ADSORPTION EQUILIBRIUM MODELING

OF SPACE STATION WASTEWATERS

By D. W. Hand,1 Member, ASCE, A. N. Ali,2 J. L. Bulloch,3

M. L. DeBraske,4 J. C. Crittenden,5 Member, ASCE, and D. R. Hokanson6

ABSTRACT: An adsorption equilibrium model was developed for predicting the total organic carbon (TOC)
removal by the International Space Station water processor’s multifiltration beds. Ideal adsorbed solution theory
is used to describe the competitive interactions between fictive components (FCs) that make up the TOC. The
FC physical properties were based on several identified compounds to represent the distribution adsorbing
compounds in the wastewaters. The TOC isotherms were performed using the wastewaters on three absorbents
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(a coconut-based granular activated carbon, a coal-based granular activated carbon, and a polymeric-based resin),
which are contained in the multifiltration beds. The isotherms were used to validate the model for all three
adsorbents. The FCs were determined in such a way that they can describe the TOC concentration for multiple
beds in series.

INTRODUCTION
Fictive component analysis (FCA) was used to model the
A substantial amount of potable water is required for life total organic carbon (TOC) adsorption equilibrium of the
support of the crew aboard the International Space Station wastewater. The FCA uses imaginary compounds called fictive
(ISS). Water for drinking, food preparation, and personal hy- components (FCs) to represent the distribution of adsorbing
giene accounts for over 90% by weight of the basic consum- compounds in the wastewater, which makes up the overall
ables (water, oxygen, and food) required for survival aboard TOC concentration (Sontheimer et al. 1988). Bulloch et al.
the ISS. Life support for a four-person crew requires transport (1997) successfully used this approach to model the adsorption
of approximately 21,000 kg (46,100 lb) of water per year to equilibrium of a surrogate water used to mimic the shower/
the ISS without onboard water recycling. The economic lim- hand-wash wastewater stream. This approach also has been
itations of transporting water to the ISS necessitate onboard used to model TOC adsorption isotherms for surface and
recovery and reuse of the aqueous waste streams (Carter et al. ground waters where each FC represented a portion of the
1991, 1992). TOC, and the sum of the FC TOC concentrations and the
The aqueous waste streams treated by the ISS water pro- nonadsorbing TOC fraction equaled the overall TOC concen-
cessor include the following: (1) Urine distillate; (2) shower tration (Frick and Sontheimer 1983; Crittenden et al. 1985a;
water; (3) hand-wash water; (4) humidity condensate; (5) oral Smith and Weber 1990; Crittenden et al. 1993).
hygiene and wet shave waste; (6) a mixture of humidity con- In this study, an FCA method for characterizing the TOC
densate and evaporated urine from the Research Animal Hold- adsorption capacity and competitive adsorption effects of the
ing Facility (RAHF); and (7) equipment off-gassing waste. shower/hand-wash, urine distillate, humidity condensate, and
These waste streams are complex mixtures of unknown com- waste mixture waters in the MFB adsorbents is presented.
position. The waste streams onboard the ISS are treated for These waste streams were the only ones considered in this
potable consumption using a combination of four processes. study because the remaining waste streams (oral hygiene and
One process is a combination of adsorbents and ion exchange wet shave waste, a mixture of humidity condensate and evap-
resins that make up the multifiltration bed (MFB) system orated urine from the RAHF and equipment off-gassing waste)
shown in Fig. 1. The MFB process was proposed for the space make up a very small volume of the overall wastewater and
station in the early 1980s as the primary process for removing they are expected to contain very little TOC. The FCs are
organic and inorganic contaminants from the waste streams. determined in such a way that they can describe the TOC
More recently, mathematical models were developed to de- concentration as it passes through each adsorbent. This re-
scribe the removal of organic contaminants by the MFBs (Bul-
loch 1995). This paper presents the development of the equi-
librium description that was used to describe contaminant
removal through the three adsorbent layers displayed in Fig. 1.
1
Assoc. Prof., Dept. of Civ. and Envir. Engrg., Michigan Technol.
Univ., Houghton, MI 49931.
2
Proj. Engr., URS Greiner Woodward Clyde, 11499 Chester Rd., Ste.
2403, Cincinnati, OH 45246.
3
Res. Engr., Dept. of Civ. and Envir. Engrg., Michigan Technol. Univ.,
Houghton, MI.
4
Envir. Engr., R.M.T. Inc., 1143 Highland Dr., Ste. B, Ann Arbor, MI
48106.
5
Presidential Prof., Dept. of Civ. and Envir. Engrg., Michigan Technol.
Univ., Houghton, MI.
6
Res. Engr., Dept. of Civ. and Envir. Engrg., Michigan Technol. Univ.,
Houghton, MI.
Note. Editor: Makram T. Suidan. Discussion open until November 1,
1999. To extend the closing date one month, a written request must be
filed with the ASCE Manager of Journals. The manuscript for this paper
was submitted for review and possible publication on December 8, 1997.
This paper is part of the Journal of Environmental Engineering, Vol.
125, No. 6, June, 1999. 䉷ASCE, ISSN 0733-9372/99/0006-0540–0547/ FIG. 1. Schematic of Multifiltration Bed for ISS’s Potable Wa-
$8.00 ⫹ $.50 per page. Paper No. 17137. ter Treatment System

540 / JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999

J. Environ. Eng., 1999, 125(6): 540-547

 quires that the FC TOC concentrations remain constant as they
move from one adsorbent into another for future fixed-bed
modeling. Equilibrium isotherm experiments were used to de-
termine the TOC adsorption capacity of each wastewater for
each adsorbent contained in the MFB. The FCA was used to
obtain the initial FC concentrations for the first adsorbent in
series [580-26 granular activated carbon (GAC)] for each
wastewater by fitting FCA model calculations to the isotherm
data.
The FC physical properties were determined based on a dis-
tribution of compounds identified in the wastewaters (Ali
1997). The APA GAC and XAD-4 resin FC Freundlich iso-
therm capacity parameters were determined from correlations
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relating the single solute Freundlich capacity for 580-26 GAC
to those for APA GAC and XAD-4 resin as outlined by Son-
theimer et al. (1988). The FC Freundlich isotherm exponent
values for all the adsorbents were determined from correlations
relating single solute Freundlich capacity parameters to the
Freundlich isotherm exponents for each adsorbent (Bulloch
1995).
Correlating the Freundlich parameters from one adsorbent
to another enables this method to describe the TOC adsorption
for the MFB adsorbents connected in series. Consequently, for
a given wastewater, the only fitting parameters are the initial
FC concentrations for the 580-26 GAC because the FC param-
eters for the APA GAC and XAD-4 resin are determined from
the 580-26 GAC FC parameters.
MATERIALS AND METHODS
Solution Preparation
Shower, hand-wash, humidity condensate, urine distillate,
oral hygiene, wet shave, animal condensate, and equipment
off-gasing water samples were generated at the National Aero-
nautics and Space Administration’s (NASA) ISS life-support
testing facility at Marshall Space Flight Center (Huntsville,
Ala.). The samples were placed in glass containers with Teflon
caps and then ice packed in coolers and transported overnight
to Michigan Technological University (Houghton, Mich.).
Each wastewater sample then was pumped through MCV resin
(iodine-releasing ion-exchange resin), filtered through a 0.45-
␮m filter (Gelman, AnnArbor, Mich.) and restored in clean 3-
L glass containers at 4.0⬚C to eliminate biological activity.
Prior to their use, the humidity condensate, urine distillate,
shower/hand-wash, and combined waste mixture streams were
pumped into individual Tedlar gas bags (SKC, Eighty Four,
Pa.) to prevent the loss of volatile compounds from solution.
The combined waste stream mixture (79.9 L) was composed
of 21.0% shower water, 31.6% hand-wash water, 18.8% hu-
midity condensate water, 13.9% urine distillate water, 2.8%
oral hygiene water, 3.2% wet shave water, 6.9% animal con-
densate water, and 1.8% equipment off-gassing water. The
urine distillate was 20% manufactured by NASA and 80% a
surrogate because not enough was collected at the NASA life-
support testing facility. The shower/hand-wash waste stream
(83.5 L) was prepared by mixing 40.0% shower water and
60.0% hand-wash water and this mixture is typical for a space
station waste.
Distilled-deionized water was produced by distilling tap wa-
ter and further purifying it with a Milli-Q UV Plus Water sys-
tem (Millipore Corp., Bedford, Mass.). The Milli-Q system
produces water with a background TOC concentration less
than 0.1 mg/L. Milli-Q distilled-deionized water was used for
waste stream dilutions and standard preparation.
Chemical Analysis
The TOC was analyzed with a Sievers model 800 portable
TOC analyzer (Boulder, Colo.) utilizing UV-persulfate oxida-
J. Environ. Eng., 1999, 125(6): 540-547
tion. The pH was determined using an Orion (Cambridge,
Mass.) model 501 pH meter.
Adsorbents
The following MFB adsorbents were used in this study:
• 580-26 coconut-shell-based GAC, 18 ⫻ 25 U.S. Standard
Sieve (Barnebey and Sutcliffe Corp., Columbus, Ohio)
• APA bituminous coal-based GAC, 12 ⫻ 40 U.S. Standard
Sieve (Calgon Carbon Corp., Pittsburgh)
• XAD-4 polymeric adsorbent resin, 20 ⫻ 50 U.S. Standard
Sieve (Rohm and Haas Co., Philadelphia)
The experiment samples were obtained by mixing and split-
ting the samples of the adsorbents as received from the man-
ufacturer. Powdered GAC (PGAC), U.S. Standard 200 ⫻ 400
sieve, was used in the isotherm studies. The PGAC was ob-
tained by crushing and sieving representative samples of the
virgin GAC until a 100% passing size of U.S. Standard 200
mesh was achieved. The PGAC used for the isotherms was
the PGAC retained on a U.S. Standard 400 sieve, which was
washed with Milli-Q water and dried overnight at 105⬚C. The
XAD-4 resin was rinsed with Milli-Q water and used in its
uncrushed form.
Isotherm Procedure
A bottle point isotherm procedure was used for all adsorp-
tion isotherms (Randtke and Snoeyink 1983). A series of 45-
and 250-mL screw-cap bottles with Teflon septa, each con-
taining different dosages of adsorbent, were filled with the
same initial aqueous phase TOC concentration and allowed to
equilibrate at room temperature for 7–10 days. During equil-
ibration, the isotherm bottles were rotated in a tumbler at 18
revolutions per minute to provide good mixing of the adsor-
bent with the solution. The equilibrium liquid-phase TOC con-
centration for compound i(Ci ), in each isotherm bottle was
measured and the equilibrium solid-phase TOC loading for
compound i(q i ) was calculated using the following mass bal-
ance:
(C0i ⫺ Ci )V
qi = (1)
M
where C0i = initial liquid-phase TOC concentration; V = so-
lution volume in the isotherm bottle; and M = mass of adsor-
bent in the isotherm bottle.
Scope of Experiments
Dilute and nondilute TOC isotherms were performed on the
waste mixture, shower/hand-wash, urine distillate, and humid-
ity condensate wastewaters for each MFB adsorbent. The di-
lute waste stream solutions were prepared by mixing equal
volumes of the wastewater solution and Milli-Q distilled-
deionized water. The isotherms were performed at 21 ⫾ 1⬚C.
FCA
In the FCA, FCs were used to represent the overall adsorp-
tion strength of the wastewaters. The TOC isotherms were
used to determine the adsorption strength for each wastewater.
The FCs were assigned physical properties and used in ideal
adsorbed solution theory (IAST) calculations to model the
competitive adsorption strength for each wastewater on each
adsorbent.
IAST
When all of the compounds present in an aqueous mixture
have been identified, IAST can be used to predict the multi-
JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999 / 541
 component adsorption equilibria of each compound (Radke
and Prausnitz 1972; Jossens et al. 1978; Fritz and Schlunder
1981; Luft 1984; Crittenden et al. 1985b; and Kuennen et al.
1989). The IAST may be used to predict multicomponent equi-
libria based on the thermodynamics of adsorption using single
solute isotherm parameters for the individual compounds and
their respective initial concentrations. The IAST development
is discussed thoroughly by Radke and Prausnitz (1972) and
Crittenden et al. (1985a). If the Freundlich isotherm equation
is used to represent single solute behavior, IAST yields (2) for
the equilibrium condition of each adsorbate in a multicom-
ponent isotherm (Crittenden et al. 1985a)
冋冘 册
NC ni
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nj q j
M qi
C0i ⫺ qi ⫺
j=1
冘
NC
= Fi (q1, . . . , qNC)
V ni Ki
qj
j=1
=0 for i = 1, . . . , NC
where NC = number of adsorbable components representing
the TOC concentration in the isotherm bottle. Given the dos-
age of the adsorbent, volume of solution in the isotherm bottle,
initial component concentrations, and Freundlich isotherm pa-
rameters of each adsorbable component, the final equilibrium
state may be determined by solving (2) simultaneously for all
components in the mixture. To apply IAST in this manner, all
the components in the mixture need to be known.
Unfortunately, the wastewaters generated on the ISS are
complex mixtures of which complete characterization is not
possible. Carter et al. (1992) identified over 250 organic com-
pounds present in the wastewaters accounting for approxi-
mately 85–90% of the wastewater TOC. In addition, the ap-
plication of IAST with over 250 compounds is not practical,
especially when it is incorporated into a fixed-bed mass trans-
fer model. Consequently, FCs were chosen based on the
known compounds in the wastewaters to characterize the ad-
sorption capacity and competitive adsorption of the ISS waste-
waters.
FC Parameter Determination
The FCs were assigned physical properties and used in
IAST calculations to model the capacity and competitive ad-
sorption of the TOC in the various wastewaters. The param-
eters required for the FC multicomponent equilibrium calcu-
lations include (1) molecular weight, (2) fraction of carbon,
(3) Freundlich capacity parameter K, (4) Freundlich intensity
parameter 1/n, and (5) initial concentration. Six FCs were cho-
sen to represent the adsorbing fraction of the TOC in the
wastewaters because they can describe the wide variation of
adsorbing compounds that make up the TOC in the waste-
waters.
Table 1 summarizes the six TOC FCs and their properties
that were used to characterize the adsorption equilibrium of
TABLE 1. Summary of FC properties based on Known Compounds in Waste Mixture and 580-26 GAC
Freundlich
Freundlich K K-weighted
FC number range average
(1) (2) (3)
FC1 0.1–10.0
FC2 10–70
FC3 70–150
FC4 150–450
FC5 450–3,000
FC6 4(104)–1.4(105) 4,000.0
Note: All K units, (mg/g)(L/mg)1/n.
542 / JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999
the waste mixture, shower/hand-wash, urine distillate, and hu-
midity condensate wastewaters for 580-26 GAC. With the ex-
ception of FC4, the FC parameters [molecular weight, fraction
of carbon (FOC), and single solute isotherm parameters] were
determined by correlation with the Freundlich K for several
identified compounds in the shower/hand-wash, urine distil-
late, and humidity condensate wastewaters. These known com-
pounds were grouped by similar Freundlich K values to cover
the range of adsorption potential present in the wastewaters.
From each group, a representative FC was chosen and prop-
erties were determined by calculating the concentration-
weighted averages of each property in each group (Ali 1997).
The FC4 was chosen as sodium-n-methyl-n-‘‘coconut oil
acid’’ taurate (SCMT) because it is the major active ingredient
in the soap used onboard the ISS. The SCMT accounts for a
large fraction of the TOC in the shower/hand-wash and waste
mixture wastewaters. For example, SCMT can account for as
much as 25–35% of the overall TOC in the waste mixture.
The Freundlich parameters for the FCs in Tables 1 and 2
(2) were determined from Polanyi potential theory (Sontheimer et
al. 1988). The Polanyi potential theory parameters were ob-
tained from several single solute isotherms performed on each
adsorbent (Bulloch 1995). The FC Freundlich 1/n values were
determined by correlating the 1/n and K values of the known
compounds in the waste mixture. A linear relationship between
the Freundlich K and 1/n values was obtained and used to
calculate the FC 1/n value for each FC Freundlich K value
(Ali 1997).
Because the MFBs contain three adsorbents in series, the
FCs for each adsorbent must be related to one another to
model the unknown waste mixture as it passes through each
adsorbent in future fixed-bed modeling. The adsorbents were
related to one another by correlating the FC Freundlich K val-
ues for the APA GAC and XAD-4 resin with those for the
580-26 GAC. The APA GAC and XAD-4 resin Freundlich K
values were determined by correlating their Freundlich K val-
ues with 580-26 GAC Freundlich K values for several single
solute isotherms (Bulloch 1995). The FC Freundlich 1/n values
for APA GAC and the XAD-4 resin were determined using
Polanyi potential theory as described earlier.
The initial FC TOC concentrations for 580-26 GAC were
determined by fitting the FC model to the TOC isotherm data
for each wastewater. The APA GAC and XAD-4 resin initial
FC concentrations were determined by taking the 580-26 GAC
initial FC concentrations and multiplying them by the total
adsorbable TOC for the APA GAC and XAD-4 resin and di-
viding by the total adsorbable TOC concentration for the 580-
26 GAC. This method of scaling the FC concentrations for the
APA GAC and XAD-4 resin allows future modeling of the
beds-in-series operation. The only fitting parameters required
are the FC initial concentrations for the 580-26 GAC on each
wastewater.
A genetic algorithm (GA) fitting routine was combined with
the FC model to determine the FC initial concentrations for
the 580-26 GAC. The GA is a stochastic search/optimization
Molecular Molecular weight
weight range weighted average FOC-weighted
(g/mol) (g/mol) FOC range average
(4) (5) (6) (7)
2.6 74–153 96.51 0.55–0.83 0.742
42.3 92–130 123.2 0.62–0.92 0.710
97.6 87–357 95.3 0.60–0.90 0.753
178.5 118–391 357.0 0.60–0.86 0.600
910.2 117–400 192.4 0.69–0.80 0.760
214–400 270.7 0.73–0.95 0.800
J. Environ. Eng., 1999, 125(6): 540-547
 TABLE 2. 580-26 GAC FCs and Their Initial Concentrations (mg/L) Determined from Fitting TOC Isotherms on Waste Mixture,
Shower/Hand-Wash, Urine Distillate, and Humidity Condensate Wastewaters

Freundlich Parameters
Waste mixture Shower/hand Urine distillate Humidity
Component K 1/n C0 wash C0 C0 condensate C0
(1) (2) (3) (4) (5) (6) (7)
TOC FC1 2.6 0.73 11.54 26.54 3.89 24.15
TOC FC2 42.3 0.47 41.64 1.81 3.88 9.00
TOC FC3 97.6 0.43 7.27 103.00 0.38 0.69
TOC FC4 178.5 0.17 49.56 113.00 0.80 2.20
TOC FC5 910.2 0.31 2.97 0.89 1.35 0.79
TOC FC6 4,000.0 0.24 5.50 4.72 0.05 0.65
Nonadsorbing. TOC concentration (mg/L) 26.6 10.50 2.40 21.00
Total TOC concentration (mg/L) 145.08 260.46 12.75 58.48
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Nondilute isotherm RPE values (%) C:7.4 C:14.8 C:9.2 C:21.7

q:11.7 q:15.2 q:9.7 q:113.4
Dilute isotherm RPE values (%) C:15.2 C:19.3 C:19.5 C:43.1
q:6.9 q:4.6 q:10.5 q:91.4

technique that has been shown to be a robust optimization

routine for complex nonlinear problems (Holland 1992; For-
rest 1993; Gallagher and Sambridge 1994; Carroll 1996). The
FC model calculations were compared with the isotherm data
and the following fitness function was maximized:

冘冋 册
N 2
1 兩 Ce,i(data) ⫺ Ce,i(model) 兩 兩 qe,i(data) ⫺ qe,i(model) 兩
fitness = 100 ⫺ ⫹
2 i=1 Ce,i(data) qe,i(data)

for i = 1, . . . , N (3)
where N = total number of isotherm points being fit; Ce,i(data)
and qe,i(data) = equilibrium liquid- and solid-phase TOC concen-
trations in each isotherm bottle; Ce,i(model) and qe,i(model) = FCA
predicted equilibrium liquid- and solid-phase concentrations
determined from the GA fitting routine. FIG. 2. FCA Fit of Dilute and Nondilute TOC Isotherms on 580-
Both the dilute and the nondilute isotherms for each water 26 PGAC for Waste Mixture
on each adsorbent were fit simultaneously to obtain a more
accurate description of the mixture’s competitive adsorption
characteristics because it accounts for changes in initial TOC
concentration (Sontheimer et al. 1988). The total TOC con-
centration for each wastewater was represented with six FCs
and a nonadsorbing TOC fraction. The nonadsorbing nondilute
TOC concentration was determined from visual inspection of
the isotherm data for each wastewater on each adsorbent. The
nonadsorbing nondilute TOC concentration is found when the
liquid-phase concentration does not change with increasing ad-
sorbent dosage. The dilute isotherm’s nonadsorbing TOC con-
centration was calculated using the following equation:
Cnonadsorbing,nondilute Ctotal,dilute
Cnonadsorbing,dilute = (4)
Ctotal,nondilute
FIG. 3. FCA Fits of Dilute and Nondilute TOC Isotherms on
where Cnonadsorbing,dilute = dilute isotherm nonadsorbing TOC con- 580-26 PGAC for Shower/Hand-Wash Wastewater
centration; Cnonadsorbing,nondilute = nondilute, nonadsorbing concen-
tration, which is observed from the nondilute isotherm data; Figs. 2–5 compare the 580-26 GAC TOC isotherm data with
Ctotal,nondilute = initial TOC concentration of the nondilute iso- the FCA isotherm fits for each wastewater evaluated. The
therm; and Ctotal,dilute = inital TOC concentration for the dilute model fit corresponds to the same isotherm dosages as shown
isotherm. for the experimental data.
For the waste mixture, shower/hand-wash, and urine distil-
RESULTS late wastewaters, Figs. 2–4 show that the TOC capacity based
580-26 GAC Isotherm Fits on using the FCs in IAST calculations is close to the experi-
mental TOC capacity. Table 2 displays the relative percent
The initial FC concentrations for the 580-26 GAC were de- error (RPE) in the liquid- and solid-phase concentrations for
termined by fitting the dilute and nondilute TOC isotherm data the dilute and nondilute TOC isotherm fits. The RPE is defined
simultaneously using the method described earlier. Table 2 as the sum of the absolute values of the percent errors divided
summarizes the FC Freundlich isotherm parameters and TOC by the number of data points. The liquid- and solid-phase
concentrations that were determined for the waste mixture, RPEs of the dilute TOC isotherms are similar to those for the
shower/hand-wash, urine distillate, and humidity condensate nondilute isotherm indicating that the FC model is able to
waters. The FC parameters used (molecular weight and frac- account for changes in initial concentration because of dilution
tion of carbon) for the 580-26 GAC were shown in Table 1. of the wastewaters.
JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999 / 543

J. Environ. Eng., 1999, 125(6): 540-547

 With the exception of the humidity condensate wastewater,
the small differences between the model and data may be at-
tributed to scatter in the data caused by experimental error and
determination of the nonadsorbing TOC concentration. There
may be some error in determining the nondilute isotherm non-
adsorbing TOC concentration because not enough data was
collected using high dosages to determine accurately this value
and it may be overestimated in some cases. Overestimating
the nondilute isotherm nonadsorbing TOC will cause an over-
estimation in the dilute nonadsorbing fraction, which will shift
the isotherm fit for the dilute isotherm to the right causing a
larger RPE value in the liquid phase for the dilute TOC iso-
therms.
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of FC Freundlich parameters that were chosen based on the
waste mixture are not representative of the adsorption strength
of compounds in the humidity condensate. The FC Freundlich
K values were chosen based on several of the known com-
pounds present in all the wastewaters. Table 2 shows that over
77% of the total adsorbing TOC concentration is contained in
the first two FCs for the best fit. The TOC in this wastewater
is composed primarily of alcohols, aldehydes, and low molec-
ular weight organic acids (i.e., acetic, butanoic, formic, etc.).
These compounds are weakly adsorbing species and have low
single solute Freundlich K values similar to those for FC1 and
FC2. Consequently, a better description of the humidity con-
densate wastewater would require a different set of FCs with

The FCA was unable to provide an adequate fit for the hu-
midity condensate isotherms as shown in Fig. 5. The solid-
phase concentrations could not be fit because the distribution
FIG. 4. FCA Fits of Dilute and Nondilute TOC Isotherms on
580-26 PGAC for Urine Distillate Wastewater
FIG. 5. FCA Fits of Dilute and Nondilute TOC Isotherms on
580-26 PGAC for Humidity Condensate Wastewater
a distribution of FC Freundlich K values that would describe
more accurately the adsorption strength of the humidity con-
densate.
Model Predictions for APA GAC and XAD-4 Resin
Using the parameter estimation methodology presented ear-
lier, FC model predictions were compared with nondilute and
dilute isotherm data on APA GAC and XAD-4 resin. Table 3
summarizes the APA GAC FC Freundlich isotherm parameters
and their initial TOC concentrations for each wastewater.
These parameters were used to predict the nondilute and dilute
TOC isotherm data for each wastewater and the RPE values
are summarized in Table 3. Reasonable predictions were ob-
tained for the waste mixture and shower/hand-wash water, be-
cause the RPE values were less than 30% in both the solid-
and liquid-phase concentrations. The FCA was able to predict
accurately the urine distillate isotherm data for APA GAC
within the same error as the fit for the 580-26 GAC. The FCA
was unable to predict the humidity condensate isotherm data
for the same reason described for the 580-26 GAC.
The FC model predictions were compared with nondilute
and dilute isotherm data on XAD-4 resin. Table 4 summarizes
the XAD-4 resin FC Freundlich isotherm parameters and their
initial TOC concentrations for each waste mixture used to per-
form the model calculations. Based on the RPE values shown
in Table 4, FCA was able to provide an accurate prediction
for the waste mixture isotherms because the RPE values in
both the solid- and liquid-phase concentrations were less than
approximately 10%. The FCA provided reasonable predictions
of the shower/hand-wash isotherms even though the RPE val-
ues for the solid-phase concentrations were approximately
30%. The FCA was able to predict the nondilute humidity
condensate isotherm but overpredicted the liquid-phase con-
centrations at the high dosages for the dilute isotherm. Con-
sidering that the distribution of adsorption potentials of the
FCs are too high for describing the low adsorption strength of
the humidity condensate wastewater, FCA was able to provide

TABLE 3. APA GAC TOC FCs and Their Initial FC Concentrations for Waste Mixture, Shower/Hand-Wash, Urine Distillate, and Humid-
ity Condensate Wastewaters
Freundlich Parameters
Waste mixture Shower/hand Urine distillate Humidity
Component K 1/n C0 wash C0 C0 condensate C0
(1) (2) (3) (4) (5) (6) (7)
TOC FC1 1.84 0.82 11.87 26.77 3.70 25.95
TOC FC2 31.48 0.56 42.83 1.83 3.69 9.67
TOC FC3 80.7 0.45 7.48 103.9 0.36 0.74
TOC FC4 152.0 0.39 50.98 114.0 0.76 2.36
TOC FC5 616.4 0.25 3.05 0.90 1.29 0.85
TOC FC6 1,496.1 0.17 5.66 4.76 0.05 0.70
Nonadsorbing. TOC concentration (mg/L) 23.2 8.3 2.9 23.0
Total TOC concentration (mg/L) 145.08 260.46 12.75 63.27
Nondilute isotherm RPE values (%) C:15.6 C:25.1 C:8.8 C:30.5
q:28.3 q:29.4 q:7.3 q:130.9
Dilute isotherm RPE values (%) C:20.1 C:30.0 C:16.4 C:15.8
q:29.0 q:17.1 q:8.0 q:29.0

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J. Environ. Eng., 1999, 125(6): 540-547

 TABLE 4. XAD-4 Resin TOC FCs and Their Initial FC Concentrations for Waste Mixture, Shower/Hand-Wash, Urine Distillate, and Hu-
midity Condensate Wastewaters

Freundlich Parameters
Waste mixture Shower/hand Urine distillate Humidity
Component K 1/n C0 wash C0 C0 condensate C0
(1) (2) (3) (4) (5) (6) (7)
TOC FC1 0.217 0.80 9.82 24.85 1.97 12.05
TOC FC2 13.52 0.53 35.42 1.70 1.97 4.49
TOC FC3 41.38 0.46 6.18 96.45 0.19 0.34
TOC FC4 76.58 0.42 42.16 105.81 0.42 1.1
TOC FC5 222.38 0.35 2.52 0.83 0.68 0.40
TOC FC6 380.59 0.31 4.68 4.42 0.025 0.32
Nonadsorbing. TOC concentration (mg/L) 4.43 26.4 7.5 43.60
Total TOC concentration (mg/L) 145.08 260.46 12.75 58.48
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Nondilute isotherm RPE values (%) C:8.6 C:14.0 C:3.2 C:8.46

q:7.7 q:32.0 q:17.8 q:38.7
Dilute isotherm RPE values (%) C:9.9 C:7.1 C:27.9 C:17.8
q:10.6 q:31.1 q:42.6 q:52.6

reasonable predictions for the XAD-4 resin nondilute and di- TABLE 5. Composition of TOC Waste Mixture Isotherms for
lute humidity condensate isotherms. 580-26 GAC
Waste Waste Waste
FC Model Predictions of Waste Mixtures with mixture 1 mixture 2 mixture 3
Different Compositions Waste stream type (%) (%) (%)
The waste mixture water onboard the ISS can vary in both (1) (2) (3) (4)
initial concentration and composition. Consequently, FC Shower 21 18.4 25.0
model calculations were compared with waste mixture TOC Hand wash 31.6 27.6 37.5
isotherm data having different initial concentrations and com- Oral hygiene 2.8 2.5 3.3
position. Because the FCs were fit simultaneously to both di- Wet shave 3.2 2.8 3.7
Humidity condensate 18.8 16.4 22.3
lute and nondilute isotherms, they can be used to predict the Animal condensate 6.9 6.0 8.2
TOC adsorption equilibrium for changes in initial TOC con- Urine distillate 13.9 26.4 0
centration. Two isotherms were performed on the 580-26 GAC Equipment off-gassing 1.8 0 0
using waste mixtures with two different compositions. Table Total TOC concentration
5 summarizes the composition for each combined waste mix- (mg/L) 145.0 144.0 199.0
Nonadsorbing TOC con-
ture isotherm. Waste mixture 1 was the waste mixture used to
centration (mg/L) 26.6 20.5 25.9
obtain the FC initial concentrations shown in Table 2. Waste
mixture 2 was similar to waste mixture 1 except it contained
more urine distillate and no equipment off-gassing water. In
addition, the urine distillate in waste mixture 2 contained all
real wastewater; whereas, waste mixture 1 contained 20% real
urine distillate and 80% surrogate. Waste mixture 3 is similar
to waste mixtures 1 and 2 but does not contain any urine
distillate or equipment off-gassing wastewaters and the initial
TOC concentration is significantly higher.
Fig. 6 compares the TOC isotherm data for waste mixture
2 with the FC model prediction using the waste mixture 1 FCs
in Table 2. The FC initial concentrations were determined by
first assuming the nonadsorbing fraction for waste mixture 2
is the same as that for mixture 1 and then scaling the TOC
concentrations of the FCs. The TOC FC concentrations for
waste mixtures 2 were determined by taking the ratio of the FIG. 6. Comparisons of FCA Predictions with the Nondilute
TOC Isotherm Data on 580-26 PGAC for Waste Mixture 2
total adsorbing TOC concentration of waste mixture 2 (118.6
mg/L) to the total adsorbing TOC concentration of mixture 1
(117.5 mg/L) times the FC concentratioins for waste mixture Because the shower/hand-wash wastewater contains the
1 shown in Table 2. Based on the RPE values, a good model largest fraction of strongly adsorbing compounds, the FCs for
prediction was obtained when considering the composition of the shower/hand-wash mixture in Table 3 also were used to
each waste mixture is different. When the TOC isotherm data predict waste mixture 2 isotherm data. Fig. 6 compares the FC
for waste mixture 1 in Fig. 2 is compared with the TOC iso- model prediction using the shower/hand-wash FCs with the
therm data for waste mixture 2 in Fig. 6, waste mixture 2 is combined waste mixture 2 isotherm data. The FCs determined
a much more strongly adsorbing mixture. Because the adsorp- from the shower/hand-wash wastewater provide an improved
tion strength for mixture 1 is less than that for mixture 2 and prediction of the isotherms.
the FCs were determined from mixture 1, it would be expected Fig. 7 compares the FC model prediction using the shower/
that FCs based on mixture 1 would under predict solid-phase hand-wash FCs with the waste mixture 3 isotherm data. As
concentrations. In addition, the nonadsorbing fraction for stated earlier, waste mixture 3 does not contain any urine dis-
waste mixture 2 is 20.5 mg/L as compared with 26.6 for waste tillate or equipment off-gassing wastewater. Consequently, it
mixture 1. If the nonadsorbing TOC concentration for waste would be similar to the shower/hand-wash wastewater but
mixture 2 was used to scale the FCs, an improved prediction have a higher total TOC concentration than waste mixtures 1
would result as the liquid-phase concentrations would be and 2. The shower/hand-wash FC parameters provide a good
shifted to the left. prediction of both the liquid- and solid-phase data.
JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999 / 545

J. Environ. Eng., 1999, 125(6): 540-547


FIG. 7. Comparisons of FCA Predictions with Nondilute TOC
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Isotherm Data on 580-26 PGAC for Waste Mixture 3
CONCLUSIONS
The FCA method was able to describe the TOC adsorption
strength of the shower/hand-wash, urine distillate, and waste
mixture waters on the 580-26 and APA GACs and XAD-4
resin. The FCA fits for the 580-26 GAC using these waste-
waters had RPE values that were less than 20% in both liquid-
and solid-phase concentration. These fits were very good when
considering that the wastewater isotherms had a considerable
amount of scatter in the data and only a small number of data
points were collected at the high isotherm dosages to deter-
mine accurately the nonadsorbing concentration.
The FCA was able to predict the APA GAC and XAD-4
resin isotherm data for these wastewaters. The APA GAC and
XAD-4 resin RPE values were less than approximately 30%
for most of the liquid- and solid-phase concentrations. Sur-
prisingly, these results are good given that the 580-26 FCs and
their initial TOC concentrations were scaled to determine the
FCs for APA GAC and XAD-4 resin and only the nonadsorb-
ing TOC concentration for the nondilute isotherm for APA
GAC and XAD-4 needed to be known for each wastewater.
This method demonstrates that for these wastewaters, the FCs
can be related from one adsorbent to another by correlating
their Freundlich K values and adjusting the initial TOC con-
centration based on the nonadsorbing TOC concentrations for
each adsorbent.
The FCA method presented earlier did not describe accu-
rately the TOC adsorption strength of the humidity condensate
wastewater for any of the adsorbents. The humidity condensate
isotherm data for 580-26 GAC could not be fit using the FCs
chosen in this study because the FC Freundlich parameters
were too high. The humidity condensate isotherm data showed
very little adsorption capacity for all the adsorbents. A differ-
ent set of FCs with a distribution of very low Freundlich K
values would be required to describe adequately the isotherm
data.
The FCs determined in this study predicted the effects from
changes in initial concentrations and composition for different
ISS waste mixtures on 580-26 GAC. For waste mixture 2,
(which has the same initial TOC concentration as waste mix-
ture 1 but contains more strongly adsorbing compounds) the
FCs determined from waste mixture 1 were able to predict the
liquid- and solid-phase concentrations within RPE values of
20 and 10%, respectively. The FCs that were determined from
the shower/hand-wash isotherm data were able to provide an
improved prediction of the isotherm data because the shower/
hand wash contains a higher concentration of more strongly
adsorbing compounds. For the liquid and solid phases, the
RPE values were 15 and 9%, respectively. For waste mixture
3 (which has a higher initial TOC concentration and contains
more strongly adsorbing compounds then waste mixture 1) the
FCs that were determined from the shower/hand-wash waste-
water were able to predict the liquid- and solid-phase concen-
trations within RPE values of 11 and 5%.
546 / JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999
J. Environ. Eng., 1999, 125(6): 540-547
This TOC modeling approach demonstrated that for waste-
waters containing a mixture of many organic compounds, FCA
model parameters can be determined from a sample distribu-
tion of known compounds in the mixture. The FC Freundlich
K values can be determined from a concentration-weighted
average sample distribution of Polanyi potential theory esti-
mated Freundlich K values. The FC Freundlich 1/n values can
be determined by correlating single solute Freundlich K values
with Freundlich 1/n values. The FC molecular weights can be
determined from the concentration-weighted average molecu-
lar weights of the sample distribution of compounds.
This TOC modeling approach also demonstrated that FC
parameters for one adsorbent could be used to determine the
FC parameters for other adsorbents. The FC Freundlich K val-
ues for other adsorbents can be determined by correlating their
single solute Freundlich K values with those of the adsorbent
in which the FC parameters are known. The Freundlich 1/n
values are determined through correlation to their Freundlich
K values. The FC initial TOC concentrations of the other ad-
sorbents are determined based on the total adsorbing TOC con-
centration of each adsorbent. This does require that the non-
adsorbing concentration of each adsorbent must be known.
The approach presented earlier is valuable for evaluating the
adsorption equilibrium of wastewaters from life-support sys-
tems such as the space station, but it may also be useful for
industrial applications in which complex mixtures of organic
compounds are present in aqueous by-product streams.
ACKNOWLEDGMENTS
The writers acknowledge ION Electronics, Inc. (Huntsville, Ala.) and
NASA Ames Research Center (Sunnyvale, Calif.) for funding this re-
search. This work also was supported by the U.S. Environmental Protec-
tion Agency Center for Clean Industrial and Treatment Technologies and
Michigan Technological University (Houghton, Mich.), although it does
not necessarily reflect their views and no official endorsement should be
inferred.
APPENDIX. REFERENCES
Ali, A. N. (1997). ‘‘Adsorption equilibrium modeling of the international
space station waste waters,’’ MS thesis, Michigan Technological Uni-
versity, Houghton, Mich.
Bulloch, J. L. (1995). ‘‘Fixed bed adsorption modeling for the interna-
tional space station water processor,’’ MS thesis, Michigan Technolog-
ical University, Houghton, Mich.
Carroll, D. L. (1996). ‘‘Chemical laser modeling with genetic algo-
rithms.’’ AIAA J., 34(2), 338–346.
Carter, D. L., Cole, H., Habercom, M., and Griffith, G. (1992). ‘‘Deter-
mination of organic carbon and ionic accountability of various waste
and product waters derived from ECLSS water recovery tests and
spacelab humidity condensate.’’ Presented at the 22nd Int. Conf. on
Envir. Sys., SAE Int., Warrendale, Pa.
Carter, D. L., Holder Jr., D. W., Alexander, K., Shaw, R. G., and Hayase,
J. K. (1991). ‘‘Preliminary ECLSS waste water model.’’ Presented at
the 21st Int. Conf. on Envir. Sys., SAE Int., Warrendale, Pa.
Crittenden, J. C., Luft, P. J., and Hand, D. W. (1985a). ‘‘Prediction of
multicomponent adsorption equilibria in background mixtures of un-
known composition.’’ J. Water Res., 19(12), 1537–1548.
Crittenden, J. C., Luft, P. J., Hand, D. W., Oravitz, J. L., Loper, S. W.,
and Ari, M., (1985b). ‘‘Prediction of multicomponent adsorption equi-
libria using ideal adsorbed solution theory.’’ Envir. Sci. and Technol.,
10(11), 1037–1043.
Crittenden, J. C., Vaitheeswaran, K., Hand, D. W., Wallace, I. E., Aieta,
I. M., Tate, C. H., and McGuire, M. J. (1993). ‘‘Prediction of the re-
moval of dissolved organic carbon removal by fixed bed adsorbers.’’
Water Res., 24(2), 715–721.
Forrest, S. (1993). ‘‘Genetic algorithms: Principles of natural selection
applied to computation.’’ Science, 361(8), 872–878.
Frick, B. R., and Southeimer, H. (1983). Treatment of water by granular
activated carbon. Am. Chem. Soc. Books, Washington, D.C., 247.
Firtz. W., and Schlunder, E. U. (1981). ‘‘Competitive adsorption of two
dissolved organics onto activated carbon:1. Adsorption equilibria.’’
Chemical Engrg. Sci., 36(3), 721–737.
Gallagher, K., and Sambridge, M. (1994). ‘‘Genetic algorithms: A pow-
erful tool for large scale nonlinear optimization problems.’’ Comp. and
 Geosciences, 20(7/8), 1229–1236.
Holland, J. (1992). ‘‘Genetic algorithms.’’ Scientific Am., July, 66–72.
Jossens, L., Prausnitz, J. M., Fritz, W., Schlunder, E. U., and Meyers, A.
L. (1978). ‘‘Thermodynamics of multisolute adsorption from dilute
aqueous solutions.’’ Chemical Engrg. Sci., 33, 1097–1013.
Kuennen, R., Van Dyke, W., Crittenden, J. C., and Hand, D. W. (1989).
‘‘Predicting the multicomponent removal of surrogate compounds by
a fixed-bed adsorber.’’ J. AWWA, 81(12), 46–58.
Luft, P. J. (1984). ‘‘Modeling of multicomponent adsorption onto granular
activated carbon in mixtures of known and unknown composition,’’
MS thesis, Michigan Technological University, Houghton, Mich.
Downloaded from ascelibrary.org by College of Engineering, Pune on 12/26/19. Copyright ASCE. For personal use only; all rights reserved.
J. Environ. Eng., 1999, 125(6): 540-547
Radke, C. J., and Prausnitz, J. M. (1972). ‘‘Thermodynamics of multi-
solute adsorption from dilute liquid solutions.’’ J. AIChE, 18(4), 761.
Randtke, S. J., and Snoeyink, V. L. (1983). ‘‘Evaluation of GAC adsorp-
tive capacity.’’ J. AWWA, 75, 406–413.
Smith, E. H. and Weber, W. J. Jr. (1990). ‘‘Comparative assessment of
the chemical and adsorptive characteristics of leachates from a munic-
ipal and an industrial landfill.’’ Water, Air, and Soil Pollution, Dor-
drecht, The Netherlands, 53, 279–295.
Sontheimer, H., Crittenden, J. C., and Summers, R. S. (1988). ‘‘Activated
carbon for water treatment,’’ 2nd Ed., DVGW-Forschungsstelle,
Engler-Bunte-Institut, Universitat Karlsruhe, Germany.
JOURNAL OF ENVIRONMENTAL ENGINEERING / JUNE 1999 / 547