EPA 670/2-73-078
September 1973
Environmental Protection Technology Series
of
Material Spills
ing Ma nsfer Media
of Research and Development
imental Protection Agency
20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1, Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
(|. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series* This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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TREATMENT OF HAZARDOUS MATERIAL SPILLS
WITH FLOATING MASS TRANSFER MEDIA
By
Basil W. Mercer
Alan J. Shuckrow
Gaynor W. Dawson
Project 15090 HGQ
Contract 68-01-0124
Project Officer
Ira Wilder
Environmental Protection Agency
Edison Water Quality Research Laboratory, NERC
Edison, New Jersey 08817
Prepared for
OFFICE OF RESEARCH AND MONITORING
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
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EPA Review Notice
This report has been reviewed by the EPA and approved
for publication. Approval does not signify that the
contents necessarily reflect the views and policies of
the Environmental Protection Agency, nor does mention
of trade names or commercial products constitute
endorsement or recommendation for use.
11
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ABSTRACT
An approach for the in situ treatment of spills of soluble
hazardous polluting substances was developed and demon-
strated on a field scale for a static body of water.
Laboratory-scale experimentation showed that floating
sorbents and ion exchange resins could be highly effective
removal agents when applied as small particles beneath
the surface of contaminated waters.
A lightweight commercial activated carbon was found to be
particularly effective for removing organic substances such
as phenol, aromatic hydrocarbons, and organophosphorus
insecticides from water. The activated carbon can be
pulverized to a small mesh size (100 x 325) which floats
slowly to the surface of the water. The small mesh size
enhances both the contact time and the sorption kinetics.
Floating ion exchange resins were also prepared for use
on spills of acid (e.g., sulfuric and hydrochloric), alkalis
(e.g., caustic soda) and toxic salts (e.g., sodium cyanide).
Hollow glass microspheres are incorporated in the resin
granules for buoyancy.
Delivery systems which show promise for field use include:
(1) ice cakes containing floating media and gravel ballast;
(2) clay cylinders; and (3) weighted plastic bottles.
Field demonstrations were conducted using carbon contained
in weighted plastic gallon bottle.s. The carbon proved
highly effective in removing an organophosphorus pesticide
spilled in a large basin, and was easily collected through
use of an oil containment boom. Ice encapsulated floating
anion exchange resin beads were similarly employed to
neutralize a spill of sulfuric acid.
This report was submitted in fulfillment of Project Number
15090 HGQ, Contract 68-01-0124 under sponsorship of the
Office of Research and Monitoring, Environmental Protection
Agency.
10.1
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CONTENTS
Section Page
I Conclusions 1
II Recommendations 5
III Introduction 7
IV The Concept 13
V Laboratory Studies 25
VI Field Demonstrations 61
VII Application 83
VIII Acknowledgments 87
IX References 89
X Appendix 91
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FIGURES
Page
1 Spill of Hazardous Material 18
2 Officials Are Notified. Response Team 19
Is Set Into Action
3 Appropriate Media Type Is Selected and 20
Loaded Onto Delivery Plane
4 Individual Media Packages Are Air Dropped 21
Into Contaminant Plume
5 Packages Sink and Begin to Decompose. Media 22
Floats to Surface Removing Contaminant
6 Standard Oil Skimmers Are Used to Retrieve 23
Media
7 Sorption Isotherm for Phenol and Nuchar C-190 28
8 Comparison of C-190 with WA for Removal of 30
Phenol
9 Titration Curves for a Strongly Acidic Cation 36
Exchange Resin and a Weakly Acidic Cation
Exchange Resin
10 Polymerized Acrylic Acid Crosslinked with 39
Divinylbenzene
11 Polymerized Acrylic Acid Crosslinked with 41
Ethylene Glycol Dimethacrylate
12 Titration Curve for Floating Acrylic Ion 42
Exchange Resin
13 Example of Structure of an Epoxypolyamine 43
Anion Exchange Resin
14 Titration Curve for Floating Epoxypolyamine 45
Anion Exchange Resin
15 Titration Curve for Diamond Shamrock Weak Base 47
Epoxypolyamine Resin
VI
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FIGURES
(Continued)
Page
16 Acrylic Floating Cationic Exchange Beads 49
17 Epoxypolyamine Floating Anionic Exchange Beads 50
18 Schematic of Carbon Filled Plastic Bottle 54
19 Photograph of Clay Container 58
20 Location of Facilities for Diazinon Spill 62
21 Aerial Photograph of Diazinon Spill 64
22 Closeup of Diazinon Spill in Sampling Grid 65
23 Results of Phosphate Analysis on Pretreatment 66
and Posttreatment Samples
24 Additional Results of Phosphate Analysis on 67
Posttreatment Samples
25 Results of TOG Analysis on Pretreatment and 69
Posttreatment Samples
26 Additional Results of TOC Analysis on Post- 70
treatment Samples
27 Photograph of Helicopter with Sling 72
28 Photograph of Air Drop Into Spill Area 73
29 Placement of the Collection Pipe and Boom 75
30 Typical "Media Cake" Employed in Basin 78
Demonstration
31 Photograph of a Resin Ice Cake 79
32 Sampling Floating Resin after Treatment 81
V1JL
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TABLES
No
1 Surface Areas and Iodine Numbers of Several
Commercial Grade Carbons4'5 25
2 Approximate Floatability of Various Mesh
Sizes of Nuchar C-190 26
3 Rise Time for Nuchar C-190 in Four Feet
of Water 27
4 Removal Effectiveness for Nuchar C-190 for
Various Organic Materials 29
5 Removal Effectiveness of Nuchar C-190 for
Organophosphorus Pesticides 31
6 Percentage Removal of Phenol, Malathion, and
Diazinon at Various Depths in the Treatment
Column After Flotation of the Carbon 32
7 Ballast and Package Size Requirements for
Selected Media 51
8 Product Evaluation of Soluble Films 56
9 Composition of Emulsifiable Diazinon Solution 61
Vlll
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SECTION I
CONCLUSIONS
The removal of selected hazardous materials from water with
floating mass transfer media was successfully demonstrated
in laboratory and field tests, using floating activated
carbon for organic removal and floating ion exchange resins
for^lectrolyte removal. The following is a list of con-
clusTons based on these studies.
GENERAL
The technical feasibility of the concept of
subsurface injection of floating mass transfer
media for treatment of hazardous polluting
substances has been established through field
demonstration.
This concept shows great promise as a spill
response technique.
Surface collection of spent floating media in
a static body of water can be accomplished with
existing oil spill cleanup equipment.
The quantity of floating media required for a
desired level of removal of spilled hazardous
material will vary with the type and concen-
tration of material being removed.
The effectiveness of spill treatment decreases
as the spilled hazardous material becomes more
dilute. Thus, rapid response to a spill sit-
uation is of paramount importance. For example,
10 grams of activated carbon will remove 97 per-
cent of the phenol from a one gram per liter
solution of this material. Sixteen grams of
carbon would be required to obtain the same
level of removal if the one gram of phenol were
dissolved in 10 liters of water.
The use of weighted packages of floating media for
treating hazardous material spills represents the
most immediate possible response to these situations
in remote areas. Where spill frequency is high
(e.g., busy harbors) bulk application with infusion
pumps is thought to be the preferred method of
application.
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FLOATING ACTIVATED CARBON
, Two commercially available activated carbons,
Nuchar C-190 and Nuchar WA, can be applied at
the bottom of a water column to effectively
sorb organic matter as they float to the surface.
, Nuchar C-190 is the carbon of choice based upon
superior sorptive ability and superior floatability,
• Fine carbon particles in the 100 x 325 mesh range
are capable of approaching equilibrium sorption
by floating once through the water column.
• Both dry and pre-wetted carbons are equally
effective in removing organics from aqueous
solution.
• Nuchar C-190 is highly effective in sorbing phenol,
toluene, benzene, styrene, Diazinon, Malathion,
and, to a lesser extent, acrylonitrile.
• A single pass of Nuchar C-190 through a water
column removes approximately 80 percent of the
Diazinon spilled in a ten million gallon water
basin.
• The granular grades of Nuchar C-190 used in this
study are no longer commercially available. A
powdered grade, Nuchar C-190-Nr is available but
this material was not evaluated.
, An impact method of crushing the carbon produced
a product superior to that obtained by ball
milling.
• The floating activated carbon can easily be herded
with the aid of a plastic containment boom and
recovered from the treated water by pumping as a
slurry from the surface of the water through a
diaphragm pump.
FLOATING ION EXCHANGE RESINS
• The use of weakly acidic and weakly basic ion
exchange resins for treating spills of acidic or
basic electrolytes has two major advantages over
the use of neutralizing chemicals. These are:
(1) application of excess resin will not cause pH
extremes and (2) the resins are effective for both
neutralization and removal of dissolved matter.
The principal disadvantage is the high cost of
the resin (approximately $290 per cu. ft.)
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Floating ion exchange resins were synthesized by
incorporating hollow glass microspheres in the
resin matrix to provide the desired buoyancy.
Bulk polymerization and suspension polymerization
techniques were found to be successful for prep-
aration of a floating weakly acidic carboxylic resin
and a floating weakly basic epoxypolyamine resin,
respectively.
Suspension polymerization is the preferred pro-
duction technique since it should be far more
economical than bulk polymerization techniques.
Both cationic and anionic resins can be produced
by suspension polymerization; however, only the
preparation of floating anion resin was
successfully demonstrated by this method.
The feasibility of commercial production of
floating resins has been demonstrated by the
production of several hundred pounds of floating
epoxypolyamine anionic resin.
A low removal level of sulfuric acid was observed
in the field demonstration, but is not considered
representative of the potential of floating ion
exchange resins for treating spills of electro-
lytes. Rather, the low removal efficiency was the
result of poor contact between the resin and the
acid due to a bottom layering effect of the acid.
PACKAGING AND DELIVERY
Ballast requirements to sink the floating media vary
from 0.2 pounds of ballast per pound of wet media
to 12 pounds of ballast per pound of dry media.
The inclusion of water or ice in the interstices
of the media significantly reduces the ballast
requirement.
Routine packaging techniques which show promise
for field use include (1) ice cakes containing
floating media and gravel ballast; (2) clay
containers; and (3) weighted plastic bottles.
Based on the work to date, the ice cake approach
appears to be preferable because of lower ballast
requirements and superior dispersion characteristics
near the bottom of the water column.
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Ice cake packaging is the only identified technique
with no potential for water quality impairment.
This technique involves a large temperature drop
near the ice cake but the average temperature
change in the treatment area will be only 1 to 2 °F.
The feasibility of packaging carbon and ballast
in plastic containers and resin and ballast in
ice cakes has been demonstrated in field tests.
The feasibility of air drops of floating carbon
packaged in plastic containers has been demonstrated
on a large scale.
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SECTION II
RECOMMENDATIONS
As a result of the success of the laboratory
studies and field demonstrations described in
this report, efforts should proceed to further
develop and implement the floating media concept
for treatment of spills of hazardous polluting
substances.
A slurry injection system should be developed
to allow routine use of floating sorbents in
ports and areas with a history of high spill
frequencies.
Packaging techniques for air transport and delivery
of floating media which were investigated in
this program should be optimized.
A program should be undertaken to extend the
current work to flowing streams.
Further studies should be initiated to establish
the optimum media mesh size with respect to
removal efficiency, cost, and in the case of the
carbon, method of pulverization.
Commercial production techniques for manufacture
of floating ion exchange resins should be refined.
Production techniques for suspension polymerization
of floating cationic resins should be developed.
Techniques for marking spills of various hazardous
materials should be developed, permitting visual
delineation of the spill area and greatly facil-
itating response activities.
Consideration should be given to the development
of a sinking sorption media which can be easily
recovered from the bottom of a watercourse.
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SECTION III
INTRODUCTION
Pollution resulting from the spillage of oil and hazardous
materials has emerged as a major national problem. It
is presently estimated that some fifteen thousand spills
involving oil and hazardous materials occur annually
in the navigable waters of the United States^'.
These spills range in size from small quantities to
millions of gallons(2) and threaten many important
waterways in the country.
Damage from such spills is often extensive. Massive spills
can render waterways unfit for some or all major beneficial
water uses and in some instances may eliminate large
segments of the biota in the affected area. Recognition
of the severe environmental threat represented by acci-
dental spillage of hazardous polluting substances has led
to legislative and administrative steps designed to
minimize acute releases and provide for immediate response '
activities when necessary. Of particular importance is
the development of methods for in situ treatment of spills.
This report describes an EPA sponsored program aimed
at the development of one such method of in situ treatment
of hazardous materials spills.
Potential treatments which conceivably can be applied iri
situ to ameliorate the effects of hazardous polluting
substances in the aquatic environment are almost as
numerous as the substances themselves. Obviously, it
would be impractical to attempt to develop a specific
countermeasure for each individual hazardous polluting
substance. Moreover, since the resources which can be
invested in developing countermeasures against hazardous
polluting substances in the aquatic environment are limited,
efforts must be directed toward those areas which promise
to produce the maximum return on this investment.
JBattelJLej-Northwest used the following criteria to evaluate
potential countermeasures.
• Countermeasures should be highly effective.
• Countermeasures should be applicable to a large
number of substances.
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• Counter-measures should be amenable to rapid, easy
deployment. Equipment and/or chemicals which
cannot be rapidly conveyed to the scene of an
incident are undesirable.
v Countermeasures should be free from potentially
harmful secondary effects in the aquatic environ-
ment, including noxious sludges,
• Countermeasures developed to combat spills of
hazardous polluting substances should take ad-
vantage of existing technology, particularly
that technology developed to combat oil spills,
to the maximum possible extent.
• Countermeasures should provide for easy isolation
and removal from water of substances added to
extract or precipitate spilled materials.
Consideration of numerous, potential methods for the in
situ treatment of spills of hazardous polluting substances
led to the following conclusions.
• Chemical degradation (transformation, oxidation-
reduction, etc.)is generally unacceptable since
in most cases the agents which must be added to
effect reaction pose an equal or greater potential
hazard to the aquatic environment than the original
pollutant. The situation is further complicated
by the nature of the spill environment which does
not allow close control of operating conditions.
Concentration changes resulting from natural
dilution processes could cause excess chemical
addition and so increase the damage to the
aquatic environment.
• Complex formation and neutralization suffer from
difficulties similar to those of chemical degrada-
tion, in the lack of control of the reaction
environment and the inherent threat to water
quality of the necessary additives.
• Precipitation techniques at first appear to be
an attractive solution; however, the ultimate
reaction poses a new type of threat. Without an
effective means for removing the precipitate, the
watercourse is subjected to a concentrated buildup
of fine particulate matter which could damage
feeding and spawning grounds, with subsequent
deleterious effects on aquatic life. The full
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impact of this type of damage has never been
satisfactorily explained, but presumably it
could rival the damages of the original pollutant
to water quality. Furthermore, the introduction
of colloidal precipitates would threaten gilled
species and would decidedly damage recreational
and aesthetic water quality characteristics.
Solvent extraction and foam separation processes
have several intriguing characteristics. With
proper choice of solvent, the product stream can
be made to rise to the surface where collection
with existing hardware should be possible. In
addition, solvent extraction and foam separation
processes are fairly broadbased, with a single
component displaying applicability to many
pollutant releases. Unfortunately, both processes
require some control over the area to be treated,
and treatment of any large body of water would
necessitate use of several types of feed mech-
anisms. This implies high capital costs and
storage facilities to stockpile such equipment
regionally. Further, in the case of solvent
extraction, the solubility of the solvent in water
would cause a considerable pollution problem in
itself due to the large quantity of solvent
required.
Skimming and booming are available techniques for
oil spills. They could be applied to light in-
soluble materials as well as slightly soluble
organics. Rapid response aimed at booming and
skimming any undissolved portion of the contaminant
could greatly reduce the severity of a spill.
Flow augmentation can be applied only in certain
circumstances. Mechanical mixers such as outboard
motors can be used to aid diffusion. Flow augmen-
tation may be utilized where stored water is
available upstream. In any event, such a practice
relies in part on good predictive models of the
aquatic environment to determine the extent of
contamination and expected duration of toxic
concentrations. This information is available for
a number of streams, as is time-of-travel data.
Such data are not gathered in a single source nor
properly referenced to allow for quick retrieval
and application in a practical emergency, however.
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• Burn-off techniques, because of safety and air
quality considerations, are probably applicable
only in very limited cases in which the material
remains confined in a small isolated area. Many
hazardous materials emit highly toxic vapors when
heated to decomposition. Consequently, burning
may intensify hazardous conditions and force
evacuation of areas surrounding a spill site.
The presence of heavy vapors which can travel
along the ground and cause flash-backs further
endangers safety when burn-off techniques are
applied.
• Oxygen addition may be an attractive alternative
for substances posing a BOD problem. The oxygen
is added to the water to maintain dissolved oxygen
levels while a spilled material is being dispersed
and degraded aerobically. There has been recent
interest in injecting air or pure oxygen into
water courses to achieve this end in areas of
chronic low dissolved oxygen. The required
apparatus is simple enough to allow mobilization
for transport to a spill site. The problems
would involve supplying enough gas to accomplish
the task and designing equipment capable of
efficiently transferring the gas into a variety
of potential stream or reservoir configurations.
• Biological degradation, while attractive in some
respects, encounters several difficulties. In
order to encourage degradation at a rapid rate
it would be necessary to have on hand large
quantities of acclimated cultures. The problems
associated with stockpiling many such cultures,
each specific to a particular substance, are
obvious. Also, many hazardous materials are
inherently resistant to biological degradation.
• Physical sorption and ion exchange processes can
remove substances from solution within a period of
a few minutes and hold the substances in a solid
form for long periods of time. The use of ion
exchange resins for acid, base, metal, or toxic
salt spills and the use of activated carbon or
sorption resins for organic matter could apply to
a large number of hazardous polluting substances.
Based on the above considerations, it was concluded that
physical sorption and ion exchange processes offer the
greatest promise for treatment of acute spills in the aquatic
environment.
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The two major problems associated with the application of
mass transfer media to counteract spills of hazardous
polluting substances in a free water environment are:
1. the mechanics of introducing the active media
into the water (a common problem with all
treatment agents) and
2. the subsequent removal of the media from the
water.
Traditionally, sorption and ion exchange processes have
been largely restricted to operation within columns.
This method of application is limited by some very real
concerns: the cost of stockpiling mobile columns for
spill treatment, the problem of rapid deployment of the
large equipment involved, and the practicality of pumping
free waters into a contained environment for treatment.
Some studies have been conducted with powdered activated
carbon in which the sorptive media was dispersed on the
water and allowed to settle(3). Although this approach
may be satisfactory for selected impoundments, in flowing
streams the aesthetic damage would be extensive and gilled
species would be subjected to the problems inherent in an
environment highly saturated with particulate and colloidal
matter.
An alternative approach is the use of floating mass trans-
fer media wherein the problems of posttreatment residual
effects would be eliminated by collection of the spent
media after use. Application problems would be reduced
to those of subsurface injection and surface collection.
Subsequent to these conclusions, a program was initiated
by Battelle-Northwest under EPA sponsorship to develop
and demonstrate the concept of floating physical sorbents
and ion exchange resins for iji situ treatment of spills
of hazardous polluting substances. This report describes
the results of the work accomplished in that program.
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SECTION IV
THE CONCEPT
Sorption processes are highly effective for removing many
different substances from water. Their principal ad-
vantages are: (1) treatment can be accomplished without
the addition of chemical reagents to the water; (2) one
sorbent can be used to remove a large number of different
substances from water; and (3) the sorbent collects and
holds a hazardous material in a less nocuous (undissolved)
form for long periods of time. The term "sorption", as
used in this report applies to both physical sorption
(e.g., surface attraction as in activated carbon) and ion
exchange.
Physical sorbents act like chemical sponges, soaking
up dissolved pollutants without releasing undesirable
materials in their place. Ion exchangers, on the other
hand, replace a hazardous material in the aqueous phase
with a less objectionable material. For acids and bases
the H+ and OH" ions are neutralized to water and the anion
or cation corresponding to the acid or base is sorbed by
the exchanger. Therefore, the acid or base is essentially
removed from the water and a corresponding amount of
salt does not remain as would be the case if the acid
or base were chemically neutralized. The treatment of
a salt spill (e.g., CuS04) would most probably involve
the replacement of the toxic ion(s) (e.g., Cu*2) with
ions (e.g., Na+) that are more compatible with the aquatic
environment.
Sorption may be accomplished either by batch treatment
or by column treatment. Batch treatment is carried out
by mixing the sorbent with the solution to be treated
for a specified period of time after which the sorbent
is separated from the solution for disposal or regeneration
and reuse. This method is simple and may be carried out
with relatively low-cost equipment. Column treatment is
accomplished by percolating the solution through a bed
of the sorbent until some level of the sorption capacity
is utilized. The sorbent in the column is usually regen-
erated at this point and the loa ng cycle repeated.
Column treatment is generally more efficient than batch
treatment and lower effluent concentration values may be
attained. However, in the case of a spill situation,
column treatment would involve the transport of large
13
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volumes of water to a treatment facility and then return
of the treated water to the lake or stream. Another
disadvantage of column treatment in the field is the
substantial time period required to set up and operate
the necessary equipment. Because response and treatment
time must be rapid to minimize dispersal of the hazardous
material from the site of the spill, batch treatment
appears most feasible for field use.
Recovery of the sorbent after treatment is necessary to
prevent slow desorption of highly toxic material and
for aesthetic reasons. Most sorbents will sink when
applied to water, which complicates their retrieval.
Moreover, dredging may result in the removal of large
quantities of benthic life and bottom materials with the
media. Floating sorbents, however, can be recovered by
oil skimming or similar well-established surface collection
techniques.
It is anticipated that floating sorbents would be injected
at the bottom of a watercourse and allowed to float to
the surface through the zone of contamination. Because
the sorbent must perform its function with only one pass
to the surface/ the kinetics of pollutant removal can pose
a problem. Kinetic problems in columns are solved by
adjustment of the throughput rate to achieve the residence
time necessary to effect the desired degree of removal.
However, kinetic problems are not so simply solved in a
buoyant sorbent system.
The controlling parameters involved in a free-water
mass-transfer system include temperature, concentration
of solute, particle velocity, and particle surface area.
Obviously, the first two parameters are functions of the
location and nature of the spill and cannot be practi-
cally controlled in a free water environment. (Indeed,
the purpose of applying a countermeasure is to reduce
the concentration of the solute [hazardous polluting
substance] to some acceptable level). However, particle
velocity and particle surface area can be controlled
through adjustment of the particle size.
Since mass transfer rates are proportional to surface
area, the division of a large particle into several
smaller ones increases the surface area and thus acceler-
ates the mass transfer rates. Reduction in particle size
also reduces the rate of rise of a floatable media since
buoyancy is a function of r3 while drag is a function of
r2. Reduction of the rate of rise increases the residence
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time as the media rises to the surface. Thus, reduction
of particle radius causes an increase in the rate of mass
transfer to occur. Adjustment of media density can also
be utilized to increase the contact time.
Effective use of floating media requires that (1) buoyant
sorption media be deposited at the bottom of the water
column so that it removes selected dissolved contaminants
(i.e./ toxic ions or organics) as it rises to the surface;
(2) means be provided to uniformly distribute the media
during the deposition step or as it rises to the surface;
and (3) the application rate be properly proportioned to
the amount of pollutant to be removed or neutralized per
unit area of water surface.
Two general methods are envisioned for applying the mass
transfer media to achieve such a distribution: (1) pumping
bulk media as a slurry through a pipe which terminates
near the bottom of the watercourse and which is installed
on a boat or vessel propelled at a speed proportional
to the application rate, and (2) dropping on the water
surface packages or media capsules weighted with ballast,
the packaging material of which disintegrates or opens
upon exposure to water after sufficient time to allow the
packages or capsules to reach the bottom.
The first method would involve the deployment of a
specialized set of equipment on boats or vessels. In all
likelihood, the equipment could be made air transportable.
Nevertheless, some delay would result from the time
required for equipment handling and setup and possibly
for training local personnel to operate the equipment.
On the other hand, the package or capsule "bombing" tech-
nique could employ aircraft as well as surface vessels.
Moreover, the distribution of packages would be manually
controlled and no special equipment would be required—
eliminating the associated deployment delays.
Once the media has been applied and allowed to perform its
function, relatively long periods can elapse before recovery
of the spent media, because the potential pollutant will
be sorbed or fixed on a material which is essentially
insoluble. The physical recovery of the spent media can
be achieved either manually or with mechanized equipment.
When treating a flowing stream, a simple but probably
effective approach would call for positioning of floating
baffles or booms at an angle across the stream and down-
stream of the spill treatment area. This would serve to
direct the floating media to an accessible shore area.
15
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Pickup of the media could then be achieved either manually
or by using simple agricultural or earth moving equipment
(e.g., drag lines, back hoes).
In the case of static waters such as lakes, ponds, re-
servoirs, bays, and harbors, a means would be needed for
collecting or concentrating the media and then removing
it from the water surface or from adjacent shore areas.
This could be partially accomplished by techniques
similar to those mentioned for a flowing stream. How-
ever, there is the added requirement for concentration
and possible removal of the spent media from the static
water surface. The techniques required for this are
parallel to those necessary for recovering floating
oil slicks. In fact, application of much of the technology
developed for oil spill countermeasures to the recovery
of spent sorption media appears feasible.
Use in saline waters will have differing effects. Sorption
processes of materials less soluble in salt water than in
fresh water will be aided by the presence of the salts,
whereas sorption of organics more soluble in salt water
will be hindered. Treatment of acid and base spills
will be more efficient in salt water than in fresh, while
treatment efficiency of toxic cations and anions will be
reduced.
The economics of such a treatment scheme depend upon the
mass transfer media selected. In commercial quantities
activated carbon and common resins are relatively in-
expensive. The opportunities for regeneration and possible
salvage of the spilled contaminant may further improve
the economics of this scheme.
The process is expected to be applicable to all types of
impounded or flowing waters, fresh or saline (however, this
work involved application to impounded waters only). A
wide range of hazardous materials can thus be treated
with a minimum of equipment and elapsed time. Stock-
piling of materials could be reduced to one or two
national centers. Oil collection equipment will in fact
be used and thus should already be deployed through the
National Contingency Plan. In many cases, the removal
efficiency should be sufficient to return receiving
waters to an acceptable water quality. In the remaining
cases, treatment will substantially minimize the amount of
dilution required to reduce the pollutant concentration
below its damage threshold.
16
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The simplicity of application and ultimate effectiveness
of floating sorption media can best be illustrated with
a hypothetical spill incident. Consider a barge which
founders while carrying 50,000 gallons of benzene.
Assuming the nature and location of the spill is reported
promptly and accurately, countermeasures could be taken
to minimize the damage to marine fisheries in the area.
Upon identification of the spilled material as an aromatic
compound, transport aircraft would be loaded with packaged
floating sorbents and dispatched to the release site.
Personnel at the spill site would maintain radio contact
with the aircraft and direct their drops to cover the
contaminant plume.1 If the aircraft arrived approximately
six hours after the spill occurred and the stream had
a one knot current and high diffusivities, the spill
would have moved approximately 11,000 meters downstream
and would be 580 meters long and the width of the stream.
While making low passes over the stream, the aircraft
would release a pattern of media packages over the affected
area.
Individual packages would sink to the bottom, disinte-
grate, and release the floatable carbon. Particles of
carbon would disperse with the eddy currents and slowly
rise to the surface, sorbing benzene as it passed.
A screen skimmer or boom could be deployed downstream
to guide the spent carbon to a surface pumping device.
The collected media could then be stored for drying
and subsequent disposal or regeneration and reuse. While
retrieval is best accomplished as soon after deployment
as possible, the carbon could be allowed to drift with
the current for several days while skimming devices
were located and put in place.
The sequential steps in treating a spill are illustrated
in Figures 1-6.
17
-------
* N. —,
•A,
oo
-
FIGURE 1
SPILL OF HAZARDOUS MATERIAL
-------
. • •-
FIGURE 2
OFFICIALS ARE NOTIFIED.
RESPONSE TEAM IS SET INTO ACTION
-------
(0
FIGURE 3
APPROPRIATE MEDIA TYPE IS SELECTED
AND LOADED ONTO DELIVERY PLANE
-------
-
•
•
'
-
/
'
-
•
.
,
•
.
FIGURE 4
INDIVIDUAL MEDIA-PACKAGES ARE AIR DROPPED
INTO CONTAMINANT PLUME
-------
to
to
.- -
FIGURE 5
PACKAGES SINK AND BEGIN TO DECOMPOSE
MEDIA FLOATS TO SURFACE REMOVING CONTAMINANT
-------
U)
FIGURE 6
STANDARD OIL SKIMMERS ARE USED
TO RETRIEVE MEDIA
-------
SECTION V
LABORATORY STUDIES
FLOATING CARBON SORBENTS
Physical sorption results from the attractive forces that
are present at the interface of two phases. The surface
of a solid will attract and hold molecules present in
either gases or liquids. The amount held per unit area
of the surface is relatively small but it becomes a
significant fraction of the total mass of the solid
phase when the surface area per unit of mass is very
large. The surface area of a good activated carbon, for
example, will be on the order of 1000 square meters or
more per gram of carbon. Surface area values and iodine
numbers are listed for several commercial grade carbons
in Table 1. The iodine number gives a general indication
of the efficiency of the carbon in adsorbing small mole-
cules .
TABLE 1
Surface Areas and Iodine Numbers of Several
Commercial Grade Carbons*4'5'
Iodine
Surface Number,
Carbon Supplier Area (BET) m /g mg^ 12/g Carbon
Darco Atlas Chemical 600-650 650
Industries
Piltrasorb Calgon 950-1050 900
300 Corporation
Filtrasorb Calgon 1000-1200 1000
400 Corporation
Nuchar WV-W Westvaco 850 850
Corporation
Nuchar WV-L Westvaco 1000 950
Corporation
Nuchar C-190 Westvaco 900 700-800
Corporation
25
-------
A number of physical sorbents are available for removing
non-polar materials such as organic substances from water
but the best known and most widely used is activated
carbon. An investigation of available activated carbons
with the desired floatability disclosed two commercial
granular carbons which resist wetting and remain floating
for long periods of time. These are Nuchar C-190 and
Nuchar WA, both products of Westvaco.
Early in the program, some qualitative observations on
the floatability of various mesh sizes of Nuchar C-190
were made. Samples of this carbon were slurried in water
and shaken for various time intervals. After shaking,
the samples were allowed to stand for five minutes and
visual observations were used to estimate the quantity
which remained floating. Table 2 summarizes the obser-
vations, which show that the finer mesh sizes are more
susceptible to wetting and sinking than the larger. Due
to the vigorous mixing in these tests, the percentage of
floating carbon is probably lower than that which would
normally be anticipated in actual spill cleanup operations,
TABLE 2
Approximate Floatability of Various
Mesh Sizes of Nuchar C-190
Shaking Time
(hours)
Mesh Size
>20
20-30
30-50
50-100
100-200
200-325
1
100
95
95
95
90
80
2
Approximate
100
95
95
90
90
80
4
Percent
95
95
95
90
85
75
6
Floating
95
90
90
90
80
70
24
85
85
85
85
80
70
26
-------
Batch contact experiments were conducted to determine the
sorption isotherms for phenol using Nuchar C-190 activated
carbon. The procedure involved mixing various quantities
of carbon with a standard solution of phenol (183 mg/1)
buffered at pH 6.5^6'. Phenol is more strongly sorbed below
pH 7 and buffering is required to prevent a significant
change in pH. Samples of 100 x 325 mesh carbon were
mixed with the phenol solution for 16 hours (to assure
equilibrium conditions) after which the solution was
filtered and analyzed for total organic carbon. Reagent
blanks with and without carbon but containing no phenol
were run simultaneously to correct for very small amounts
of extraneous organic matter or carbon which may have
penetrated the filter. The quantity of phenol sorbed
by the carbon was determined by the difference in phenol
concentration before and after contact with the carbon.
The results of the experiments are illustrated as a
sorption isotherm in Figure 7. The sorption isotherm
compares favorably with data reported in the literature.
The relationship between mesh size and rise time was
investigated using a two inch diameter glass column and
a water depth of four feet. Carbon was placed on the
water surface and the column was inverted. The time
required for the bulk (-95 percent) of the carbon to
rise through the water column to the surface was
recorded. The results of these experiments are pre-
sented in Table 3.
TABLE 3
Rise Time for Nuchar C-190 in Four Feet of Water
Time for ~95 Percent
of Carbon to Surface
Mesh Size (minutes)
30-50 5
50-100 10
100-200 15
200-300 15
Various mesh sizes of Nuchar C-190 and Nuchar WA in both
wetted and dry form were evaluated for their uptake of
phenol by floating the carbons through a five foot
column of phenol solution (185 mg/1) buffered at pH
27
-------
1000
0
2
X
Q.
CT
O
CO
O£
•<
O
E
100
00
10
J L
10
100
1000
SOLUTION PHENOL, mg/l
FIGURE 7
SORPTION ISOTHERM FOR PHENOL AND NUCHAR C-190
-------
6.5. The carbon was released from a bottle at the
bottom of the column at an application ratio of 2000
mg of carbon per liter of solution. The results of
these experiments are illustrated in Figure 8. The dry
carbon was prepared by oven drying at 100°C for 16 hours
and the wet carbon was contacted with water for two
hours and then filtered to remove interstitial water
before use. The time required to float approximately 95
percent of the carbon through the five foot column varied
from 3 to 12 minutes for the dry and wet 30 x 50 mesh carbon,
respectively to 20 to 25 minutes for tne dry and wet
200 x 325 mesh carbon, respectively. Nuchar C-190
was selected for further study on the basis of its
superior sorptive ability and floatability. The Nuchar
C-190 was found to contain a smaller percentage of
sinking granules than the Nuchar WA. A mesh size of
100 x 325 was selected for further study because phenol
removal is near maximum with carbon particles in this
size range.
In order to assess the effectiveness of Nuchar C-190 in
sorbing other hazardous organic materials, a set of
batch removal experiments was conducted. Toluene, benzene,
styrene and acrylonitrile were selected for study. Sam-
ples containing 50 microliters of each of these materials
in 200 ml of water were contacted with 400 mg of 100 x
325 mesh carbon and were shaken vigorously for one hour.
Each sample was allowed to stand overnight in a closed
container and the aqueous phase was then analyzed for
TOC with the results given in Table 4.
TABLE 4
Removal Effectiveness for Nuchar C-190
for Various Organic Materials
Initial Final
TOC TOC Removal
Material (mg/1) (mg/1) Percent
Toluene 184 8 96
Benzene 198 12 94
Styrene 174 8.5 96
Acrylonitrile 146 90 38
Nuchar C-190 Dose = 1000 mg/1
29
-------
100
o
80
60
40
20
0
O DRY CARBON
D WET CARBON
C-190
WA
DOSE 2000 mg/lCARBON
PHENOL CONCENTRATION 185 mg/1
TEMPERATURE
pH 6.5
I
30-50
MESH
50-100
MESH
100-200
MESH
200-325
MESH
FIGURE 8
COMPARISON OF C-190 WITH WA FOR REMOVAL OF PHENOL
-------
Two organophosphorus pesticides were similarly examined
with the results shown in Table 5. In addition to TOC
measurements, phosphate analyses were conducted using
the perchloric acid digestion technique for total phos-
phate as described in Standard Methods(7).
TABLE 5
Removal Effectiveness of Nuchar C-190
for Organophosphorus Pesticides
Carbon
Dose
Material (g/1)
Diazinon
Mai a th ion
0
1
2
0
1
2
TOC
TOC
Concentration Removal
(mg/1) Percent
114
8
6
120
8
9
___
93.5
94.5
___
93.0
92.5
Total
P04
(mg/1)
21.4
2.8
1.4
20.0
0.6
1.0
PO4
Removal
Percent
___
87.0
93.0
_....
97.0
95.0
Diazinon
Active Ingredients
0,0 diethyl 0-(2-isopropyl-4 methyl-
6-pyrimidinyl) phosphorothioate
Aromatic Petroleum Derivative Solvents
Inert Ingredients
Malathion
Active Ingredients
0,0-dimethyl dithiophosphate of diethyl
mercaptosuccinate
Aromatic Petroleum Derivative Solvents
Inert Ingredients
16.75%
68.875%
14.375%
57%
33%
10%
31
-------
Larger scale experiments were conducted in a six inch
diameter, six foot deep column of tap water containing
200 mg/1 of (1) phenol, (2) an oil emulsion of Malathion,
and (3) an oil emulsion of Diazinon. Removals of 86
percent, 82 percent, and 86 percent, respectively, were
obtained by floating 1000 mg/1 of 100 x 325 mesh carbon
through the water. The percent removal of phenol and
pesticide did not vary significantly at various depths
through the column after flotation of the carbon (see
Table 6). Carbon containing sorbed phenol was observed
to remain floating for at least two days following
application.
TABLE 6
Percentage Removal of Phenol, Malathion, and
Diazinon at Various Depths in the
Treatment Column After Flotation
of the Carbon
Depth,
ft.
1
2
3
4
Composite
Sample
Phenol
Removal,
Percent
82
86
88
87
86
Malathion
Removal,
Percent
79
76
82
82
82
Diazinon
Removal,
Percent
90
84
86
Column experiments were also conducted with a more con-
centrated Diazinon mixture (48 percent in xylene) added to the
six inch diameter column containing 28 liters of tap water.
In the first experiment, 4 ml of 48 percent Diazinon oil
emulsion were rapidly mixed with 8 ml of tap water to form
a stable emulsion. The emulsion was then added to the
column followed by the introduction of a weighted bottle
containing 40 g of 40 x 325 mesh Nuchar C-190 which floated
through the diluted emulsion. Diazinon removal in this
first experiment was 89 percent as determined on a total
phosphate basis. A second experiment was conducted wherein
32
-------
both the Diazinon and carbon were reduced to 25 percent
of that used in the first experiment. The Diazinon
removal in the second experiment was 85 percent which
illustrates the higher removal efficiency obtained at
higher concentrations by the same proportion of carbon.
Final laboratory work was aimed at identifying the best
means of producing large quantities of floating carbon
in the appropriate mesh sizes. A comparison was made
between a sample of ball-milled Nuchar C-190 and a
sample of Nuchar C-190 that had been hand crushed on a
100 mesh screen. When floated through a two inch diameter,
four foot deep column of 200 mg/1 phenol solution, the
hand crushed carbon removed 62 percent of the phenol
compared to 57 percent removal by the ball-milled carbon.
Both carbons were applied at the 1000 mg/1 level. The
ball-milled carbon appeared to flocculate to a greater
degree than the hand crushed carbon when released from
the bottle at the bottom of the column of phenol solution.
The greater degree of flocculation would tend to reduce
contact of the carbon with the phenol solution and thereby
reduce the amount of phenol sorbed from solution.
Two mesh sizes of Nuchar C-190 were commercially avail-
able: (1) +30 mesh which is essentially 12 x 30 mesh,
and (2) "unground" material which is largely 14 x 325
mesh. In view of the lower uptake of phenol by ball-
milled carbon it was decided to employ an impact method
of crushing a large quantity of Nuchar C-190 for use in
a field demonstration. A jet pulverizer, marketed by
Majac, Inc., Pittsburgh, Pennsylvania, was initially
considered for crushing the carbon. This device pulver-
izes granular material by impacting the particles in
opposing jet streams. The +30 mesh Nuchar C-190 was
selected for crushing on the basis that the narrow mesh
size range would provide a higher anticipated yield of
a 100 x 325 mesh size using the jet pulverizer. On the
basis of prior performance with similar materials, a yield
of about 50 percent was anticipated.
A 4000 pound order of +30 mesh Nuchar C-190 was shipped
to a pilot plant facility for crushing. Subsequent
testing with a jet pulverizer showed a yield of only 20
percent in the 100 x 325 mesh range. Further testing
indicated that a similar mesh range could be obtained at
a higher proct ssing rate and lower cost with an air impact
pulverizer. The bulk of the 4000 pounds of carbon was
then subjected to the impact pulverizer and air classi-
fied to give 2387 pounds of +325 mesh material which was
reported to contain 38 percent of the desired 100 x 325
33
-------
mesh size. Subsequent analysis of a sample of the +325
mesh fraction showed only 17 percent 100 x 325 mesh
carbon. The mesh size used for the field demonstration
was therefore broadened to 40 x 325 mesh to give a
maximum recovery of 49 percent of the +325 mesh fraction
or 29 percent of the total carbon that was pulverized.
The actual recovery was 23 percent of the total prior
to breakdown of the sieving apparatus, which was used
to classify the carbon. A total of 675 pounds of 40 x
325 mesh carbon was obtained which was supplemented with
170 pounds of 12 x 325 mesh carbon for the field demon-
stration. As a result of the low yield of the desired
mesh size from processing +30 mesh Nuchar C-190, it is
believed that the "xmground" Nuchar C-190 may have been a
more desirable starting material. Alternate sources of
floating activated carbon will have to be investigated for
future work because neither the unground nor +30 mesh
Nuchar C-190 are commercially available any longer. Since
the completion of these studies, Westvaco has discontinued
sales of unground and +30 mesh Nuchar C-190 and will soon
discontinue sales of the same grades of Nuchar WA. West-
vaco is continuing to market a powdered grade of Nuchar
C-190 which has a significant fraction of the carbon
particles in the +325 mesh size. This and other potential
sources of floating activated carbon are discussed in
the Appendix.
FLOATING ION EXCHANGE RESINS
Ion exchange resins are effective for removing and/or
neutralizing a broad spectrum of hazardous ionic substances
from water. These substances include acids, bases, and
toxic salts where either the cation or the anion or both
are toxic to some degree.
The degree of sorption for a particular ion under equil-
ibrium conditions is largely a function of: (1) the
concentration of that ion; <2) the concentration and
types of competing ions; and (3) temperature. A number
of different types of ion exchange resins are available
under the categories of cation exchangers or anion exchang-
ers. The cation exchangers can be divided into different
types depending on the acid strength of the groups.
Strong acid groups such as -SO3 remain ionized even at
low pH and can function in acid solutions.
In contrast, weak acid groups such as -COO" are ionized
only at high pH. At low pH they combine with H+ to form
undissociated -COOH and no longer act as fixed charges
34
-------
where an exchange of ions can take place. For example,
a weakly acidic cation exchange resin would not be
effective for removing ammonium ion from a solution at
pH 3 because of the resin's strong affinity for hydrogen
ion. Under neutral to basic conditions, as in the case
of an ammonia spill, a weakly acidic cation exchange
resin could be effective for both neutralizing the basic-
ity and sorbing the ammonia. The titration curve of a
weakly acidic resin is illustrated in Figure 9
along with that of a strongly acidic resin. Using a
weakly acidic ion exchanger for treating a caustic
spill would have an advantage in that an overdose would
not cause an overreaction which would produce acidic
instead of neutral conditions. Anion exchangers which
vary in base strength and act in a manner similar to
cation exchangers are also available.
(8)
Boyd, e_t a_l note that for organic zeolites in the
60 to 70 mesh range, up to 90 percent of the theoretical
capacity can be achieved within 30 seconds. Kressman
and Kitchener(9) found phenolsulphonic resins reach
90 percent of capacity in two to nine minutes with
simple cations. Helfferich(1Q) makes similar obser-
vations for strong acid and base exchanges. At the
beginning of this program it was postulated that
adjusting the rise rate of the selected media to provide
the several minutes required for utilizing the major
portion of the media's capacity should be possible.
The first attempts to produce floating ion exchange beads
employed suspension polymerization techniques. Preliminary
experimentation centered around the inclusion of hollow
glass microspheres (Eccospheres ® manufactured by Emerson
and Gumming Inc., Canton, Massachusetts) in the resin matrix.
Standard styrene-divinylbenzene ion exchange resin beads
are generally prepared by polymerizing a mixture of
styrene and divinylbenzene in a stirred aqueous suspension
containing a suspension stabilizer (e.g., starch, gelatin,
polyvinyl alcohol). The size of the resin beads produced
is determined by the stirring rate. Polymerization
usually requires several hours after the addition of a
catalyst (e.g., 1 percent benzoyl peroxide). Ion exchange
groups are normally inserted into the resin matrix after
preparation of the beads.
Initial attempts to include the hollow microspheres in
the monomer phase during aqueous-suspension polymeriza-
tion with styrene-divinylbenzene mixtures were not
successful. Though mixed with the monomer phase prior
to suspension, the glass micros-pheres quickly transferred
35
-------
12
10 -
8 -
WEAKLY ACIDIC
RESIN
-------
to the aqueous phase when the phases were mixed. This can
be attributed to hydrophilic characteristics on the
surfaces of the microspheres. Treatment of the beads
with silicone formulations failed to alter the hydro-
philic characteristics sufficiently to favor the organic
phase.
Parallel efforts were directed to formulation of resins
via bulk polymerization techniques. Here, the glass
ndcrospheres are stirred into the catalyzed monomer
as it begins to set, resulting in the formation of a
solid mass of resin with individual microspheres trapped
throughout the resin matrix. The resin mass is then
fractured and sieved to obtain the mesh size desired.
This technique showed promise with soft aqueous gels of
weak acid acrylic polymer resins, but did not produce
satisfactory yields of small mesh sizes with hard resin
masses. Excessive shattering of the glass microspheres
occurred when crushing the hard resin masses to produce
small grain sizes.
An initial attempt was made to produce a resin with acry-
lamide crosslinked with N, N'-methylenebisacrylamide.
These two organic monomers are water soluble and can be
readily polymerized at room temperature. A floating ion
exchange resin was prepared by mixing hdllow glass micro-
spheres in the monomers prior to polymerization. (Hy-
drolysis converts the amide group in the resin structure
to carboxyl groups with ion exchange capability).
Unfortunately, the product beads were found to be
structurally weak and consequently unsatisfactory.
Two types of resin were successfully prepared and
selected for further study in preparation and evaluation
of floating ion exchangers. These were (1) a weak acidic
carboxylic resin prepared from acrylic acid and a suit-
able crosslinking agent using bulk polymerization tech-
niques which included a soft gel intermediate, and (2)
a weakly basic epoxypolyamine resin prepared from
epichlorohydrin and polyethyleneimine using suspension
polymerization.
The acrylic resin granules were produced in a modified
bulk polymerization technique from acrylic acid cross-
linked with ten percent ethylene glycol dimethyacrylate.
The hollow glass microspheres were incorporated into the
resin matrix by trapping an aqueous mixture of the monomers
and microspheres in the interstices of a packed bed of
small glass beads or other granular material (e.g., gypsum)
prior to polymerization. After the monomers polymerized,
37
-------
the solid mass of resin was crushed and the usable resin
granules separated by filtration with water. The grain
size and shape of the bed material dictates the size of
the resin granule produced. An alternative method of
preparation was used which employed a soluble salt (e.g.,
NaCl) rather than insoluble granules to trap resin monomers
and hollow microspheres together for polymerization.
This method is more adaptable to production of small
resin particles. The salt can be removed to a large degree
by dissolution, thus avoiding excessive crushing which
tends to fracture the glass microspheres. Some crushing,
however, is still required which increases the number of
hollow microspheres required. Microspheres constitute
the greatest single cost for production of floating
resins.
Weak acid acrylic ion exchange resins have very high
exchange capacities due to the relatively large number
of carboxylic (-COOH) groups on the resin matrix. An
example of the resin structure of polymerized methacrylic
acid crosslinked with divinylbenzene is illustrated in
Figure 10. The H+' on a COOH group is exchangeable to a
large degree with other cations providing that the solution
pH does not fall below a minimum level (5-7). This
ability to act as a buffer is desirable since an excess
of the resin applied to counteract a caustic spill will
not result in "salt splitting" to produce acids which may
cause as much difficulty as the spilled caustic. For
example, a carboxylic exchanger has a high affinity for
hydrogen ion with the result that this resin displaces
sodium ion from a solution of sodium chloride with great
difficulty due to the formation of a strong acid, HC1,
as one of the reaction products. Thus, the equilibrium
is shifted far to the left as illustrated by the following
reaction:
RCOOH + NaCl RCOONa + HC1
For the case of reaction with sodium hydroxide, the
equilibrium shifts far to the right since water is the
reaction product rather than acid:
RCOOH + NaOH RCOONa + H20
The resin illustrated in Figure 10 is the standard weak-
acid acrylic resin of commerce (Amberlite IRC-50), which
is made from methacrylic ester and divinylbenzene by the
aqueous suspension polymerization process. This resin has
an ultimate exchange capacity (at high pH) of 10 milli-
equivalents per gram of dry resin. At pH 7, the capacity
is about eight milliequivalents per gram of dry resin.
38
-------
\D
COOH
CH — CH.
COOH
COOH
COOH
COOH
CH—CH;
CH — CH—CH CH — CH — CH
COOH
•CH? CH—CH2-
COOH
-CH—CH2—CH-
COOH
\
—CH., CH—CH;
COOH
-CH—CH2—CH
•CH.
COOH
-CH CH;
COOH COOH COOH
\ \ \
CH—CH2 CH — CH- CH
COOH
-CH — CH
COOH
-CH — CH2—CH
COOH
-CH—CH;
COOH COOH
\ \
-CH—CH—CH
COOH
CH
COOH
CH
FIGURE 10
POLYMERIZED ACRYLIC ACID CROSSLINKED WITH DIVINYLBENZENE
-------
The ultimate exchange capacity of the floating acrylic
resin, prepared in the laboratory from acrylic acid
crosslinked with 10 percent ethylene glycol dimethacrylate
was found to be eight milliequivalents per dry gram
(including the weight of the hollow microspheres). The
structure of this resin is illustrated in Figure 11. Two
different batches of floating resin, 20 x 50 mesh and
25 x 70 mesh, were used to determine the uptake of alkali
from a 200 mg/1 solution of NaOH in distilled water.
Six grams of resin of each mesh size were released at the
bottom of a four foot by two inch column of 200 mg/1 NaOH
solution; the uptake of alkali by the 25 x 70 mesh resin
was determined to be 82 percent as compared to 66 percent
removal by the coarser 20 x 50 mesh resin. The 82 percent
removal represents about 25 percent utilization of the
ultimate exchange capacity of the resin. Uptake of alkali
from a dilute distilled water solution is expected to be
somewhat slower than that for a solution containing
neutral salts. Natural waters found in lakes and streams
will contain varying concentrations of neutral salts
which should increase the efficiency of alkali removal by
this resin. A titration curve for the floating acrylic
resin is given in Figure 12.
Samples of floating epoxyamine anion exchange resin were
prepared for evaluation in the laboratory. The formula
used consisted of a 3:1 ratio of epichlorohydrin to
tetraethylene pentamine. Epichlorohydrin was partially
reacted with tetraethylene pentamine in an ice bath to
form an aqueous syrup containing 49 percent water. This
syrup was then allowed to reach room temperature and
remain there for 45 minutes or more. A dilute sodium
hydroxide solution was added as a catalyst and hollow
glass microspheres were mixed into the syrup at a ratio
of two cubic centimeters of microspheres to one gram of
epichlorohydrin and tetraethylene pentamine. The mixture
was then added to rapidly mixed hot mineral oil to
complete the polymerization and produce resin beads.
The mineral oil contained a small amount (1 percent) of
turkey red oil (sulfated castor oil) to aid in reducing
the size of the aqueous globules prior to polymerization.
Initial batches of resin beads were generally larger in
mesh size than desired. Subsequent batches were prepared
in smaller mesh sizes by increasing both the mixing
speed and the oil to syrup ratio from about 10:1 to about
50:1. The structure of an epoxypolyamine anion exchange
resin is shown in Figure 13.
40
-------
COOH CH
CH— CH2 - C
C
t
COOH
\
COOH COOH COOH
CH? - CH— CH2 - CH— C^— CH -
COOH
COOH
CH-
— CH — CH — CH— CH— C
r*
0
COOH C = 0 COOH
\ I \
CH^^~ CH^^^~ C ~^~™ CH»" " Cn^^~ Cn^
CH,
COOH
\
C\H>
CH — CH2—C
COOH
CH — CH;
1
= 0
COOH
CH - CH
COOH
\
COOH
\
COOH
\
COOH
-CH
CH — CH2 - CH - CHg- - CH — O^ - CH — CHj—
CH3
FIGURE 11
r*
0
1
c=o
1
C
1
COOH
\
CH2 CH — C
COOH
\
H2 CH C
COOH
\
Hg— CH
COOH
— CHj CH
POLYMERIZED ACRYLIC ACID CROSSLINKED WITH ETHYLENE GLYCOL DIMETHACRYLATE
-------
10
10
I I 1 1 I I
024 6 8 10 12
HILLIEQUIVALENTS OF ALKALI ADDED/GRAM OF RESIN
FIGURE 12
TITRATION CURVE FOR FLOATING ACRYLIC ION EXCHANGE RESIN
Titration in 0.2 M NaCl
-------
1
N CH2
CH — OH
1
N — CH2—
CH0
I2
CH — OH
j
f2
N— CH2—
CH,
I2
CH — OH
1
-CH — CH2— N
CH,
I2
OH CH — OH
CH
FIGURE 13
EXAMPLE OF STRUCTURE OF AN EPOXYPOLYAMINE ANION EXCHANGE RESIN
-------
The floating anion exchange resin prepared in the manner
described above was found to have an ion exchange capacity
of four milliequivalents per gram of resin. A titration
curve for the resin is given in Figure 14. The resin
beads used for evaluation were largely in the 30 to 50
mesh size with 12 percent +30 mesh and 9 percent -50
mesh. When released from an ice cake to float up through
a four foot column of water containing 183 mg/1 HC1 and
200 mg/1 NaCl, the resin removed 61 percent of the acid
at an application ratio of two grams resin per liter of
water. This removal is somewhat less than the removal of
NaOH by floating acrylic cation exchange resin under
comparable conditions; this is believed due to the smaller
ion exchange capacity of the epoxyamine resin (4 meq/g vs
8 meq/g). In both cases, however, only a small fraction
of the available ion exchange capacity is utilized. A
smaller mesh size is considered to be more important in
increasing the removal efficiency than adjusting the
resin bead density to a level just under that of water.
Resin bead density cannot be made too nearly that of
water since the density of the bead will increase as it
adsorbs ions from the water to replace either H+ or OH-
ions. Thus, the resin bead rise rate will decrease as
the exchange process proceeds. If the resin bead density
were initially very close to that of water, the bead
might initially rise and then sink as heavier ions are
exchanged for H+ or OH~.
Following the laboratory development phase, Diamond
Shamrock Chemical Company was engaged to investigate the
possibility of preparing several hundred pounds of floating
epoxyamine resin in their facilities at Redwood City,
California. Diamond Shamrock manufactures both a weak
base epoxyamine resin (Duolite A30T) and an intermediate
base resin (Duolite A30B). These anion exchange resins
are reported to have ion exchange capacities of 8-9 meq/
gram. It was considered that except for the addition of
the hollow glass microspheres, the technique of manufacture
of the epoxyamine resin would not be drastically altered
from standard production techniques. The major problem
lay in the mixing of the microspheres in the syrup just
prior to introduction into the oil.
Diamond Shamrock was successful in preparing a floating
epoxypolyamine resin both in their laboratory and sub-
sequently with their commercial production equipment. A
sample of laboratory prepared epoxypolyamine floating beads
was delivered to Battelle for evaluation prior to pro-
duction of a large batch. Figure 15 shows the titration
44
-------
12
10
8
6
4
2
0
I
I
I
_L
1234
MILLIEQUIVALENTS HC1 ADDED/GRAM DRY RESIN
FIGURE 14
TITRATION CURVE FOR FLOATING EPOXY-
POLYAMINE ANION EXCHANGE RESIN
Titration in 0.2 M NaCl
-------
curve for this sample. The exchange capacity for this
resin was approximately 70 percent greater than that for
the resin previously produced. The beads also appeared
to have greater structural integrity.
Once the acceptability of the floating resin was substan-
tiated, Battelle contracted with Diamond Shamrock to
produce a single lot of 14 cubic feet for use in a field
demonstration. The resulting product had the same physical
appearance as the earlier sample but showed a greater mesh
size dispersion favoring the fraction of larger particle
size. The larger mesh size of the resin caused a reduced
rate of exchange such that only 37 percent of the acid in
a 0.005 N HC1 solution was removed at 2000 mg/1 resin
application. This compares with 53 percent removal under
the same conditions with a -30 mesh fraction of resin.
It is felt that these size deviations will not be a
problem in commercial production once preparation tech-
niques are refined.
Since it is probable that higher concentrations of acid
than 0.005 N will be encountered under actual field
conditions, an experiment was conducted to measure the
uptake of sulfuric acid from a0.025N solution with 10
g/1 of applied floating epoxypolyamine resin. The re-
moval of acid at this higher level was 94 percent, which
is believed to be due to the more rapid diffusion of
acid from the solution to the surface of the resin bead
since both the acid and the resin were increased by a
factor of five. Film diffusion is usually rate limiting
for removal of constituents from a. dilute solution by ion
exchange, whereas particle diffusion becomes rate limiting
at the higher concentrations. The higher rate of uptake
from concentrated solutions again emphasizes the import-
ance of rapid response to treatment of spills.
While both the bulk polymerized acrylic resin and the
suspension polymerized epoxypolyamine resin were success-
fully produced and demonstrated to be effective for
neutralizing contaminated waters when allowed to float
up through a water column, suspension polymerization
is the preferred production technique.
46
-------
PH
10
MILLIEQUIVALENTS H2$04 ADDED/GRAM DRY RESIN
FIGURE 15
TITRATION CURVE FOR DIAMOND SHAMROCK WEAK BASE EPOXYPOLYAMINE RESIN
-------
Bulk techniques prove to be far more expensive because
of the associated losses of microspheres. Although no
suspension polymerized cationic resins were produced
during the program, there is no reason to believe that
acrylic resins could not be so produced if acrylic acid-
dissolved ethylene glycol dimethacrylate or water soluble
sodium acrylate were employed as reagents. Results in
the laboratory have demonstrated that the microspheres
will remain in the monomer phase, but production techniques
were not investigated for the length of time needed to
derive a procedure which would produce beads with sufficient
strength. The approach still shows great promise.
Regardless of the production technique selected, two
considerations remain paramount: 1) small bead sizes are
always preferred because of the accelerated exchange
kinetics; and 2) resins perform much better in concentrated
spills than in dilute ones.
Photomicrographs which show the hollow glass microspheres
incorporated in the resin matrices of a floating acrylic
resin and a floating epoxypolyamine resin are presented
in Figures 16 and 17, respectively.
APPLICATION METHODS
Mechanical subsurface injection by means of slurry pumps
installed on ships is probably the most desirable method
of delivery in areas such as ports and harbors where
equipment of this nature is readily available. However,
in remote areas rapid transport of subsurface injection
equipment may not be feasible. Therefore, techniques
which lend themselves to air transport and injection of
the floating sorbents were selected for development in
this program.
Air delivery would involve "bombing" the affected area
with packages containing the sorption media. In addition
to the active media each package unit must contain an
appropriate amount of ballast so that it will sink to the
bottom of a waterway prior to release of the media. The
optimal size of an individual package is dependent upon
two separate considerations: 1) achieving uniform dis-
tribution of the packages (and thus the media) over a
spill area, and 2) overall economics of the concept.
While the former consideration tends to favor smaller
packages, the latter biases the decision toward larger
units.
48
-------
Microspheres
4
FIGURE 16
ACRYLIC FLOATING CATIONIC EXCHANGE BEADS
-------
01
o
FIGURE 17
EPOXYPOLYAMINE FLOATING ANION1C EXCHANGE BEADS
-------
Ballast requirements can be determined from the bulk
density of the media employed. Media which must be
delivered in a dry state will obviously require both
larger packages and greater amounts of ballast than media
which can be delivered wet. Table 7 contains data on the
measured densities of various media and subsequent ballast
and package size requirements. Cement ballast with a
bulk density of 180 pounds per cubic foot was assumed for
the calculation of package size.
TABLE 7
Ballast and Package Size Requirements for Selected Media
Media
Furnace
Dried Carbon
Air Dried
Carbon
Wet Carbon
Dry Epoxy
Resin
Wet Epoxy
Resin
Required
Density Ballast
(Ib/ft3) (Ib/lb Media)
8
12
58.7
15.7
56.0
11.5
7.9
0.21
5.1
0.26
Size of Package
Containing
One Pound of Media,
(ft3)
0.188
0.127
0.018
0.092
0.019
51
-------
It is evident that potential packaging techniques for
the floating media and ballast for aerial delivery fall
into two categories: (1) methods employing retrievable
containers, and (2) methods employing non-retrievable
containers or containers which will decompose in water
over a period of time. Of prime importance in the program
has been the identification of a packaging technique which
would not result in significant degradation of water quality
if the packages were used in spill response activities.
Packaging techniques which were considered include plastic
containers, soluble synthetic films, unfired clay containers,
and ice cakes.
Plastic Bottles
Plastic bottles are an inexpensive/ standardized container
form potentially useful for packaging floating media.
Plastic containers were employed in column tests to
evaluate the effects of various bottle mouth widths on
media release rate and release patterns. It was observed
that media release from wide mouthed bottles was accomp-
anied by simultaneous release of quantities of large air
bubbles. These air bubbles tended to convey clusters of
media rapidly to the surface, thus preventing dispersion
of the media in the water column. Further tests indicated
that this problem could be virtually eliminated by using
containers with walls which sloped upward to a mouth of
about one inch diameter. Using this type of container,
there was a short period of media release followed by a
longer period in which small air bubbles escaped but
little media was emitted. This venting period preceded a
sustained release of clouds of media from the bottle which
distributed the media throughout the water column.
Either cement or sand and gravel proved satisfactory
as ballast in partially filled plastic bottles. One
gallon polyethylene bottles half-filled with cement were
found to withstand the impact of a fall from a fifty foot
height to a gravel bed. Similarly, these containers
withstood drops from a 100 foot height into water.
It was determined that the mouths of the plastic bottles
could be sealed with a water soluble material, Quicksol
A, to prevent the media from falling from the containers
during the air drop. However, in field trials with
carbon filled containers, it was observed that no signif-
icant quantity of media was spilled during a drop from
bottles with open mouths.
52
-------
Figure 18 is a schematic diagram of a plastic bottle of
the type used in the field demonstration containing
ballast and floating carbon.
The major drawback associated with plastic containers is
the potential aesthetic and/or ecological damage which
might result if weighted plastic bottles were allowed to
remain permanently in a waterway after treatment of a
spill.
Retrieval of plastic containers could be accomplished
either manually (e.g., by divers or with grappling hooks)
or by use of containers which will surface and float
some time after release of the media, thus permitting
surface collection. A limited laboratory study showed
that cement ballast could be attached to polyethylene
bottles with water soluble connections. After several
hours' exposure to water these connections dissolved,
causing the ballast to separate and allowing the bottles
to rise to the surface. However, this or some other tech-
nique for producing containers amenable to surface
collection would involve significant fabrication costs
for the containers. In fact, use of commercially available
plastic containers and subsequent manual retrieval from
the bottom of a waterway probably would represent a cheaper
approach. If plastic containers are to be given further
consideration as a potential packaging technique, a
thorough economic evaluation will be required in order
to determine the most viable alternative from a cost
standpoint.
Another approach which was considered but which was not
examined in great detail in this program is the use of
biodegradable containers. If a container could be
identified which would eventually degrade without creating
a significant oxygen demand or other pollution problems,
it might offer an attractive alternative. Since such
materials are still in the experimental development
stage, an adequate technical and economic assessment
of the feasibility of this approach cannot be made at
this time.
Soluble Films
Contacts with several major pharmaceutical firms indi-
cated that both the technology and equipment are presently
available for large scale encapsulation of a mixture of
ballast and floating media in water soluble capsules.
53
-------
CONCRETE BALLAST
FIGURE 18
SCHEMATIC OF CARBON FILLED PLASTIC BOTTLE
54
-------
Several samples of water soluble films and bottles were
obtained from vendors and subjected to a cursory exam-
ination to determine their suitability for containing
floating media. Individual packets with volumes of
approximately four cubic inches were prepared from each
material and loaded with sand ballast and polystyrene
chips to simulate media "bombs". Each packet was then
immersed in four gallons of tap water (@25°C) to determine
the time required for release of the'polystyrene chips.
Results of this test and pertinent product data are
given in Table 8.
Most of the films dissolved uniformly and released the
polystyrene chips cleanly with little or no partially
dissolved film adhering to them. There was some tendency
for the chips to stick to the gelatin capsules and Klucel
bottles which dissolved much more slowly. The immersion
time required for release could be adjusted by using
thicker films or multiple layers of film.
One pound of polymer will yield about 7500 square inches
of film with a thickness of three mils. If individual
packets with volumes of four cubic inches each were fab-
ricated, a pound of polymer would provide containment
for a volume of approximately 1200 cubic inches. The
weight of dry carbon thus packaged would be approximately
five pounds or a 5:1 ratio of carbon to soluble film.
This quantity of soluble film would be equal to or perhaps
greater than the spilled organic material being removed
from the water.
Experiments were conducted to study the effects resulting
from dissolution of one of the films, Quicksol A. It
was determined that 160 mg of Quicksol A dissolved in water
yielded a total organic carbon concentration of 88 mg/1.
Activated carbon at 2000 mg/1 removed 47 percent of this
TOC. The same dose of activated carbon removed 91 percent
of the 171 mg/1 phenol solution, but could adsorb only 75
percent of a phenol-Quicksol A mixture. The dissolved
film showed a definite tendency to use up available carbon
sorption capacity. Biochemical oxygen demand (BOD) tests
indicate that a 1000 mg/1 solution of Quicksol P has a
five day BOD of only 8.2 mg/1. Although the use of these
films should not cause excessive oxygen depletion at a
spill site, the addition of relatively large quantities
of soluble organic matter to the water is a questionable
approach. In addition, the tendency of the dissolved
films to use up a significant portion of the available
sorption capacity of activated carbon is not a desirable
characteristic.
55
-------
in
TABLE 8
Product Evaluation of Soluble Films
Trade
Name
Quicksol A(a)
Quicksol Pfa)
Quicksol P-U(aJ
Edisol-M(a)
Klucellb)
Polymer
Type
polyvinyl
alcohol
polyethylene
oxide
urethane
hydroxypropyl
cellulose
(food grade)
hydroxypropyl
cellulose
(food grade)
PH a Y"fTia f*& 11+" 1 (^fl 1
* net .L iiiaw^ u i. ^^cu.
gelatin capsule
Thickness
(mil)
1.25
2.0
2.25
3.0
10
12
^> &
Release
Time
(minutes)
0.5
0.25
0.75
1.25
30-50
7 Af\
£*t\J
Cost
($/lb in 1000 Ib lots)
1.94
1.94
2.00
2.22
1.75
-------
Clay Containers
In an attempt to find a packaging agent which could also
serve as the ballast material, an effort was initiated
to study the feasibility of unfired clay containers. A
local pottery shop was engaged to produce various clay
container shapes and sizes through a slip molding technique.
The resulting products were dried but were not fired so
that they displayed an affinity for water which soon
caused them to collapse when immersed.
It was found that sand could be added to the clay in
varying amounts to increase the speed with which the
package lost integrity. Inclusion of approximately 30
percent sand resulted in a decomposition time of 2 to 5
minutes. Pyramidal and cylindrical shapes displayed the
cleanest release characteristics, trapping little of the
floating media under the collapsed clay.
An impact evaluation was made to determine whether clay
containers could withstand the forces encountered when
dropped into water. Vessels shaped somewhat like artillery
shells (Figure 19) with a one quart capacity (approximately
1 ft. high x 3 in. O.D.) were dropped from a height of
100 feet into the Columbia River. Each clay container was
attached to 185 feet of light cord so that it could be
retrieved and inspected. Vessels with a wall thickness of
0.25 inch or greater withstood the impact. Those having wall
thicknesses of 0.125 inch or less collapsed. Several align-
ment modifications could potentially increase the effective-
ness of the clay cylinders. Walls could be tapered so that
heavy sections would absorb the impact while thinner walls
at the top would rapidly disintegrate when immersed in water.
Alternatively, lids could be loosely molded into place so
that soon after coming to rest on the bottom of the water
body they would fall off, allowing the media to escape. It
might also be desirable to add fins to the design since the
models tested continued to tumble when initially given
angular momentum.
Clay containers would require use of dry media and would
thus have a low payload to ballast ratio. A further dis-
advantage of unfired clay is the turbidity caused by
suspension of the fine clay particles in water. The mixing
57
-------
FIGURE 19
PHOTOGRAPH OF CLAY CONTAINER
58
-------
action caused by the release of air and media suspends
a significant amount of clay in the water. Use of a
fired clay container with an unfired clay seal is a
possible alternative to minimize the amount of suspended
clay formed.
Ice Cakes
The search for a completely innocuous encapsulation agent
led to an attractive possibility—the use of ice as a
binding agent. Ballast and media could either be layered
and frozen into discrete packages for aerial distribution
or intimately mixed and frozen into blocks which could
be shattered into any size desired at the time of release.
Advance production and stockpiling of media ice cakes
would have associated high storage costs since refrig-
erated storage would be required. In addition, sub-
limation might be a problem associated with long term
storage of ice cakes. One possible solution to these
drawbacks would be dry storage of components (media and
ballast) and subsequent quick freezing when use of the
media is required. Transport of the ice cakes might not
involve too many difficulties since low temperatures
prevail in the higher altitude flying lanes.
Column evaluations showed media release from ice packages
to have several excellent characteristics. Media release
begins almost immediately after the ice cake reaches the
bottom of the water column and the media soon distributes
itself evenly throughout the water column. Release of the
media is spread out over the period of time required for
the ice to melt and thus the release is smooth. Problems
with air bubbles are avoided and ballast requirements
are much less than when dry media is utilized.
Freezing the media in an ice matrix was found to have no
debilitating effects on the performance of floating ion
exchange resins. Packaging in ice did, however, appear
to result in some loss of capacity in the case of the
floating carbon. Parallel column removal tests run with
a standard phenol solution showed that unfrozen carbon
removed 65 percent of the phenol while an equal quantity
of carbon frozen in an ice cake achieved only 51 percent
phenol removal. Removal differences fluctuated in sub-
sequent tests, but the carbon ice cakes were always found
to be somewhat less effective than unfrozen carbon.
59
-------
Parallel column runs with unfrozen carbon at solution
temperatures of 0°C and 17°C showed little difference
in phenol removal efficiencies (75 percent at the lower
temperature and 77 percent at the higher) . This ob-
servation .led to the conclusion that the reduced
efficiency -of the carbon frozen in ice cakes was not a
function of temperature so much as the result of inter-
actions between the ice and the carbon. It was noted
that finer carbon particles appeared to floe when
released from the ice cake. Flocculation of carbon
particles was not observed in release from plastic
bottles. This flocculation effect could reduce the
actual coverage of the media and hence reduce removal
efficiency. In addition, it is possible that residual
ice crystals on the carbon may interfere with surface
forces and hence reduce sorption.
In deference to the major objectives of the program,
these apparent interactions were not fully explored.
Because of the lower ballast requirements and superior
dispersion of the carbon near the bottom of the stream
or lake, the carbon ice cake approach appears preferable
in spite of the somewhat lower sorption capacity or rate.
However, further work is needed to establish the feasi-
bility of the carbon ice cake packaging concept. Clearly,
there is great promise-in the use of ice with floating
ion exchange resins.
60
-------
SECTION VI
FIELD DEMONSTRATIONS
In order to test the effectiveness of the floating media
concept on the scale and under the conditions of actual
hazardous materials spills, field demonstrations were
conducted using both the floating epoxypolyamine anion
exchange resin and the floating Nuchar C-190 carbon.
These demonstrations concerned application of the floating
media concept to static or impounded water only. Treat-
ment of flowing streams may involve different techniques
because of the turbulence of the water.
DIAZINON SPILL
A 10 million gallon water storage basin was selected for
the spill treatment demonstration. The basin was filled with
Columbia River water to a depth of 12 feet and calibrated
ropes were placed across the western end of the 200 x 400
foot structure as illustrated in Figure 20.
A commercial grade of the organophosphorus pesticide,
Diazinon, was selected for the spill. Diazinon is highly
toxic to aquatic life forms and hence causes major concern
when spilled. It is not persistent beyond several weeks,
however, so immediate complete cleanup by the floating
carbon was not required in the event discharge of the basin
water was required at some future date. The composition
of the 48 percent Diazinon in an emulsifiable solution is
given in Table 9. Seventy-eight pounds of the organic
solution emulsified in 160 pounds of water was employed
for the spill.
TABLE 9
Composition of Emulsifiable Diazinon Solution
Ingredient Percent
0,0-diethyl 0-(2-isopropy1-4-methyl- 48
6-pyrimidinyl) phosphorothioate
Xylene 36
Inert Ingredients 16
61
-------
10
400'-
I
-N-
SPENT CARBON
COLLECTION TANK
CALIBRATED
ROPES
INITIAL SPILL ZONE
400 SO. FT.
COLLECTION
PIPE
DIAPHRAGM PUMP
BUOY
DEPLOYED
BOOM
HATER STORAGE BASIN
200'
FIGURE 20
LOCATION OP FACILITIES FOR DIAZINON SPILL
-------
The Diazinon was spilled at 0700 by spreading the 25
gallons of emulsion from a rowboat in a 20 foot by 20
foot square as illustrated in Figure 20. Aerial photo-
graphs of the spill taken at 0715 are given in Figures
21-22. Sampling of the spill area began at 0730. Samples
were taken with ten foot aluminum tubes connected by
flexible tubing to peristaltic pumps. One liter glass
bottles were filled with water withdrawn from 1, 5, and
10 foot depths. Sample lines were thoroughly flushed
between sampling points.
A total of 845 pounds of Nuchar C-190 activated carbon was
employed in treating the spill which is about a 10:1 ratio
of carbon to Diazinon. The carbon included 675 pounds of
40 x 325 mesh carbon and 170 pounds of 12 x 325 mesh
carbon packaged in 1,128 one gallon polyethylene bottles
each of which contained 1/2 gallon of carbon (3/4 pound)
and 1/2 gallon of concrete (8 pounds).
Bottles of carbon and ballast were dropped into the spill
area from a helicopter equipped with a platform suspended
beneath the helicopter with a sling. Servo-motors mounted
on a drop gate of the platform were wired for control from
within the helicopter. The slings were fixed with an offset
harness so that under normal flight conditions they would
hang at an oblique angle with 60 carbon-filled bottles
(540 pounds) resting against the drop gate. Over the drop
site the gate was opened and the bottles were allowed to
slide down into the water. Figure 23 shows the platform
in place beneath the helicopter. Two platforms were employed
so that one could be loaded while the other was in use.
The actual treatment phase of the demonstration was begun
at 0810 when the first of 17 loads of carbon were dropped
into the spill area as shown in Figure 24. Flags were used
to mark the drop lane and a flagman was employed to signal
the helicopter pilot to release the gate. In this manner
drops were distributed evenly across the contaminant plume.
Due to a failure in the gate control of both platforms, the
18th and final load could not be dropped from the helicopter.
These bottles were subsequently distributed by hand from the
side of the basin and from a rowboat. The application work
was completed by 1100; however more than half the carbon was
dropped by 0915. Intermittent failure of the tailgate
release on the platforms increased the time between subse-
quent drops after 0915. Three of the 1128 bottles contained
insufficient ballast and consequently floated to the surface
without releasing their carbon.
63
-------
FIGURE 21
AERIAL PHOTOGRAPH OF DIAZINON SPILL
-------
en
Ul
FIGURE 22
CLOSEUP OF DIAZINON SPILL IN SAMPLING GRID
-------
cr>
FIGURE 23
PHOTOGRAPH OF HELICOPTER WITH SLING
-------
FIGURE 24
PHOTOGRAPH OF AIR DROP INTO SPILL AREA
-------
By 1000 carbon was very evident in the surface waters around
the spill. Many portions of the contained area were too dark
to allow observance of objects more than six inches beneath
the surface. A thin oil slick was also visible on the water
since, as previously mentioned, prior to this field demonstra-
tion the basin was used for numerous oil spill contaminant
demonstrations and residue oils remained behind after this
work. As the bottles disturbed the water and moved down
through the weeds on the bottom of the pond, globules of
this residual oil were freed to rise and form a slick. The
carbon appeared fairly effective in removing this oil as
well as the Diazinon.
At 1400 two sampling boats set out to scoop random carbon
samples from the surface of the spill area. These were
composited for evaluation at a later time. Post spill
water sampling was then initiated using the same procedure
as before but this time with a greater number of sampling
points.
The samples were analyzed for both phosphate and total
organic carbon (TOC). The latter determination may be
subject to some error due to the presence of oil slicks
from previous spill studies in the basin water. Phosphate
was determined by digesting an aliquot of the sample with
a sulfuric acid-nitric acid mixture prior to colorimetric
measurement of the phosphate concentration by the ascorbic
acid-phosphomolybdate method(7). Analysis of basin water
with known concentrations of Diazinon gave 98 percent
recovery of the phosphate by this procedure. The TOC
analyses were performed with a Beckman Model 915 carbon
analyzer.
Results of the phosphate analyses of the pretreatment and
posttreatment samples are given in Figure 25, with the
locations on the sample grid. Several increases in phos-
phate concentrations are noted between pretreatment and
posttreatment samples which are believed to be largely
caused by analytical variations. Additional posttreatment
phosphate analyses are given in Figure 26. The data illus-
trate that the emulsion was relatively dense and the bulk
of the spilled Diazinon formed a layer near the bottom of
the basin. Laboratory studies conducted with the six inch
diameter column did not indicate bulk movement of a fine
emulsion to the bottom of the column. The density of the
Diazinon is greater than water while the density of the
xylene in the emulsifiable solution is less than water.
Large droplets of the emulsifiable solution will float when
initially dropped in water but will slowly sink after a few
minutes. It is believed that the lighter xylene is either
evaporated or extracted into the water causing the density
of the droplet to increase.
68
-------
10 FT II
* (I 8-0 0) 100
B I* 9-0 2) *t
C |4 0-0.9) 78
ZO FT U
I (1 1-1 2) «(.
B (12 4-0 0) 100
C (1} 6-0 9) fS
10 FT H
A (1 9-0 2) 89
B (7 6-0 0) 100
C (13 0-0 4) 97
is FT H
• (0 0-0.0) 0
B ID 0-0 0) 0
C (0 0-0.1) ---
5 FT H
K (0 2-0.2) 0
B (1 4-0 2) 16
c t) 1-0.6) ai
• CENTER
A (2 0-0 2) 90
I (4 «-Q 4) 91
C (10 3-0 9] 91
I FT DEPTH
S FT DEPTH
10 FT DEPTH
DISTANCE AflO DIRECTION FBOM CENTO
mm»lHEM1 W>4 COHCUimTlON. rag/1
POSttREATHEHI P04 CONCf»TB*TIOI1, aq/l
PERCENT REOUC1IOH
S FT C
A (O.S-O.Z) 60
a (i 1-0 o) 100
C (10 9-0 2) 98
15 FT E
A (0.7-0.3) 57
B (1 6-0 it 18
C (10 5-0 1) 97
Zi FT C
A (O.B-0.2) 7S
B (I 0-0 II 60
C (7 1-0.4) 95
FIGURE 25.
RESULTS OF PHOSPHATE ANALYSIS ON
PRETREATMENT AND POSTTREATMENT SAMPLES
69
-------
39 FT SH
A 0.2
B 0.2
C 0.9
25 FT NW
A 0.2
B 0.0
C 0.4
25 FT SW
A 0.3
B 0.2
C 0.3
A = 1 FT DEPTH
B = 5 FT DEPTH
C = 10 FT DEPTH
(P04 IN mg/1}
39 FT HE
A 0.0
B 0.0
C 0.4
25 FT NE
A 0.0
B 0.0
C 0.2
11 FT NW
A 0.2
e o.o
C 0.5
11 FT SH
A 0.0
B 0.2
C 0.6
X^
11 FT NE
A ---
B 0.0
C 0.0
n FT SE
A 0.2
B 0.2
C 0.4
25 FT SE
A 0.3
B 0.5
C 0.3
39 FT SE
A 0.2
B 0.0
C 0.3
FIGURE 26
ADDITIONAL RESULTS OF PHOSPHATE ANALYSIS
ON POSTTREATMENT SAMPLES
70
-------
Observations indicated that the wind drifted the emulsion
briefly to the south and east while the emulsion was near
the surface, but once the emulsion settled several inches
into the water it appeared to remain stationary. The bulk
movement to the west as indicated in the data of Figure 25
and in the aerial photograph, Figure 21, was not observed
visually at ground level following the spill.
Results of the TOC analyses presented in Figures 27 and 28
correlate reasonably well with the phosphate'analyses. As
in the case of the phosphate results, several increases
occurred between pretreatment TOC concentrations and post-
treatment TOC concentrations. Analytical variations and
oil contamination of the samples are believed to have
caused these increases. Interpolation of the TOC data over
the affected water column accounts for 66 pounds of the
Diazinon solution or 85 percent of the 78 pounds originally
spilled. Similarly, the phosphate data accounts for 68
pounds or 87 percent of the original solution spilled.
Based upon the water sampling data, the total quantity of
Diazinon remaining in the water column after treatment was
calculated in the same manner as had been the spill account-
ability numbers from the pretreatment data.
Phosphate analyses indicated a total of 4.2 pounds of Diazinon
solution left in the water, or five percent of the original
78 pounds. Total organic carbon analyses indicated a residual
of five pounds or six percent of the original spill. This
suggests an average of 94.5 percent removal from combined
dilution and treatment effects. However, examination of
the post treatment data revealed that low concentrations of
Diazinon might occur for some distance outside the sampling
grid. Since most of the carbon was applied rapidly to the
major dispersion of the spill in the southwesterly direction
it is believed that good contact was made between the carbon
and the bulk of the spill. Eddy currents set up by bottles
descending to the bottom of the basin may have persisted for
some time after the treatment and may have caused dispersion
of the treated water containing low concentrations of the
Diazinon. As a worst case estimate, a volume six times that
of the sample grid could be assumed to have the same average
posttreatment Diazinon concentration as that found within
the sample grid. In such a case the removal would be 67
percent. The volume of water would then include both that
in the sample grid and all of the water contained outside the
grid in the basin west of the eastern edge of the sample grid.
Thus, the actual removal of Diazinon should be between 67
and 94 percent.
Composite samples of carbon collected after treatment of the
Diazinon spill were analyzed in an effort to determine the
amount of Diazinon recovered by the carbon. The results of
71
-------
is rr *
» (7.1-1.5) 79
I (1.7-0.1) SI
C (1.8-4 1) -131
IS FT »
» (7 3-1.5) -1
6 (I.I-I.4) -17
C (J.6-I.I) ii
JO rr v
I (H 7-2 1) SI
e (id 5-2 6) 87
C (IS 3-1 i) 7)
.
20 Fl U
« (12 7-1 4) 89
B (39 6-0 2) 49
C (43 2-3 0} 41
•
10 FT H
» 17 J-1.4) 81
B (2« 0-0 7} 97
C (47 8-J 6] »
—
Cdrrti
* (a s-o si 94
B (17 8-2 1) 88
C (IS 6-5 0) 86
•
S Fl E
A (4 0-2 3) 4)
B (11.0-1 0) 91
C (33.0-0 1} 98
m
IS Fl (
« (4 6-4.7) -2
8 (6 8-1.6) 76
C (37 1-2.2) 94
M
15 FI c
* (4 5-1 8) «0
8 (8 0-2 2) 73
C (22.0-1 2) 94
0
• (©-Q)i ©
8
C
» i n OIPIN
10 FT S
* (IS 2-1 0)
B (16 7-1 8)
C (SI 4-2 S)
93
89
9i
I
25 FT S
1 (3 2-1 1)
1 (14 3-1 4)
C (30 S-? <)
6(
90
91
1
40 FT S
(4 0-1 OJ
(4 6-0 8)
(2 5-3 0) .
t 10 n DIPIH
Q OISTIIICE >ND OlXCIlOn ritOM CEJIHH
© pRtrRCurHEnr 100 ccncciirMrioii. ««/)
Q POSTixiiHiM ioc co»ctmii«iioii, 19/1
© PEBCtNJ «EOUCIION
75
83
20
FIGURE 27
RESULTS OF TOC ANALYSIS ON PRETREATMENT
AND POSTTREATMENT SAMPLES
72
-------
25 FT NW
A 3.2
B 2.0
C 5.0
A = 1 FT DEPTH
B = 5 FT DEPTH
C = 10 FT DEPTH
(TOC IN mg/1)
25 FT SH
A 1.7
B 1.8
C 4.6
25 FT NE
A 1.9
B 1.2
C 1.5
11 FT NW
A 0.4
B 0 6
C 2.7
11 FT SU
A 0.4
B 0.9
C 2.9
y
11 FT NE
A
B 1 5
C 1.0
11 FT SE
A 1 4
B 7 1
C 11 .9
25 FT SE
A 1.8
B 1.4
C 1.8
39 FT SH
A 1.8
B 1.4
C 3.0
39 FT SE
A 2.6
B 1.3
C 1.8
FIGURE 28
ADDITIONAL RESULTS OF TOC ANALYSIS
ON POSTTREATMENT SAMPLES
73
-------
these analyses were inconclusive, however, due to considerable
variation between analytical results. Insufficient informa-
tion was found in the literature concerning the extraction of
Diazinon from carbon for subsequent analyses. The develop-
ment of adequate analytical procedures for analyzing the
carbon for Diazinon content would require a level of effort
for which time and funding were not available.
Sediment samples were analyzed to verify that the pesticide
had not settled and associated itself with the bottom sedi-
ments. No change in sediment phosphate levels was detected.
Sediment supernatant samples showed a slight increase in
phosphate level. This increase, however, when extrapolated
to the total spill area could account for less than 50 grams
of Diazinon. It is clear that the floating carbon proved
highly effective in removing the spilled Diazinon emulsion.
Even greater efficiencies could be expected for light organics
which would remain near the surface. In such cases, the
rising carbon would simulate a countercurrent contacting pro-
cess. Carbon resting on the surface or gently circulating
nearby with wave action would remain in contact for greater
periods of time and thus remove larger amounts of the organic
contaminant.
Booming operations were begun at 1415. A 200 foot spliced
section of a plastic Rodeorm Oil Containment boom manufactured
by Trelledorg, Inc. was used to herd the carbon into the
southeast corner of the basin.
The boom was pulled through the water manually with the aid
of rope attached to the end of the boom. The northern end
was first brought into the western wall, and then the tri-
angle thus formed was diminished by moving both ends of the
boom towards the apex. It was found that the carbon herded
easily with no underwash evidenced.
At the beginning of the booming operation the wind had driven
most of the carbon to the collection corner. During the
operation the wind shifted causing the carbon to drift out
against the boom. Some carbon escaped by moving out through
the gap left between the end of the boom and the basin wall.
Most of the carbon, however, appeared to pile up against the
boom.
When the boom was well into the corner, carbon appeared to
form a blanket up to two inches deep in places. A "J" shaped
pipe was lowered into the corner of the basin and connected
to a gasoline powered diaphragm pump. Figure 29 illustrates
the placement of the pipe. The suction from the pump drew
down a vortex from-the surface of the basin and thus removed
the carbon, which was then pumped to a 15 foot diameter
portable swimming pool. The booming operation was completed
by 1645. Water in the pond appeared to have returned to its
original clarity with no noticeable carbon residues.
74
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PUMP TO
COLLECTION
BASIN
BOOM
2" x 4" BELL REDUCER
RETAINER
WALL
FIGURE 29
PLACEMENT OF THE COLLECTION PIPE AND BOOM
75
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Water was subsequently drained from the carbon storage tank
and the remaining carbon was allowed to dry. Measurements
of the total volume and bulk density of the recovered carbon
indicated that 90 percent of the original volume of carbon
was recovered. Laboratory tests show that two percent of
the carbon employed in the demonstration does not float and
an additional one percent remains in the plastic container.
A substantial portion of the remaining seven percent lost in
the demonstration may have been trapped on weeds in the
bottom of the basin and may not have floated to the surface.
The 90 percent recovery was considered to be good.
No alternative skimming or booming devices were tested for
comparison of effectiveness.
SULFURIC ACID SPILL
An abandoned sedimentation basin on the Hanford Reservation
was selected for evaluation of the floating epoxypolyamine
anion exchange resin. The 30 x 50 foot concrete lined basin
was filled to a depth of six feet with water from a nearby
fire hydrant.
Sulfuric acid was selected for the field demonstration since
it is the chemical produced in the greatest quantity in the
United States and it represents one of the major hazardous
spill threats. During predemonstration tests it was found
that concentrated solutions of sulfuric acid would rapidly
sink and spread out over the bottom of the test basin when
introduced at the surface of the water.
It was also observed that lateral movement of a dilute acid
spill was too rapid in the basin to allow effective spill
treatment with the quantity (13.7 cu. ft.) of floating ion
exchange resin available for the demonstration. Water
currents in the basin appeared to be largely responsible for
the movement rather than dispersion of the acid in the water.
It was therefore decided to conduct the demonstration spil'l
of sulfuric acid in a small submerged open tank (five feet
in diameter by two feet high) placed in the basin. The tank
served to simulate the kind of natural depression found in
most river beds or lake bottoms. Further predemonstration
testing with a submerged tank showed some loss of sulfuric
acid when the spill occurred at the surface of the water
directly over the center of the submerged tank. The concen-
trated acid descended rapidly, thereby gaining sufficient
momentum to travel across the bottom of the tank and up the
wall to spill a portion of the acid over the wall of the
tank. In order to avoid any loss of acid from the simulated
depression, a subsurface spill of concentrated sulfuric acid
was planned for the spill treatment demonstration.
76
-------
The acid spill treatment demonstration was conducted with 45
pounds of concentrated sulfuric acid containing one ounce of
m-cresol purple indicator which imparted a red color to the
acid, thus allowing visual observation of the acid beneath
the water surface. Sulfuric acid was transferred to the
submerged tank in the basin via a one inch diameter PVC pipe.
At the completion of the transfer, the acid blanketed the
floor of the tank in a thin layer less than two inches deep.
Pretreatment sampling was performed using a six foot length
of 1/4 inch diameter stainless steel tubing connected to
flexible tubing and a peristaltic pump. Analysis of the pre-
treatment samples showed acid to be virtually completely
contained in the thin layer on the bottom of the tank. A pH
reading of 3.8 was recorded at the top wall (two feet above
the bottom) of the tank. Directly above the tank and one
foot below the water surface the pH was determined to be 6.9
as opposed to a prespill pH of 7.2.
Fifty media ice blocks containing epoxypolyamine anion resin
and gravel ballast were used in the spill treatment operations.
The media ice blocks were prepared by covering a layer of
gravel in a mold with a layer of 30 percent resin slurried in
water and freezing in a home freezer unit. Each media ice
block was packaged in a plastic bag and stored in a freezer
until use. A schematic diagram and a photograph of the media
ice blocks used in the demonstration are given in Figures 30
and 31, respectively.
During the spill treatment operation, the media ice blocks
were removed from the plastic bags and were dropped into the
spill area approximately 30 minutes after the sulfuric acid
was spilled. Nearly half of the media was dropped around the
periphery of the submerged tank and the remainder was fairly
evenly distributed on the bottom of the tank. It was planned
that a substantial portion of the resin ice cakes should fall
outside of the tank to provide resin for acid sorption above
tne periphery of the submerged tank. Laboratory studies had
suggested that resin rising from the tank would cause vertical
mixing and dispersion of the acid above the tank. However,
little of the anticipated mixing actually occurred, because
transferring the acid directly to the bottom of the tank
caused formation of a thin, dense acid layer. It is believed
that the layer of gravel ballast on the bottom of the resin
ice cakes held the resin above the acid layer thus virtually
eliminating contact between the resin and the acid.
Analysis of samples taken after the spill confirmed that only
a small portion of the acid was removed from the water by the
resin. Post spill sampling was carried out in the same manner
as the pretreatment sampling. The only real change in acidity
appears to have occurred in the center of the tank near the
top, where the pH rose from 3.8 to 6.6. Apparently a small
amount of vertical mixing occurred at this point.
77
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-o
to
FLOATING EPOXYPOLYAMINE
ANION EXCHANGE RES IN
2" RES IN-ICE LAYER
1.25" GRAVEL BALLAST LAYER
FIGURE 30
TYPICAL "MEDIA CAKE" EMPLOYED IN BASIN DEMONSTRATION
-------
FIGURE 31
PHOTOGRAPH OF RESIN ICE CAKE
-------
Within two hours, all of the resin had reached the surface (Fig-
ure 32). Samples of the floating resin were continuously taken
and composited as the media surfaced. The resin samples were
thoroughly mixed and a composite sample was then analyzed to
determine the capacity utilization and sulfate sorption. The
unused ion exchange capacity of the spent resin was determined
by titrating samples of the resin with standard acid. The
results showed a difference of 0.405 milliequivalents per gram
when compared to the capacity of virgin floating resin. This
represents 4.43 pounds of sulfuric acid when extrapolated to
the total of 13.7 cubic feet of resin dropped, or ten percent
of the original 45 pounds of concentrated acid spilled.
Similarly, analysis of the spent resin for sorbed sulfate
ion revealed 22.1 mg more sulfate per gram of resin than in
the virgin floating resin. This accounts for 5.3 pounds of
sulfuric acid or 12 percent removal. The sorbed sulfate on
the spent resin was determined by eluting samples of the
resin with 1 N NaOH and measuring the eluted sulfate by a
turbidimetric 83804 procedure.
This low level of removal is not considered representative of
the potential of the floating ion exchange resins for treat-
ing spills of electrolytes. There is no reason to believe
that the resin would not be effective for a diffuse or diluted
spill. A demonstration of this type to treat an unconfined
spill would require considerably more resin than could be
feasibly produced in this program.
The acid spill demonstration does, however, point out the
need for sufficient contact of the sorbent with the material
to be removed since densely layered spills are certainly
within -the realm of possibility. The sorbent-ice cake repre-
sents the most logical approach to attaining good bottom
contact. Neither bottles nor clay containers would approach
the same degree of bottom contact. Placement of the ballast
in the center of the resin-ice cake rather than on the bottom
would be expected to improve bottom contact. To be fully
effective, however, the material to be removed must be
dispersed above the resin-ice cake for good contact with
the main plume of resin rising above the cake.
Two days after the acid spill, operations to recover the ion
exchange resin were initiated. The resin was easily boomed
and herded to a corner of the water basin where it was
skimmed from the surface and dewatered by screening through
a 100 mesh screen. Virtually complete recovery of the total
quantity of floating resin used in the spill treatment demon-
stration was achieved in this manner.
80
-------
00
-
g
FIGURE 32
SAMPLING FLOATING RESIN AFTER TREATMENT
-------
SECTION VII
APPLICATION
Although the basic concept of utilizing floating media for
spill treatment has been successfully dfcmonstrated/ it is
emphasized that neither media production methods nor
application techniques have been fully optimized. The
following discussion will summarize the status of the
technology developed for treating hazardous material
spills with floating mass transfer media/ however/ and
provide some understanding of its use.
Floating activated carbon represents thfi most versatile
media evaluated in this work because of its ability to
remove a broad range of hazardous materials/ principally
organics, from water. Although only a few hazardous
materials (phenol/ benzene, toluene, styrene, Diazinon,
Malathion, and acrylonitrile) were investigated in this
study, activated carbon could be effectively used for
adsorbing many other organic substances which have limited
solubility in water and/or consist of long-chained
molecular structures. Included in this category are a
wide variety of hydrocarbons; organic halogen compounds
(e.g., pesticides); long-chained monofunctional alcohols,
aldehydes, ketones, and fatty acids; low solubility esters;
and many others. Examples of common organic compounds
which are not readily adsorbed from aqueous solutions are
methanol, ethanol, urea, sugars, and ethylene glycol.
Effective treatment of hazardous organic material spills
with floating activated carbon will depend on the following
factors.
1. The material must be readily adsorbed by the
carbon from aqueous solutions.
2. The carbon grain size should be small, prefer-
ably in the 50 x 325 mesh size range, with a
significant fraction passing a 100 mesh sieve.
3. The carbon must be pretreated by soaking in
water and drying at a low temperature (100°C
or less) to assure proper wetting and disper-
sion when released from packages beneath the
spill zone.
83
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4. The spill zone must be accurately defined and
the carbon applied accordingly. On-the-spot
judgments may necessitate application of a
larger amount of carbon where higher concen-
trations of spilled material are believed to
exist. A 10:1 ratio of carbon to spilled
material is recommended for application.
5. Response to the spill must be rapid since dis-
persion of the spilled material over a wide
area will decrease the effectiveness of the
carbon and may prevent accurate location of
the material.
6. The floating carbon containing the sorbed haz-
ardous material must be collected and removed to
prevent desorption of the material into uncon-
taminated water (desorption will be slow unless
wave action or other surface turbulence disperses
the carbon in the water).
Release of the floating carbon from weighted plastic
bottles in a hazardous material spill zone has been demon-
strated, but only in static or impounded waters. Application
to flowing streams may require a different technique.
Other methods of application such as subsurface injection
by infusion pumps and release from ice cakes or unfired
clay containers appear practical but have not been demon-
strated on a large scale.
The use of a floating epoxypolyamine ion exchange resin
for removing hazardous substances has also proved successful.
The resin was prepared by incorporating buoyant hollow
glass microspheres in the resin matrix. As is the case
with activated carbon, a small resin particle size is
required to maximize the effectiveness of this medium. The
floating epoxypolyamine ion exchange resin obtained for
the field demonstration had a particle size range of 16 x
100 mesh with the bulk of the resin particles in the 16 x
40 mesh range. A particle size passing a 50 mesh screen
would be more desirable; however, production methods must
be refined to accomplish this.
The floating epoxypolyamine resin evaluated during this
program was found to be quite effective in removing acid
from water. The field demonstration pointed out, however,
that spills of high density acids may be difficult to
treat because the acid forms a dense layer at the bottom
84
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which cannot- be readily contacted by the resin. The ice
cake method of applying the resin represents the most favor-
able packaging concept investigated for use in treating
hazardous materials concentrated near the bottom of a body
of water. Although the floating epoxypolyamine resin has
been evaluated for use in treating only acids in this study
it is anticipated that the resin will be useful for
removing toxic anions (e.g., cyanide) also.
The effective use of the floating ion exchange resin in
treating spills will be governed by the same conditions
as those for carbon listed above with the exception of
pretreatment (item 3}. The ion exchange resin is maintained
in a moist condition and should not be allowed to dry out.
The feasibility of commercial production of floating
activated carbon and floating epoxypolyamine resin has been
demonstrated. Although production methods have not been
optimized, .sizable quantities of these materials can be
obtained for further studies or for application in the
field. The sources of these materials and costs are
given in the Appendix.
85
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SECTION VIII
ACKNOWLEDGMENTS
The assistance and advice provided by Mr. Ira Wilder, EPA
Project Officer, are gratefully acknowledged. The authors
also wish to express their appreciation to Westvaco for
samples of activated carbon provided for experimental
studies; to Dr. Irving M. Abrams, of the Diamond Shamrock
Chemical Company, who provided information and suggestions
concerning the preparation of ion exchange resins; and to
Battelle-Northwest personnel, Mr. James Coates, Mr. Marvin
Mason, Mr. Richard Parkhurst, Mr. Greg Swank, Mr. Robert
Upchurch, Mr. Gary Schiefelbein, and Mr. Terry Brix, who
assisted in the carrying out of the experimental work.
87
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SECTION IX
REFERENCES
1. Thompson, C. H., and P. R. Heitzenrater. "The Environ-
mental Protection Agency's Hazardous Material Spill
Program." Presented at the American Institute of
Chemical Engineers Workshop, Charleston, West Virginia,
October 27-29, 1971.
2. Thompson, C. H., and K. E. Biglane. "Oil and Hazardous
Materials—The Chemical Industry's Liability or Asset.11
Presented to Chemical Markets Research Association in
Chicago, 111., Feb. 24, 1971.
3. Hyndshaw, A. Y. "Use of Activated Carbon to Prevent
Water Supply Contamination." Water and Waste Engineering,
February, 1969.
4. Swindell-Dressier Company. "Process Design Manual
for Carbon Adsorption." Environmental Protection Agency,
Technology Transfer, Program 117020 GNR, Contract
#14-12-928, p. 4-4, October, 1971.
5. Product Data Bulletin, Nuchar Granular Activated
Carbon, Grade WV-L 8 x 30, Westvaco Chemical Division,
West Virginia Pulp and Paper Company.
6. Hassler, J. W. Activated Carbon. Chemical Publish-
ing Company, New York, NY, p. 330, 1963.
7. Standard Methods for the Examination of Water and Waste-
water . 13th Edition, APHA, AWWA, WPCF, 1971.
8. Boyd, G. E., A. W. Anderson, and L. S. Meyers, Jr.
"The Exchange Adsorption of Ions from Aqueous Solutions
by Organic Zeolites II. Kinetics." Journal ACS, Vol.
69, November, 1947.
9. Kressman, T. R. E. , and J. A. Kitchener. "Cation^
Exchange with a Synthetic Phenolsulphonate Resin."
Faraday Society Discussion, No. 7, 1949.
10. Helfferich, F. Ion Exchange. McGraw Hill, San Francisco,
California, 1962.
89
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SECTION X
APPENDIX
SOURCES, PREPARATION, AND COSTS OF
FLOATING MASS TRANSFER MEDIA
ACTIVATED CARBON
The floating activated carbon used in the field demonstration
was prepared from Nuchar C-190, +30 mesh carbon manufactured
by Westvaco of Covington, Virginia. Four thousand pounds
of this carbon were purchased at a cost of $1,693 delivered
to Majac, Inc., of Pittsburgh, Pennsylvania. The carbon
was pulverized and air classified to remove the fines
(-325 mesh) by Majac at a cost of $1,200. The carbon
was then shipped to Battelle-Northwest for the remaining
processing steps which consisted of dry sieving to separate
the 40 x 325 mesh fraction and washing and drying to condition
the carbon to wet and disperse properly when applied for
spill treatment.
The production rate of the continuous sieving apparatus
used to separate the desired mesh fraction was limited to
about four pounds of 40 x 325 mesh carbon per hour. Wash-
ing was accomplished by mixing the carbon with water in a
50 gallon tank to thoroughly wet the carbon particles. The
carbon was then allowed to rise to the surface, removed
from the tank by skimming, and placed in canvas bags for
draining.
Drying was accomplished in about one week at ambient air
temperatures by spreading the damp carbon to a depth of
1-2 inches on diamond mesh sisal paper in well ventilated
rooms. The average temperature and relative humidity
during the drying period were 70°F and 48 percent, res-
pectively .
Seventy-one percent or 1700 pounds of the carbon received
from Majac was processed throuah the sieving apparatus.
The final yield of treated 40 x 325 mesh carbon was 675
pounds which cost $1539 to process through the sieving,
washing, and drying steps. The total cost of the 675
pounds of 40 x 325 mesh carbon was $3,593, which includes
the $1,539 above and 71 percent of the purchase and
pulverizing/air classifying costs.
91
-------
Since the completion of this work Westvaco has discontinued
sales of the +30 mesh and unground grades of Nuchar C-190
and will soon discontinue sales of the same grades of
Nuchar WA. Westvaco will continue to market a fine mesh
size of Nuchar C-190 (Nuchar C-190 N) with about one-third
of the carbon in the 100 x 325 mesh range. This material
costs approximately 17 cents per pound (excluding delivery
costs) in quantities of 30,000 pounds or more, which is
about half the cost of the +30 mesh grades formerly
marketed. The Nuchar C-190 N carbon has not been evaluated
as a floating mass transfer media; however, there is no
reason to expect that it would not function as well as
the other grades tested. In addition to the lower purchase
price, the Nuchar C-190 N could be processed to give the
desired mesh size at a lower cost since no pulverization
would be required.
Westvaco also markets another grade of powdered carbon,
Nuchar C-115 N, which has about one-third of the carbon
in the 100 x 325 mesh range. A cursory examination indicates
a high percentage of floating particles in the desired
mesh size range.
EPOXYPOLYAMINE RESIN
The floating epoxypolyamine ion exchange resin was obtained
by special order from the Diamond Shamrock Chemical Company,
Nopco Chemical Division, Duolite Ion Exchange Resins,
Redwood City, California. Five hundred pounds (14 cu. ft.)
of this resin were purchased for $4,000.
The floating anion exchange resin prepared in the Diamond
Shamrock Chemical Company's development laboratories was
characterized as follows:
Reference number 1,219, 67
Free base form 100 percent floaters
Chloride form 100 percent floaters
Sulfate form 95 percent floaters
Total acid absorption 7.2 mg/gm
capacity (dry weight basis)
Moisture retention capacity 59 percent
Granule strength Fairly hard
Particle size 30 to 70 mesh
92
-------
The 500 pounds of resin produced in plant facilities had
essentially the same characteristics except that the
particles were largely in the 16 to 100 mesh size range.
•OS GOVERNMENT PRINTING OFFICE 1973 546-312/162 1-3 93
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
/. Report No
3. Accession No
w
4 Title
TREATMENT OF HAZARDOUS MATERIAL SPILLS
WITH FLOATING MASS TRANSFER MEDIA
7 Author(s)
Mercer, B. W., Shuckrow, A. J., and Dawson, G. W.
9 Organization
Battelle Memorial Institute
Pacific Northwest Laboratories
Richland, WA 99352
12. Sponsoring Organization
15 Supplementary Notes
Environmental Protection Agency report number,
EPA-670/2-73-078, September 1973.
5. Report Date
6.
8 Performing Organization
Report No.
W Protect No
15090 HGQ
11 Contract/Grant No
Contract 68-01-0124
13 Type of Report and
Period Covered
16 Attract An approach for the in situ treatment of spills of soluble haz-
ardous polluting substances was developed and demonstrated on a field scale
for a static body of water. Laboratory scale experimentation showed that
floating sorbents and ion exchange resins could be highly effective removal
agents when applied as small particles beneath the surface of contaminated
waters.
A lightweight commercial activated carbon was found to be partic-
ularly effective for removing organic substances such as phenol, aromatic
lydrocarbons, and organophosphorus insecticides from water.
Floating ion exchange resins were also prepared for use on spills
jf acid, alkalis, and toxic salts. Hollow glass microspheres are incorpor-
ated in the resin granules for buoyancy.
Field demonstrations were conducted using carbon contained in
weighted plastic gallon bottles. The carbon proved highly effective in
removing an organophosphorus pesticide spilled in a large basin, and was
sasily collected through use of an oil containment boom. Ice encapsulated
floating anion exchange resin beads were similarly employed to neutralize
i spill of sulfuric acid.
17a Descriptors
"Activated Carbon, *Ion Exchange,*Resins,*Water Pollution Treatment, Water
Pollution Control
776 Identifiers
"Spills, *Hazardous Materials, -"Hazardous Chemicals ,*Mass Transfer Media
17c COWRR Field & Croup 05G
18. Availability
19. Security Class.
(Report)
20. Security Class,
(Page)
21. No of
Pages
22. Price
Send To:
WATER RESOURCES SCIENTIFIC INFORM ATION CENTER
US DEPARTMENT OF THE INTERIOR
WASHINGTON. D C 20240
Abstractor A. j. Shuckrow
{institution Battelle Memorial Institute
WRSICI02(REV JUNE 1171)
Pacific Northwest Laboratories u.a«t
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