Removal of Lead and Cadmium from Aqueous

Waste Streams Using Granular Activated Carbon

(GAC) Columns
Brian E. Reed and Selvam Arunachalam
Department of Civil and Environmental Engineering,
West Virginia University, Morgantown, WV 26506
and
Bob Thomas
Norit Americas Inc., 1050 Crown Pointe Parkway, Atlanta, GA 30338
The use of granular activated carbon ( GAC) columns to treat metal-bearing
wastewaters was investigated. Synthetic wastewaters containing Pb and Cd ( I0 or
50 mg/ L) , acetic acid (0.001 N ) or EDTA (1:O.I or 1:1 Me:EDTA molar ratios)
were studied. For metal-only and metal-acetic acid experiments, significant
quantities (as high as 325 bed volumes ( BV) ) of wastewater were treated prior
to breakthrough (Ce=0.03 Co). X/ M values were as high as about 30 mg Pb/g
carbon. For EDTA experiments, C, was always>0.03 C,. The amount of metal
not removed corresponded to the amount that was complexed by EDTA. Column
pH is the critical parameter influencing column performance. The increase in
effluent metal concentration corresponded with the decrease in column pH. GA C
columns were successfully regenerated using a 1 L ( = 8 B V) 0. I N HNO, rinse
followed by a I L 0.1 N NaOH rinse. Column performance was not adversely
affected by regeneration. When the regeneration step was used on virgin carbon,
a dramatic improvement in column performance was observed and was attributed
to the increase in carbon surface pH ( pH= II) and the deposition of OH- in the
pore liquid. Possible removal mechanism are precipitation on the carbon surface
and in the pore liquid, and adsorption.
INTRODUCTION
The presence of heavy metals in the environment is of major
concern because of their toxicity and threat to human life and
the environment. I n 1983, an estimated 7.9 billion gallons of
heavy metal-bearing wastewaters were generated in the U.S.
[I]. Lead, cadmium, and mercury are examples of heavy metals
that have been classified as priority pollutants by the U.S.
Environmental Protection Agency. Anthropogenic sources of
heavy metals include wastes from the electroplating and metal
finishing industries, metallurgical industry, tannery opera-
tions, chemical manufacturing, mine drainage, battery man-
ufacturing, leachates from landfills, and contaminated
groundwater from hazardous waste sites.
For wastes with high metal concentrations, precipitation
processes (e.g., hydroxide, sulfide) are the most economical.
However, many metal-bearing wastes contain substances, such
as complexing agents, that decrease the effectiveness of pre-
cipitation processes leading to relatively high metal concen-
trations in the effluent. In addition, the current regulatory
trend is for heavy metal discharge limits approaching those of
drinking water standards. Thus, additional treatment proc-
esses, downline from the precipitation process, may berequired
to polish the effluent prior to discharge. These tertiary
processes may also be the primary metal removal process for
waste streams having low concentrations of metals. Examples
of such processes are ion exchange, reverse osmosis, and ad-
sorption. Ion exchange and reverse osmosis, while effective in
producing an effluent low in metals, have high operation and
maintenance costs and are subject to fouling. Adsorption by
activated carbon is an established treatment method for organic
contaminants. Although the ability of activated carbons to
remove heavy metals has been established by numerous re-
searchers [2-6], they have not been used in an actual treatment
setting for inorganic adsorbates. The majority of these studies
were conducted in the batch mode. If activated carbon is to
be considered as a viable method for heavy metal removal,
additional information on its efficiency in the column mode
must be gathered.
The goal of this research was to demonstrate the efficacy
of using granular activated carbon (GAC) columns to treat
heavy-metal bearing waste streams. Lead and cadmium were
60 February, 1994
Environmental Progress (Vol. 13, No. 1)
Table 1 Characteristics of Hydrodarco 4000
Surface Area (N2 BET Method), m2/g
Slurry pH
Ash Content, %
Molasses Number
Iodine Number
Mean Pore Radius, angstroms
Total Pore Volume, mL/g
Apparent Density, g/mL
Particle Density Wetted, g/mL
Mean Particle Diameter, mm
Effective Size
Uniformity Coefficient
Particle Size Distribution, U.S. Sieves
+12
12x 16
16 x 20
20 x 30
30 x 40
40 x 50
- 50
625
5.2
23
812
647
29
1.04
0.37
1.4
1.09
0.74
1.44
Percent
5.86
19.12
34.87
38.75
1.05
0.13
0.23
chosen as the study heavy metals because of their presence on
the USEPA priority pollutant list. Darco HD4000 (American
Norit Company, Inc.) was selected as the study activated car-
bon because the authors have investigated this carbon in earlier
work. Specific objectives of the research were to: 1) conduct
GAC column studies using synthetic waste streams containing
lead and cadmium, organic compounds (EDTA and acetic
acid), and different influent pH values, and 2) study the effect
of regeneration on GAC column performance.
METHODOLOGY
Lead and cadmium concentrations of 10 and 50 mg/L, were
used for each of three synthetic wastewaters investigated. The
characteristics of the column influents were as foIlows: 1) lead
or cadmium only at pHs of 4 (Pb only) and 5.4, 2)10-3 M
acetic acid at pH =4.7, and 3) EDTA at Me:EDTA molar
ratios of 1:O.l and 1:1, pH =5.4. Wastewaters 2 and 3 were
used to simulate wastes containing weak organic acids and
strong complexing agents, respectively. Lead and cadmium
were analyzed by flame atomic absorption spectrophotometry
using a Perkin-Elmer 2380 atomic absorption spectropho-
tometer. Samples were stored in polyethylene bottles and ac-
idified using concentrated HN03 immediately following sam-
pling. The pH was measured using a Fisher Scientific Accumet
mini pH meter (Model 640 A). All stock solutions were for-
mulated using reagent grade chemicals. Experiments were con-
ducted at an ionic strength of 0.01 (added as NaNO,) and a
temperature of about 22C. Hydrodarco 4000, the study ac-
tivated carbon, was supplied by Norit Americas Inc. Selected
characteristics of Hydrodarco 4000 are presented in Table 1.
Approximately 50 g (dry) of the carbon was weighed, sieved
through a U.S. No. 50 sieve, and washed with distilled water
to remove fines. The carbon was placed in 15 inch long, 1 .I25
inch inner diameter acrylic columns such that the formation
of air voids was minimized. Rounded stones and glass wool
were used as the column support media. The length of the
adsorptive bed was approximately 7.5 inches and the bed vol-
ume was 0.12 L. A hydraulic flow rate of 40 mL/min (6.24
cm3/cm2, 1.5 gal/ft*.min) was maintained using a Cole-Parmer
peristaltic pump with Masterflex speed controller. Columns
were operated in the up flow mode. Effluent samples were
InfIuent pH: 5.47
Dar co HD4000: 50 g
0. 8 -
0
0
U
2
0.4
0. 2
v Run 2
0 Run 3
A Run 4
0.0
0 100 200 300 400
Be d Volumea
1 2 , I I I I I
-
0 100 zoo 900 400
Be d Volumea
FIGURE 1. Breakthrough and effluent pH curves for 10
mglL Pb and pH =5.4.
collected either every 30 or 60 minutes, measured for pH, and
acidified. During the course of the column cycle (opera-
tion +regeneration) the volume and metal concentration of the
influent, effluent (including samples), and regenerants were
measured and used in mass balance calculations. Mass balance
results were used to calculate surface concentrations (X/M),
mass of metal removed, and desorption efficiencies. Following
each column run, carbon was regenerated using a procedure
consisting of 0.1 N HN03 and 0.1 N NaOH rinses.
Approximately 1 liter of 0.1 N HNO, was pumped through
the column at a flow rate of 10 mL/min. Samples of the acid
rinse were taken periodically and measured for pH and metal
content. This procedure was repeated using 1 liter of 0.1 N
NaOH. The 0.1 N NaOH remaining in the column after the
base rinse was allowed to contact the carbon for approximately
five days. The five day contact time was chosen strictly on
logistics (i.e., it was the minimum amount of time before the
new column run could begin). Following regeneration, the
column cycle was repeated. Depending on the experiment, the
column cycle was repeated either three or four times. Metal
removal dramatically increased following the first regeneration
step. Thus, in later experiments, the regeneration procedure
was used as a carbon pretreatment step for virgin carbon (i.e.,
before the first column run). Desorption efficiency was de-
termined using mass balance calculations.
RESULTS AND DISCUSSION
For ease of presentation, results from each of the synthetic
wastewaters are presented separately.
Environmental Progress (Vol. 13, No. 1)
February, 1994 61
1.0
0.8
50 mg/L Cadmium
Influent pH: 5.4
0.6 Carbon: 50 g
EBV: 0. 12 L
0 Run 1
v Run 2
o Run 3
0 50 100 150 200 250 300 350 400 450
Bed Volumes
0 50 100 150 200 250 300 350 400 450
Bed Volumes
FIGURE 2. Breakthrough and effluent pH curves for 5
mglL Cd and pH =5.4.
Metal-Only
Normalized effluent lead concentration (C,/C,) versus num-
ber of bed volumes (BV) treated for 10 mg/L, pH =5.47 are
presented in Figure 1. These curves will be referred to as break-
through curves for the remainder of this article. Breakthrough
was defined at C, =0.03 C,. Breakthrough occurred at about
50 BV for Run 1. Lead removal increased by approximately
600 percent following the 0.1 N HN03 - 0.1 NaOH N regen-
eration step. Based on the lead-only results, the regeneration
procedure was used as a pretreatment step for virgin carbon
for the remainder of the column experiments. Also presented
in Figure 1 is the effluent pH versus BV treated. Effluent pH
for Run 1 decreased from about 7 at the beginning of column
operation to 5.4 at the end. Initial effluent pH for Runs 2
through 4 were greater than 11 and decreased to about 8 at
breakthrough. Breakthrough and effluent pH curves for 50
mg/L Cd, pH =5.4 are presented in Figure 2. While the shape
of the breakthrough and pH curves are similar, much less
cadmium was removed compared to lead. In Table 2, a sum-
mary of column performance for the metal-only column studies
is presented.
It is hypothesized that lead was removed in greater quan-
tities, compared to cadmium, because of its solution chemistry.
Lead begins to form hydroxide species at pH =5 and forms
Pb(OH)* (s) at about pH =5.5 to 6 while, cadmium begins to
form hydroxide species at pH=8 and forms Cd(OH), (s) at
pH= 8.5 to 9. The lower the pH at which metal hydroxide
species form, the better the removal. Thus, it was expected
that lead would be better removed compared to cadmium.
Table 2 Summary of Column Performance for Metal-
Onlv ExDeriments
Influent BV Treated
10 mg/L Pb - pH =4
Run 1 40
Run 2 250
Run 3 240
Run 4 235
10 mg/L Pb - pH =5.4
Run 1 50
Run 2 325
Run 3 315
Run 4 300
Run 1 20
Run 2 110
Run 3 110
Run 4 110
Run 1 25
Run 2 125
Run 3 120
Run 4 120
10 mg/L Cd - pH =5.4
Run 1 80
Run 2 80
Run 3 80
Run 1 40
Run 2 40
Run 3 40
50 mg/L Pb - pH =4
50 mg/L Pb - pH =5.4
50 mg/L Cd - pH =5.4
Me Removed, X/M, mg
mg Me/g carbon
48 0.97
306 6.11
272 5.43
249 5.00
23 0.46
35 1 7.01
359 7.18
368 7.36
282 5.64
1280 25.6
1320 26.4
1370 27.4
341 6.81
1340 26.8
1440 28.7
1550 31.0
88 1.76
91 1.83
101 2.00
290 5.76
240 4.76
230 4.63
GAC columns were successfully regenerated using a rela-
tively simple procedure consisting of 1 liter (= 8 BV) rinses of
0.1 N HN03 and NaOH. Column performance was not ad-
versely affected by the regeneration procedure. The dramatic
improvement in column performance after the first regener-
ation is attributed to an increase in OH available for surface
and pore liquid precipitation as well as an increase in the
number of surface sites available for adsorption. The regen-
eration procedure as a pretreatment step for virgin carbon is
recommended.
Lead-Acetic Acid
Acetic acid was used to simulate a moderately acidic waste-
water such as a landfill leachate. Breakthrough and effluent
pH curves for 0.001 M acetic acid and 10 mg/L Pb and Cd
are presented in Figures 3 and 4, respectively. A summary of
column performance for acetic acid experiments is presented
in Table 3.
Approximately 120 BV of 10 mg/L Pb and 70 BV of 50
mg/L Pb were treated at breakthrough for each of the three
column runs. The presence of acetic acid caused a deterioration
of the column performance compared to the lead-only exper-
iments. Because of differences in influent pH, it is not possible
to directly compare the two systems. However, if results for
the lead-only system are interpolated to pH =4.7, the presence
of acetic acid decreased the BV treated by about two-thirds
for 10 mg/L and one-third for 50 mg/L. As in the lead-only
column studies, the deterioration in column performance co-
incided with the rapid drop in column pH. The increase in
waste acidity accelerated this phenomenon and caused break-
through to occur earlier than in the lead-only experiments. At
10 mg/L Pb, the run number did not appear to effect column
performance. For 50 mg/L Pb, the BV treated, mass of lead
62 February, 1994 Environmental Progress (Vol. 13, No. 1)
2.2
, I I I I
0. 6
0.4
0.2
2.0
1.0
1.6
1.4
Q 1.2
u 1.0
0. 8
0.6
0.4
0.2
0.0
U
2
-
-
-
Influent pH: 4. 7
0.001 M CH,COOH
Darco HD4 0 0 0 : 50 g
BV: 0.12 L
0 100 200 so0 400
Bed Volumes
g 10
4
*
2 6
A
0 100 200 a00 400
Bed Volumer
FIGURE 3. Breakthrough and effluent pH curves for 10
mglL Pb, 0.001 M acetic acid, and pH =4.7.
removed, and lead surface concentration decreased slightly
after Run 1 but, were constant for Runs 2 and 3. Exhaustion
of the columns (defined as the point where the breakthrough
curve first intersects the CJC, =1 line) occurred between 150
and 175 BV for 10 mg/L and between 100 and 120 BV for 50
mg/L Pb. At exhaustion, effluent and influent pH were equal
The presence of acetic acid did not appear to significantly
affect cadmium removal compared to the cadmium-only sys-
(pH =4.7).
Y v B
10 mg/L Cadmium
Influent pH: 4.7
0.001 M CH,COOH
Carbon: 50 g
BV: 0.12 L
v Run 2
0 Run 3
0 50 100 150 200 250 300 350 400 450
Bed Volumes
FIGURE 4. Breakthrough and effluent pH curves for 10
mglL Cd, 0.001 M acetic acid, and pH =4.7.
tems. It is unclear why the increase acidity (via acetic acid) did
not decrease removal. Possibly, the solution chemistry of cad-
mium played a role. In the future, additional research will be
conducted to shed light on this phenomenon.
For both lead and cadmium, desorption occurred as the
column pH decreased. For metals present in cationic form,
Table 3 Summary of Column Performance for Metal-Acetic Acid Experiments
Influent BV Treated' Me Removed', mg X/M', mg Me/g carbon
10 mg/L Pb - pH =4.7
Run 1 120; 155
Run 2 100; 145
Run 3 120; 170
Run 1 75; 120
Run 2 70; 110
Run 3 70; 110
10 mg/L Cd- pH=4. 7
Run 1 80; 120
Run 2 75; 110
Run 3 70; 120
Run 1 40; 95
Run 2 40; 90
Run 3 40; 115
50 mg/L Pb - pH =4.7
50 mg/L Cd - pH =4.7
' First number at breakthrough; second number at exhaustion.
127; 162
129; 153
149; 179
483; 626
421; 522
416; 523
87; 110
80; 100
78; 106
225; 350
175; 320
240; 375
2.55; 3.23
2.57; 3.06
2.97; 3.58
9.66; 12.5
8.42; 10.4
8.32; 10.5
1.73; 2.20
1.59; 2.00
1.56; 2.13
4.50; 7.00
3.50; 6.43
4.77; 7.53
Environmental Progress (Vol. 13, No. 1) February, 1994 63
10 mg/L Lead
Influent pH: 5.47
Pb:EDTA 1:O.l
Darco HD4000: 50 g
BV: 0. 12 L
0
V
\
V
0.2 1
v Run 2
0 Run 3
0. 0 I I
I I I I
0 100 200 so0 400
Bed Volumes
i
4
0 100 200 300 400
Bed Volumes
FIGURE 5. Breakthrough and effluent pH curves for 10
mglL Pb, Pb:EDTA ratio of l:O.l, and pH =4.7.
adsorption decreases with a decrease in pH. Thus, as the col-
umn pH decreased towards the influent pH (pH =4.7), metal
desorbed from the carbon. Cadmium desorbs at a higher pH
compared with lead because Cd2' is formed at a higher pH
(as was discussed earlier, Me2+is less adsorbable than
Me(OH)+) and, Cd(OH);! (s) dissolves at a higher pH compared
to Pb(OH);! (s). It is apparent that solution chemistry plays a
key role in metal removal by activated carbon.
Lead-EDTA
Breakthrough and effluent pH curves for 10 mg/L Pb at a
Pb:EDTA molar ratio of 1:O.l are presented in Figure 5 . For
all runs, C, was greater than 0.03C0 at the beginning of the
column run. Thus, based on the definition of breakthrough,
zero BV were treated. According to thermodynamic calcula-
tions, 10 percent of the lead forms complexes with EDTA at
this pb:EDTA molar ratio. For the entire column run about
10 percent of the lead was not removed. Thus, it is hypothesized
that the Pb-EDTA complex was not adsorbed by the carbon.
Similar results were observed for the Pb:EDTA molar ratio
of 1 : 1 and Cd:EDTA molar ratios of 1 :O. 1 and 1 : 1.
CONCLUSIONS
Significant quantities of metal-bearing wastewaters were
treated using GAC columns. Column pH and influent char-
acteristics appear to be the critical parameters influencing GAC
column performance. The sudden increase in the column ef-
fluent lead concentration corresponded noticeably with a de-
crease in the effluent pH. Acetic acid at 0.001 M decreased
column performance compared with the lead-only experiments
but large amounts of lead were still removed from solution.
It is hypothesized that acetic acid reacted with the carbon
associated OH- (on the surface and in the pore liquid), which
produced a more rapid decrease in column pH and a subsequent
decrease in lead removal. The presence of EDTA adversely
affected column performance most likely because of solution
complexation. Wastewaters containing strong complexing
agents will either have to undergo pretreatment prior to en-
tering the GAC column or an activated carbon that adsorbs
the organic-metal complexes will have to be identified.
GAC columns were successfully regenerated using a rela-
tively simple procedure consisting of 1 liter (= 8 BV) rinses of
0.1 N HNO, and NaOH. Column performance was not ad-
versely affected by the regeneration procedure. When the re-
generation step was used on virgin carbon, a dramatic
improvement in column performance was observed. This was
attributed to an increase in OH- available for surface and pore
liquid precipitation as well as an increase in the number of
surface sites available for adsorption. The use of the regen-
eration procedure as a pretreatment step for virgin carbon is
recommended. Given the encouraging performance of the GAC
columns in treating several lead wastewaters and the relative
ease of column regeneration, the use of GAC columns to treat
metal-bearing waste streams should be considered.
LITERATURE CITED
1. Grosse, D. W., JournalAir Polhtion ControlAssociation,
36, p. 683, (1986).
2. Reed, B. E., and Matsumoto, M. R., Journal of Envi-
ronmental Engineering Division, ASCE, 119(2), p. 332,
(1993).
3. Reed, B. E., and Nonavinakere, S. K., Separation Science
and Technology, 27(14), p. 1985, (1992).
4. Corapcioglu, M. O., and Huang, C. P., Water Research,
9(9), p. 1031, (1987).
5 . Netzer, A., and Hughes, D. E., Water Research, 18(8),
p. 927, (1984).
6. Huang, C. P., and Ostovic, F. B., Journal of Environ-
mentalEngineering Division, ASCE, 104(5), p. 863, (1978).
64 February, 1994 Environmental Progress (Vol. 13, No. 1)