svEPA
United States
Environmental Protection
Agency
Office of Emergency and
Remedial Response
Washington, DC 20460
Office of
Research and Development
Cincinnati, OH 45268
Superfund
EPA/540/2-91/024
October1991
Engineering Bulletin
Granular Activated
Carbon Treatment
Purpose
Section 121(b) of the Comprehensive Environmental Re-
sponse, Compensation, and Liability Act (CERCLA) mandates
the Environmental Protection Agency (EPA) to select remedies
that "utilize permanent solutions and alternative treatment
technologies or resource recovery technologies to the maximum
extent practicable" and to prefer remedial actions in which
treatment "permanently and significantly reduces the volume,
toxicity, or mobility of hazardous substances, pollutants, and
contaminants as a principal element." The Engineering Bulletins
are a series of documents that summarize the latest information
available on selected treatment and site remediation technolo-
gies and related issues. They provide summaries of and refer-
ences for the latest information to help remedial project man-
agers, on-scene coordinators, contractors, and other site cleanup
managers understand the type of data and site characteristics
needed to evaluate a technology for potential applicability to
their Superfund or other hazardous waste site. Those documents
that describe individual treatment technologies focus on reme-
dial investigation scoping needs. Addenda will be issued peri-
odically to update the original bulletins.
Abstract
Granular activated carbon (GAC) treatment is a physico-
chemical process that removes a wide variety of contaminants
by adsorbing them from liquid and gas streams [1, p. 6-3]. This
treatment is most commonly used to separate organic con-
taminants from water or air; however, it can be used to remove
a limited number of inorganic contaminants [2, p. 5-1 7]. In
most cases, the contaminants are collected in concentrated
form on the CAC, and further treatment is required.
The contaminant (adsorbate) adsorbs to the surfaces of
the microporous carbon granules until the GAC becomes ex-
hausted. The GAC may then be either reactivated, regenerated,
or discarded. The reactivation process destroys most contami-
nants. In some cases, spent GAC can be regenerated, typically
using steam to desorb and collect concentrated contaminants
for further treatment. If GAC is to be discarded, it may have to
be handled as a hazardous waste.
* [reference number, page number]
Site-specific treatability studies are generally necessary to
document the applicability and potential performance of a
GAC system. This bulletin provides information on the tech-
nology applicability, technology limitations, a technology de-
scription, the types of residuals produced, site requirements,
latest performance data, status of the technology, and sources
for further information.
Technology Applicability
Adsorption by activated carbon has a long history of use as
a treatment for municipal, industrial, and hazardous waste
streams. The concepts, theory, and engineering aspects of the
technology are well developed [3]. It is a proven technology
with documented performance data. GAC is a relatively non-
specific adsorbent and is effective for removing many organic
and some inorganic contaminants from liquid and gaseous
streams [4].
The effectiveness of GAC as an adsorbent for general con-
taminant groups is shown in Table 1. Examples of constituents
within contaminant groups are provided in "Technology
Screening Guide for Treatment of CERCLA Soils and Sludges"
[5]. This table is based on current available information or
professional judgment when no information was available. The
proven effectiveness of the technology for a particular site or
waste does not ensure that it will be effective at all sites or that
the treatment efficiency achieved will be acceptable at other
sites. For the ratings used for this table, demonstrated effec-
tiveness means that, at some scale, treatability was tested to
show that, for that particular contaminant and matrix, the
technology was effective. The ratings of potential effectiveness
and no expected effectiveness are based upon expert judge-
ment. Where potential effectiveness is indicated, the technology
is believed capable of successfully treating the contaminant
group in a particular matrix. When the technology is not
applicable or will probably not work for a particular combina-
tion of contaminant group and matrix, a no-expected-effective-
ness rating is given.
The effectiveness of GAC is related to the chemical com-
position and molecular structure of the contaminant. Or-
-------
Table 1
Effectiveness of Granular Activated Carbon on
General Contaminant Groups
Table 2
Organic Compounds Amenable to
Adsorption by GAC [1 ]
Contaminant Groups
u
o
6
.0
o
ET
o
.c
1
u
o
ce
Halogenated volatiles
Halogenated semivolatiles
Nonhalogenated volatilesa
Nonhalogenated semivolatiles
PCBs
Pesticides
Dioxins/Furans
Organic cyanides a
Organic corrosives a
Volatile metals-1
Nonvolatile metals a
Asbestos
Radioactive materials a
Inorganic corrosives
Inorganic cyanides b
Oxidizersb
Reducers
Liquid /Gas
m
m
m
m
m
m
m
T
•
•
•
j
•
j
•
m
j
• Demonstrated Effectiveness: Successful treatability test at some scale
completed
V Potential Effectiveness: Expert opinion that technology will work.
J No Expected Effectiveness: Expert opinion that technology will not work
a Technology is effective for some contaminants in the group; it may not
be effective for others.
b Applications to these contaminants involve both adsorption and chemical
reaction.
ganic wastes that can be treated by GAC include com-
pounds with high molecular weights and boiling points and
low solubility and polarity [6]. Organic compounds treat-
able by GAC are listed in Table 2. GAC has also been used to
remove low concentrations of certain types of inorganics
and metals; however, it is not widely used for this application
[1, p. 6-13].
Almost all organic compounds can be adsorbed onto
GAC to some degree [2, p. 5-1 7]. The process is frequently
used when the chemical composition of the stream is not fully
analyzed [1, p. 6-3]. Because of its wide-scale use, GAC has
probably been inappropriately selected when an alternative
technology may have been more effective [7]. GAC can be
used in conjunction with other treatment technologies. For
example, GAC can be used to remove contaminants from the
offgas from air stripper and soil vapor extraction operations
[7] [8, p. 73] [9].
Class
Aromatic solvents
Polynuclear aromatics
Chlorinated aromatics
Phenolics
Aromatic amines and
high molecular weight
aliphatic amines
Surfactants
Soluble organic dyes
Fuels
Chlorinated solvents
Aliphatic and aromatic acids
Pesticides/herbicides
Example
Benzene, toluene, xylene
Naphthalene, biphenyl
Chlorobenzene, PCBs, endrin,
toxaphene, DDT
Phenol, cresol, resorcinol,
nitrophenols, chlorophenols,
alkyl phenols
Aniline, toluene diamine
Alkyl benzene sulfonates
Methylene blue, textile dyes
Gasoline, kerosene, oil
Carbon tetrachloride,
perchloroethylene
Tar acids, benzoic acids
2,4-D, atrazine, simazine,
aldicarb, alachlor, carbofuran
Limitations
Compounds that have low molecular weight and high
polarity are not recommended for GAC treatment. Streams
with high suspended solids (> 50 mg/L) and oil and grease (>
10 mg/L) may cause fouling of the carbon and require frequent
backwashing. In such cases, pretreatment prior to GAC, is
generally required. High levels of organic matter (e.g., 1,000
mg/L) may result in rapid exhaustion of the carbon. Even lower
levels of background organic matter (e.g., 10-100 mg/L) such
as fulvic and humic acids may cause interferences in the adsorp-
tion of specifically targeted organic contaminants which are
present in lower concentrations. In such cases, GAC may be
most effectively employed as a polishing step in conjunction
with other treatments.
The amount of carbon required, regeneration/reactivation
frequency, and the potential need to handle the discarded GAC
as a hazardous waste are among the important economic con-
siderations. Compounds not well adsorbed often require large
quantities of GAC, and this will increase the costs. In some
cases the spent GAC may be a hazardous waste, which can
significantly add to the cost of treatment.
Technology Description
Carbon is an excellent adsorbent because of its large surface
area, which can range from 500-2000 m2/g, and because its
diverse surfaces are highly attractive to many different types of
contaminants [3]. To maximize the amount of surface available
Engineering Bulletin: Granular Activated Carbon Treatment
-------
Figure 1. Schematic Diagram of Fixed-Bed GAC System
(CONTAMINATED
LIQUID)
CARBON BED
(3)
EFFLUENT
(TREATED WATER)
(2)
SPENT CARBON
for adsorption, an activation process which increases the sur-
face-to-volume ratio of the carbon is used to produce an exten-
sive network of internal pores. In this process, carbonaceous
materials are converted to mixtures of gas, tars, and ash. The tar
is then burned off and the gases are allowed to escape to produce
a series of internal micropores [1, p. 6-6]. Additional processing
of the CAC may be used to render it more suitable for certain
applications (e.g. impregnation for mercury or sulfur removal).
The process of adsorption takes place in three steps [3].
First the contaminant migrates to the external surface of the
GAC granules. It then diffuses into the GAC pore structure.
Finally, a physical or chemical bond forms between the con-
taminant and the internal carbon surface.
The two most common reactor configurations for GAC
adsorption systems are the fixed bed and the pulsed or moving
bed [3]. The fixed-bed configuration is the most widely used
for adsorption from liquids, particularly for low to moderate
concentrations of contaminants. GAC treatment of contami-
nated gas streams is done almost exclusively in fixed-bed reac-
tors. The following technical discussion applies to both gas and
liquid streams.
Figure 1 is a schematic diagram of a typical single-stage,
fixed-bed GAC system for use on a liquid stream. The contami-
nant stream enters the top of the column (1). As the waste
stream flows through the column, the contaminants are ad-
sorbed. The treated stream (effluent) exits out the bottom (2).
Spent carbon is reactivated, regenerated, or replaced once the
effluent no longer meets the treatment objective (3). Although
Figure 1 depicts a downward flow, the flow direction can be
upward, depending on design considerations.
Suspended solids in a liquid stream or paniculate matter in
a gaseous stream accumulate in the column, causing an in-
crease in pressure drop. When the pressure drop becomes too
high, the accumulated solids must be removed, for example by
backwashing. The solids removal process necessitates adsorber
downtime, and may result in carbon loss and disruption of the
mass transfer zone. Pretreatment for removal of solids from
streams to be treated by GAC is, therefore, an important design
consideration.
As a GAC system continues to operate, the mass-transfer
zone moves down the column. Figure 2 shows the adsorption
pattern and the corresponding effluent breakthrough curve [3].
The breakthrough curve is a plot of the ratio of effluent concen-
tration (Ce) to influent concentration (C0) as a function of water
volume or air volume treated per unit time. When a predeter-
mined concentration appears in the effluent (CB), breakthrough
has occurred. At this point, the effluent quality no longer meets
treatment objectives. When the carbon becomes so saturated
with the contaminants that they can no longer be adsorbed,
the carbon is said to be spent (Ce=C0). Alternative design
arrangements may allow individual adsorbers in multi-adsorber
systems to be operated beyond the breakpoint as far as com-
plete exhaustion. This condition of operation is defined as the
operating limit (Ce=CL) of the adsorber.
The major design variables for liquid phase applications of
GAC are empty bed contact time (EBCT), GAC usage rate, and
system configuration. Particle size and hydraulic loading are
often chosen to minimize pressure drop and reduce or elimi-
nate backwashing. System configuration and EBCT have an
impact on GAC usage rate. When the bed life is longer than 6
months and the treatment objective is stringent (Ce/C0 < 0.05),
Engineering Bulletin: Granular Activated Carbon Treatment
-------
Figure 2
Breakthrough Characteristics of Fixed-Bed GAC Adsorper [3]
C(z,t)
Co
Saturated
Zone
(S)
Adsorption
Zone
(A)
Co
ce=o
Co
_L
T
Ce 0.3), blending of
effluents from partially saturated adsorbers can be used to
reduce GAC usage rate. When stringent treatment objectives
are required (Ce/C0 < 0.05) and GAC bed life is short (less than
6 months) multiple beds in series may be used to decrease GAC
usage rate.
For gas-phase applications, the mass transfer zone is usu-
ally very short if the relative humidity is low enough to prevent
water from filling the GAC pores. The adsorption zone (Figure
2) for gas-phase applications is small relative to bed depth, and
the GAC is nearly saturated at the breakpoint. Accordingly,
EBCT and system configuration have little impact on GAC
usage rate and a single bed or single beds operated in parallel
are commonly used.
GAC can be reactivated either onsite or offsite. The choice is
usually dictated by costs which are dependent on the site and on
the proximity of offsite facilities that reactivate carbon. Generally
onsite reactivation is not economical unless more than 2,000
pounds per day of GAC are required to be reactivated. Even so,
an offsite reactivation service may be more cost effective [10].
The basic evaluation technique for initial assessment of the
feasibility of GAC treatment is the adsorption isotherm test.
This test determines if a compound is amenable to GAC adsorp-
tion and can be used to estimate minimum GAC usage rates.
More detailed testing such as small-scale column tests and pilot
tests should be conducted if the isotherms indicate GAC can
produce an effluent of acceptable quality at a reasonable carbon
usage rate [10].
Process Residuals
The main process residual produced from a GAC system is
the spent carbon containing the hazardous contaminants. When
the carbon is regenerated, the desorbed contaminants must be
treated or reclaimed. Reactivation of carbon is typically accom-
plished by thermal processes. Elevated temperatures are em-
ployed in the furnace and afterburners to destroy the accumu-
lated contaminants. If the carbon cannot be economically
reactivated, the carbon must be discarded and may have to be
treated and disposed of as a hazardous waste. In some cases,
the influent to GAC treatment must be pretreated to prevent
excessive head loss. Residues from pretreatment (e.g. filtered
suspended solids) must be treated or disposed. Solids collected
from backwashing may need to be treated and disposed of as a
hazardous waste.
Site Requirements
GAC equipment generally has small space requirements
and sometimes can be incorporated in mobile units. The
rapidity of startup and shutdown also makes GAC amenable to
mobile treatment. Carbon beds or columns can be skid-mounted
and transported by truck or rail [2, p. 5-19].
As previously stated, spent carbon from the treatment of
streams containing hazardous substances is generally considered
hazardous, and its transportation and handling requires that a
site safety plan be developed to provide for personnel protection
and special handling measures. Storage may have to be provided
to hold the GAC-treated liquid until its acceptability for release
has been determined. If additional treatment is required, ad-
equate space must be provided for these systems.
Engineering Bulletin: Granular Activated Carbon Treatment
-------
Performance Data
Performance data on full-scale GAC systems have been
reported by several sources including equipment vendors.
Data on GAC systems at several Superfund sites and other
cleanup sites are discussed in this section. The data presented
for specific contaminant removal effectiveness were obtained
from publications developed by the respective GAC system
vendors. The quality of this information has not been deter-
mined; however, it does give an indication of the efficiency of
GAC.
A GAC system was employed for leachate treatment at the
Love Canal Superfund site in Niagara Falls, New York. The
results of this operation are listed in Tables 3 and 4 [11 ].
Table 5 summarizes a number of experiences by Calgon
Corporation in treating contaminated groundwater at many
other non-Superfund sites. Table 5 identifies the sources of
contamination along with operating parameters and results
[12]. While these sites were not regulated under CERCLA, the
type and concentration of contaminants are typical of those
encountered at a Superfund site.
The Verona Well Field Superfund site in Battle Creek, Michi-
gan used GAC as a pretreatment for the air stripper. This
arrangement reduced the influent concentrations which allowed
the air stripper to comply with the National Pollution Discharge
Elimination System (NPDES) permit. The system had two paral-
lel trains: a single unit and two units in series. Approximately
one-third of the total flow was directed to the first train while
the remaining flow went to the other train. Performance data
for removal of total volatile organic compounds (TVOC) on
selected operating days are given in Table 6 [1 3].
A remediation action at the U.S. Coast Guard Air Station in
Traverse City, Michigan, resulted in GAC being used to treat
contaminated groundwater. The groundwater was pumped
from the extraction well system to the GAC system. The treated
water was then discharged to the municipal sewer system.
Concentrations of toluene in the monitoring wells were reduced
from 10,329 parts per billion (ppb) to less than 10 ppb in
approximately 100 days [14].
Technology Status
GAC is a well-proven technology. It has been used in the
treatment of contaminated groundwater at a number of Super-
fund sites. Carbon adsorption has also been used as a polishing
step following other treatment units at many sites. In 1988, the
number of sites where activated carbon was listed in the Record
of Decision was 28; in 1989, that number was 38.
Costs associated with GAC are dependent on waste stream
flow rates, type of contaminant, concentrations, and site and
timing requirements. Costs are lower with lower concentration
levels of a contaminant of a given type. Costs are also lower at
higher flow rates. At liquid flow rates of 100-million gallons per
day (mgd), costs range from $0.10 -1.50/1,000 gallons treated.
At flow rates of 0.1 mgd, costs increase to $1.20 - 6.30/1,000
gallons treated [12].
Table 3
Love Canal Leachate Treatment System0 (March 1979) [11]
Priority Pollutant
Compounds Identified
Hexachlorobutadiene
1,2,4-trichlorobenzene
Hexachlorobenzene
a-BHC
y-BHC
(3-BHC
Heptachlor
Phenol
2,4-dichlorophenol
Methylene chloride
1,1 -dichloroethylene
Chloroform
Carbon tetrachloride
Trichloroethylene
Dibromochloromethane
1,1,2,2-tetrachloroethylene
Chlorobenzene
Carbon System
Influent
Carbon System
Effluent
109
23
32
184
392
548
573
4,700b
10
180
28
540
92
240
21
270
1,200
<20
<20
<20
<0.01
0.12
<0.01
<0.01
<5b
<5
' Samples were analyzed by Recra Research, Inc., according to EPA
protocol dated April 1977 (sampling and analysis procedures of
screening for industrial effluents for priority pollutants).
b The data represent phenol analysis conducted by Calgon in June 1979,
as earlier results were suspect.
Table 4
Love Canal Leachate Treatment System0 (June 1979) [11]
Raw Carbon System
Priority Pollutant Leachate Effluent
Compounds Identified \\g/l y.g/1
2,4,6-trichlorophenol 85 <10
2,4-dichlorophenol 5,100 N.D.
Phenol 2,400 <10
1,2,3-trichlorobenzene 870 N.D.
Hexachlorobenzene 110 N.D.
2-chloronaphthalene 510 N.D.
1,2-dichlorobenzene 1,300 N.D.
1,3 & 1,4-dichlorobenzene 960 N.D.
Hexachlorobutadiene 1,500 N.D.
Anthracene and phenanthrene 29 N.D.
Benzene 28,000 <10
Carbon tetrachloride 61,000 <10
Chlorobenzene 50,000 12
1,2-dichloroethane 52 N.D.
1,1,1-trichloroethane 23 N.D.
1,1-dichloroethane 66 N.D.
1,1,2-trichloroethane 780 <10
1,1,2,2-tetrachloroethane 80,000 <10
Chloroform 44,000 <10
1,1-dichloroethylene 16 N.D.
1,2-trans-dichloroethylene 3,200 <10
1,2-dichloropropane 130 N.D.
Ethylbenzene 590 <10
Methylene chloride 140 46
Methyl chloride 370 N.D.
Chlorodibromomethane 29 N.D.
Tetrachloroethylene 44,000 12
Toluene 25,000 <10
Trichloroethylene 5,000 N.D.
a Samples were analyzed by Carborundum Corporation according to EPA
protocol dated April 1977 (sampling and analysis procedures for screening
of industrial effluents for priority pollutants).
N.D. = nondetectable.
Engineering Bulletin: Granular Activated Carbon Treatment
-------
Table 5
Performance Data at Selected Sites [12]
Source of
Contaminants
Truck spill
Methylene chloride
1,1,1-trichloroethane
Rail car spills
Phenol
Orthochlorophenol
Vinylidine chloride
Ethyl acrylate
Chloroform
Chemical spills
Chloroform
Carbon tetrachloride
Trichloroethylene
Tetrachloroethylene
Dichloroethyl ether
Dichloroisopropyl ether
Benzene
DBCP
1,1,1-trichloroethane
Trichlorotrifloroethane
Cis-1,2-dichloroethylene
Onsite storage tanks
Cis-1,2-dichloroethylene
Tetrachloroethylene
Methylene chloride
Chloroform
Trichloroethylene
Isopropyl alcohol
Acetone
1,1,1-trichloroethane
1,2-dichloroethylene
Xylene
Landfill site
TOC
Chloroform
Carbon tetrachloride
Gasoline spills, tank leakage
Benzene
Toluene
Xylene
Methyl t-butyl ether
Di-isopropyl ether
Trichloloethylene
Chemical by-products
Di-isopropyl methyl phosphonate
Dichloropentadiene
Manufacturing residues
DDT
TOC
1,3-dichloropropene
Chemical landfill
1,1,1-trichloroethane
1,1 -dichloroethylene
21
25
63
100
2-4
200
0.020
3.4
130-135
2-3
70
1.1
0.8
0.4
2.5
0.42
5.977
.005
0.5
7.0
1.5
0.30-0.50
3-8
0.2
0.1
12
0.5
8.0
20
1.4
1.0
9-11
5-7
6-10
0.030-0.035
0.020-0.040
0.050-0.060
1.25
0.45
0.004
9.0
0.01
0.060-0.080
0.005-0.015
<10.0
<100
<100
<1.0
<10.0
<10.0
<5.0
<5000
<100 Total
<5.0
<50
<0.5
0.005
Carbon Usage
Rate
(Ib./IOOOgal.)
3.9
3.9
5.8
5.8
2.1
13.3
7.7
11.6
11.6
11.6
11.6
0.45
0.45
1.9
0.7-3.0
1.5
1.5
0.25
0.8
0.8
4.0
1.19
1.54
1.54
1.54
1.0
1.0
1.0
1.15
1.15
1.15
<1.01
<1.01
<1.01
0.62
0.10-0.62
0.62
0.7
0.7
1.1
1.1
1.1
<0.45
<0.45
Total Contact
Time
(min.)
534
534
201
201
60
52
160
262
262
262
262
16
16
112
21
53
53
121
64
64
526
26
36
36
36
52
52
52
41
41
41
214
214
214
12
12
12
30
30
31
31
31
30
30
Engineering Bulletin: Granular Activated Carbon Treatment
-------
Table 6
TVOC Removal with GAC at
Verona Well Superfund Site [13]
Effluent
REFERENCES
Influent
Feed
Concentration
(ppb)
18,812
12,850
9,290
6,361
7,850
7,643
7,577
5,591
10,065
6,000
3,689
4,671
Train (1)
Concentration
(ppb)
NA
11
41
260
484
412
405
452
377
444
13
246
Train (2)
Concentration
(ppb)
25
7
17
426
575
551
524
558
475
509
702
263
Operating
Day
1
9
16
27
35
42
49
57
69
92
106
238
NA = not available
EPA Contact
Technology-specific questions regarding GAC treatment
may be directed to:
Dr. James Heidman
U.S. Environmental Protection Agency
Risk Reduction Engineering Laboratory
26 West Martin Luther King Drive
Cincinnati, Ohio 45268
FTS 684-7632 or (51 3) 569-7632
Acknowlegements
This bulletin was prepared for the U.S. Environmental Pro-
tection Agency, Office of Research and Development (ORD),
Risk Reduction Engineering Laboratory (RREL), Cincinnati, Ohio,
by Science Applications International Corporation (SAIC) under
contract No. 68-C8-0062. Mr. Eugene Harris served as the EPA
Technical Project Monitor. Mr. Gary Baker was SAIC's Work
Assignment Manager. This bulletin was authored by Ms. Mar-
garet M. Groeber of SAIC. The author is especially grateful to
Mr. Ken Dostal and Dr. James Heidman of EPA, RREL, who have
contributed significantly by serving as a technical consultant
during the development of this document.
The following other Agency and contractor personnel have
contributed their time and comments by participating in the
expert review meetings and/or peer reviewing the document:
Dr. John C. Crittenden
Mr. Clyde Dial
Mr. James Rawe
Dr. Walter J. Weber, Jr.
Ms. Tish Zimmerman
Michigan Technological University
SAIC
SAIC
University of Michigan
EPA-OERR
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America. Paper presented at First US/USSR Conference
on Hydrology. Moscow, U.S.S.R. July 3-5, 1989.
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Air Stripper Off-Gas, journal AWWA, 80(5):73-84, May
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