maine Department of
Environmental Protection (DEP) also
performed a study of the sources and
causes of foam along the entire length
of the Androscoggin River. Generally,
organic concentrations were found to
be low or undetectable in ambient
waters, but the data are insufficient to
produce obvious or easily substantiated
conclusions. The DEP report is also
appended.
Conclusions and
Recommendations
The data presented in this report
clearly documents the complexity of the
foaming problem on the Androscoggin
River. An extremely complex chemical
composition of riverine as well as up-
stream pristine foam, ambient factors,
and contribution by various point sources
all have yet to be fully explored.
At this point in the study of And-
roscoggin River foam, it has not been
determined whether any of the industrial
or municipal point sources acting alone,
or in combination with one another
and/or ambient conditions, is respon-
sible for the foaming condition on the
river.
Conclusions
Detailed conclusions may be found in
Sections 3 and 4 of the Project Report.
The following is a summary of conclu-
sions:
The Chemical Composition of Foam:
River foam downstream of Topsham
was found to contain a plethora of
organic matter, including neutrals,
weak acids, polyaromatic pulping prod-
ucts, as well as inorganics. "Pristine"
foam (foam upstream of all points
sources) lacked certain of the above
components, such as resin acids and
chloroguaiacols, but was also found to
be extremely complex. An attempt to
mass balance a downstream sample of
foam accounts for approximately 50
percent of both organic and inorganic
matter.
Origin of Foam Constituents: The
Rumford-Mexico and Lewiston-Auburn
municipal treatment plant effluents did
not produce collectible quantities of
foam when subjected to pneumatic
treatment. Most of the pulp, paper, and
paperboard mill treatment plant effluent
samples produced foam when subjected
to pneumatic treatment. The Lisbon
municipal treatment plant effluent (which
contained paperboard mill treated waste-
water) also foamed. Samples foamed for
up to one-half hour and then stopped.
Collectible foam was found to be en-
riched in methylene blue active sub-
stances (MBAS), while polyaromatic
pulping products were not concentrated
in the foam.
Factors Affecting Foam Formation:
International Paper's Androscoggin Mill
was sampled at the brownstock washer
effluent (BS) and the bleach plant acid
sewer (BP), as well as at the secondary
clarifier effluent (FE). The BS effluent
contained resin and fatty acids, methyl-
ene blue active substances (MBAS), and
polyaromatic pulping products, while
the BP effluent contained only MBAS
and polyaromatic pulping products.
Factors known to affect foam formation,
including pH, sodium, hexametaphos-
phate, and addition of surfactants were
analyzed for their effect on BS, BP, and
FE samples as'shown in Table 1.
The table shows that several param-
eters increase the foaming tendency of
the BS and FE effluents. As expected,
only the addition of surfactant increased
the foaming tendency of BP. The adjust-
ment of pH or the addition of chelating
agents should not enhance the BP
effluent foaming tendency because
strongly acidic or neutral surfactants
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are not affected by these parameters.
The same parameters that enhanced
foaming tendency in the BS effluent
also increased removals of MBAS, resin
and fatty acids by foaming. In the FE the
data shows removals of polyaromatic
pulping products by addition of a surfac-
tant.
Recommendations
In order to solve the Androscoggin
River foaming problem, the sources and
chemistry of the foam must be identified.
Also, a better method of testing samples
for foaming tendency would help in
determining the relative contributions.
A better foaming tendency test alone,
however, may not solve the problem
economically. Mechanical defoaming
equipment has been developed that is
effective, but economically prohibitive.
Therefore, another reason for studying
foam chemistry is to determine if there
are major foam constituents that could
be selectively removed at a reduced
cost.
The following seven points suggest
further areas of study of the foaming
problem on the Androscoggin River:
1. Elucidation of the chemical com-
position of foam. The Battelle and
DEP results indicate that a con-
siderable amount of material in
Androscoggin River foam remains
to be characterized. Low recoveries
of organics, both neutral and acidic,
in the extractable fraction suggest
that HPLC/MS should be employed.
The aqueous phase, with its ap-
parently substantial level of un-
identified MBAS should also be
studied further using more sophis-
ticated techniques such as HPLC/
MS. Additional inquiry into the
variability of chemical composition
of foam at various points on the
river should lead to a clearer
understanding of the factors con-
tributing to the foaming condition.
2. The results from chemical analysis
of various point sources, ambient
foams, and pristine foams should
be correlated to determine the
origin of contributing surfactants.
3. Determination of the chemical
composition of MBAS in various
point sources: All samples analyzed
contained MBAS which can be
strong surfactants. It should also
be determined whether the MBAS
are of domestic or industrial origin.
The action of sulfide ion to accel-
erate dissolution of wood to re-
lease cellulose fibers has been
known for many years. The accel-
eration is chemically described as
a reaction between the sulfide ion
and lignins. Subsequent to the
direct reaction of sulfide in the
digester, oxidative reactions can
lead to the production of polyaro-
matic pulping products. The com-
mercial preparation of lignosulfates
gave a weak MBAS reaction. It is
possible that different forms of
organic sulfates and sulfonate
surfactants could be produced in
the pulping process that would be
positive to the MBAS test.
4. Testing of the foamability of pure
solutions containing various levels
Table 1. Data Summary of Factors Affecting Foam Formation at International
Paper Corporation, Jay. Maine
Increased Removals by Foaming of
Sample
Location
BS
BP
FE
Treatment
that Enhanced
Foaming Tendency"
1.2,3.4
4
1,2.4*
MBAS"
1.2,3
3
d
Resin and Fatty Acids
1.2,3.4
Limited data
a
Polyaromatic
Pulping
Products
No
No
4
'Treatment effects of the following four conditions were examined:
1 = adjusting pH
2 = addition of sodium sulfate
3 - addition of sodium hexometaphosphate
4 = addition of a surfactant (Joy dishwashing detergent)
"Because the surfactant addition, treatment 4, resulted in high levels of MBAS
addition, removals of relatively low levels of MBAS in the original solution could
not be assessed.
"The FE did not foam without treatment.
^Original levels were too low to determine effects of treatment.
and combinations of the com-
pounds present in river foam should
be performed.
5. Development of improved methods
for analysis of surfactants: The
present methods for the levels of
surfactants of the type found in
river foam require improvement.
In particular, the MBAS, polyaro-
matic pulping products, and neu-
tral surfactants will require high
resolution HPLC coupled with MS
for resolution and identification.
6. The effect of ambient conditions,
i.e. flows, temperature, humidity,
and wind, on the persistence of
river foam: DEP has shown a pos-
sible correlation to river flow and
foaming, but substantiating data
has not been collected.
7. Further work should be performed
on the following: foam composition
as it relates to the possible con-
centration of toxic substances
from the river and its sediments;
the resolution, transport and dep-
osition of priority pollutants and
other substances by surfactant
aggregates; stabilization or desta-
bilization of toxic pollutants and
other substances by surfactant
aggregates; and the synergistic
effect of toxicity of various priority
pollutants and other substances
when in the presence of surfac-
tants.
8. A method for assessing foaming
tendency in ambient conditions
should be developed. Two tech-
niques were used in this study: a
blender technique as outlined in
ASTM D3519-76 and'a pneumatic
technique developed by B.C. Re-
search. Both techniques are stan-
dard techniques that have been
used by others. However, both
failed to produce foam on some
samples which would have been
expected to foam because of the
observed foaming condition in the
river during sampling. Also, both
techniques fail to detect trace
amounts of surfactants. Therefore,
a more sensitive technique should
be developed.
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Bruce K. Wallin and Brian T. Bisson are with E. C. Jordan Co., Portland, ME
04112.
Michael R. Strutz and Donald L. Wilson are the EPA Project Officers (see
below).
The complete report, entitled "Origin and Chemical Composition of Andro-
scoggin River Foam," (Order No. PB 81-208 167; Cost: $18.50, subject to
change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at:
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
t US GOVERNMENT PRINTING OFFICE. 1981 -757-012/7231
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