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831113

Urine Pretreatment for Waste

Water Processing Systems

H. Eugene Winkler and Charles E. Verostko

National Aeronautics and Space Administration
Lyndon B. Johnson Space Center
Houston, TX

Gerard F. Dehner
Hamilton Standard
Division of United Technologies Corp.
Windsor Locks, CT

Thirteenth Intersociety Conference

on Environmental Systems
San Francisco, California
July 11-13, 1983
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Copyright 1983 Society of Automotive Engineers, Inc.

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ABSTRACT
Recovery of high quality water from urine
is an essential part of life support on a Space
Station to avoid costly launch and resupply
penalties. Water can be effectively recovered
from urine by distillation following pretreat-
ment by a chemical agent to inhibit microorgan-
ism contamination and fix volatile ammonia
constituents. This paper presents the results
of laboratory investigations of several pre-
treatment chemicals which were tested at several
concentration levels in combination with sulfur-
ic acid in urine. The optimum pretreatment
formulation was then evaluated with urine in the
Hamilton Standard Thermoelectric Integrated
Membrane Evaporation Subsystem (TIMES). Over
2,600 hours of test time was accumulated.
Results of these laboratory and system tests are
presented in this paper.
INTRODUCTION
LONG DURATION SPACE MISSIONS with large crews
such as on an earth-orbiting space station, will
require the recovery of water from wastewater
such as urine to avoid costly launch weight and
resupply penalties. The optimum method for
recovery of water from urine is by distillation.
Two distillation processes currently under
development are Vapor Compression Distillation
(VCD) and Thermoelectric Integrated Membrane
Evaporation System (TIMES). With either of
these systems, the urine must first be treated
to prevent microbial organisms and volatile
contaminants from carrying over in the distil-
lation process.
Urine normally contains from 2-4 percent of
dissolved material. Approximately one-half of
this dissolved material is urea. Certain
microorganisms, which multiply readily in
collected urine produce an enzyme, urease, which
aids in the hydrolysis of urea to form ammonia.
The ammonia, as well as other volatile contam-
inants, are then free to be distilled over with
the water, giving the water a noxious odor and
making it unfit for consumption.
Previous research in this area has resulted
in several chemical pretreatments. In order to
stabilize urine for distillation, D. Putnam'1)
investigated urine pretreatment formulas that
would produce four effects: act as a bacteri-
cide; maintain pH between 2 and 4; oxidize
volatile organic compounds; and fix free
ammonia and ammoniated compounds. Putnam found
that a formula of sulfuric acid and chromium
trioxide was effective. The sulfuric acid fixes
ammonia as ammonium sulfate and maintains urine
pH between 2 and 4. The chromium trioxide
disinfects the urine and oxidizes some of the
volatile odoriferous organic compounds. This
formula has been used with success in earlier
water recovery systems and recently in the
TIMES. There is concern, however, that hexaval-
ent chromium could present a severe toxic hazard
were it to end up in the product water.
Another pretreatment chemical used in
combination with sulfuric acid is Biopal, an
organic iodophor. The Biopal has almost 20
percent available iodine to maintain disinfec-
tion. The Biopal/sulfuric acid formula was
originally developed at the Chemtric Corporation
under NASA/JSC Contract NAS9-9191 for use in the
VCD subsystem (2) . Additional pretreatment
studies were conducted at the Lockheed Missiles
and Space Company under NAS9-15136(3) and at
Life Systems, Inc. under NA9-15267(4). Varia-
tions of the Biopal/sulfuric acid urine pre-
treatment formula have been used extensively in
VCD water recovery subsystem tests, both at the
contractors' facilities and at the Johnson Space
Center. Several undesirable characteristics
have been observed during operation of the VCD
with Biopal-pretreated urine. Although the
Biopal initially has almost 20 percent available
iodine, evaporation and reaction with various
constituents in the urine rapidly deplete the
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iodine and reduce the disinfection effect. tests are depicted in Table 1. For convenience,
During VCD testing at the Johnson Space Center, formulas were assigned the nomenclatures Biopal
the Biopal/sulfuric acid pretreatment formula- 1, Biopal II, Chromium Trioxide (CrO3) and Oxone
tion failed to keep the urine stable on several Formulations. For these tests urine was col-
occasions. This occurred when pretreated urine lected in large containers stored on ice to
was not processed within three days from the provide a composite, representative sample batch
time of collection. Microbial growth occurred, for the comparison tests.
the pH of the recycle fluid increased rapidly,
and large quantities of ammonia carried over
into the product water. An excessive amount of
solids formed in the VCD, requiring complete
disassembly and cleaning. In addition to these
problems, the Biopal material has been shown to
contribute volatile organic contaminants to the
urine which carryover into the product water.
Also, the Biopal is a thick, viscous material
which hinders formulation with sulfuric acid and
addition to the urine. The addition of an
antifoam agent is also necessary since Biopal
causes the urine to foam excessively.
At Crew Systems Division, Johnson Space
Center, a series of investigaions have resulted
in a new improved urine pretreatment formula.
Oxone (a potassium monopersulfate product of the
DuPont Corporation) mixed with sulfuric acid has
shown promise for use as a urine pretreatment
agent. The Oxone is a strong oxidizing compound
and exhibits biocidal properties. Since the
decomposition product of Oxone is sulfuric acid,
the compound also aids in pH control. One
difference with this formula is that the Oxone PRETREATED URINE STABILITY TEST - Urine
is a solid material and has to be added to the pretreated per the basic formulations in Table 1
urine in solid form prior to addition of the was placed in glass containers with loose tops
acid. Pellets of Oxone have been developed to for 30 days. Two control samples, one with
make the addition more convenient. A series of nontreated urine and the other with just sulfur-
tests were conducted to derive the optimum ic acid treatment were also included in the
formulation for Oxone and sulfuric acid. Then, tests. The results of these tests are presented
comparison tests in urine were conducted with in Table 2. The pH, acid content, and visual
the Oxone, Biopal, and chromium trioxide formu- observations were recorded once a week during
lations. The comparison tests included the the test duration. Since these values changed
following: very slightly during the test period, only the
initial and final values are reported. Micro-
1. Urine samples were pretreated with the bial samples were taken and assayed at the
various agents at several different concentra- beginning and end of the test. Odor was also
tions and monitored to assess stability with monitored during the tests and was considered
time. objectionable for all of the samples, although
2. Urine, pretreated with the various there was some variation in odor and intensity.
formulas, was seeded with microorganisms and
assayed over a period of time to assess the
long-term disinfection effects.
3. Offgassing products of urine with the
different pretreatments were measured and
identified.
4. Representative metallic samples were
exposed to urine pretreated with the various
formulas to assess material compatibility.
5. Water recovery tests were completed
with urine using the TIMES system at Hamilton
Standard Division. Gas Chromatography/Mass
Spectrometry analyses were obtained on the water
recovered from urine pretreated with the chrom-
ium oxide and the oxone formulas.
6. Laboratory tests were conducted to
assess foaming of urine treated with the various
agents.
These tests and their results are presented
in detail in the following pages. The basic
urine pretreatment formulations used for the
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As can be seen in Table 2, all of the
formulas, even the sulfuric acid control,
maintained the pH of the urine in the 2 to 4
range. Microbial contamination occurred in the
Biopal II pretreated sample, the sulfuric acid
control , and the untreated urine. The Oxone
pretreated sample was clear with a pale yellow
color throughout the test and did not develop
any suspended solids. Suspended solids and
turbidity developed in all of the other samples.
In addition to these results, a variety of
other parameters were measured during the test.
These included total organic carbon, ammonia,
urea, and iodine. For the most part, no con-
clusive results could be drawn from these
additional measurements. However, the measure-
ments did indicate that iodine does not persist
in the urine pretreated with the Biopal formu-
las. In the Biopal II pretreated urine, iodine
was immediately depleted. In the Biopal I
pretreated urine, iodine was completely depleted
after one day.
MICROBIOLOGICAL SEEDING TESTS - Two tests
were conducted to evaluate the lasting biocidal
effects of the urine pretreatment. In each of
the tests, the pretreated urine and control
urine samples were seeded with 10(3} quantita-
tions of Escherichia coli, Pseudomonas species,
and Candida albicans. The urine samples were
thoroughly mixed and plated in duplicate on
Tryptose Glucose Agar for the following time
periods: 0 hours, 24 hours, 48 hours, and once
a week for a total of four weeks. All plates
were incubated at 35°C for 48 hours and quanti-
tated.
The first test was conducted with Oxone to
determine the minimum amount necessary for long-
term disinfection. Five (5) urine samples were
prepared with Oxone concentrations varying from
0.1 to 10 mg per cc of urine and with sulfuric
acid at 2.32 mg/cc of urine. Also blanks
(control samples) were prepared of urine and
urine with sulfuric acid only. The samples were
not kept open to the atmosphere. The results of
the microbiolgoical seeding of these samples are
presented in Table 3. As can be seen, a minimum
concentration of 5 mg of Oxone per cc of urine
was needed to obtain complete microbial kill for
the four week period.
A second test was performed with Oxone
amounts of 0.5 to 10 mg per cc of urine with
2.32 mg sulfuric acid per cc of urine. Biopal
I, Biopal II, and CrO 3 formulations were also
tested. As in the first test, blanks of urine
and acidified urine were tested identically.
The same procedure as in the first test was
followed except that Pseudomonas flourescens was
used instead of the general Psuedomonas species.
Also, the pretreated urine samples were kept
open to the atmosphere. The results are depict-
ed in Table 4. As shown, the 5 mg Oxone per cc
of urine sample and the Biopal I sample had
enough biocide to maintain disinfection through-
out the test period. A fourth bacteria species,
Cladosporium, grew on its own in the Biopal II
pretreated sample during the fourth week of the
test.
OFFGASSING ANALYSES - Analysis of the
offgassing products of the pretreated urine was
completed to assess the quantity and identity of
the volatile constituents from the urine recov-
ery feedstock. The quality of the recovered
water will be affected by those offgassing
products which can be condensed. In addition,
this information should be useful for spacecraft
trace contaminant control and/or system venting
requirements. For each analysis, a 5 ml portion
of the pretreated urine was purged with high
purity helium and volatile organics evolved were
concentrated on a Tenax-GC trap. Then, the
organics were thermally desorbed into a liquid
nitrogen cooled precolumn which was transferred
to a Gas Chromatograph/Mass Spectrometer system
for analysis of the concentrated organics.
Analyses were performed on three samples: urine
with Biopal and sulfuric acid, urine with Oxone
and sulfuric acid, and urine with sulfuric acid
only. the same concentration of acid was used
in each urine sample. The concentrations of
Biopal and Oxone were the same as in the Biopal
II and Oxone formulations, respectively. The
results are shown in Table 5.
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The results showed that in the Oxone/

sulfuric acid pretreated urine, the following
materials showed no corrosion at 3X magnifica-
tion: 304 stainless steel, titanium, 316L
welded tubing and 21-6-9 stainless steel.
As can be seen in the table, the least The 316 stainless steel showed only minor
contaminants were produced by the urine with pitting at the liquid/atmosphere interface on
sulfuric acid only. However, dimethylfuran, a the sample coupon. Under 3X magnification, the
compound with a spacecraft maximum allowable 347 stainless steel exposed to Oxone was seen to
concentration (MAC) of 0.04 ppm, was produced in be slightly pitted over the entire surface of
low quantities(6). Sulfur dioxide was the the coupon. Excessive corrosion was evident on
predominant contaminant generated by the Biopal the 440C stainless steel and all of the aluminum
pretreated urine. Sulfur dioxide is corrosive samples, in both Oxone and Biopal II pretreated
and has a spacecraft MAC of 1.0 ppm. The 1,4 urine. For Biopal II no corrosion was observed
dioxane has been shown to be a product of the for the 21-6-9 stainless steel and 316L welded
Biopal iodophor compound itself. The siloxane tubing.
compounds are from the antifoam agent. Major
undesirable contaminants generated by the Oxone TIMES WATER RECOVERY SUBSYSTEM TESTS - As
pretreated urine were sulfur dioxide, cyanogen part of the TIMES water recovery subsystem
chloride (MAC of 0.1 ppm), and the organic testing at Hamilton Standard Division (HSD),
nitriles. These results clearly indicate that both the Chromium Trioxide/Sulfuric acid and the
the volatiles from a spacecraft urine pretreat- Oxone/Sulfuric acid pretreatments were used to
ment and water recovery system will have to be compare performance. The TIMES is a vacuum
vented to space or scrubbed through trace distillation subsystem that utilizes a hollow
contaminant control equipment. Also, some of fiber membrane (HFM) evaporator, a porous plate
these volatiles will condense with the product condenser, and a thermoelectric heat pump. A
water during the distillation process and will schematic of this system is shown in Figure 1.
require posttreatment.
MATERIALS COMPATIBILITY TESTS - Metallic
materials, selected for use in the VCD and the
TIMES water recovery systems, were exposed to
pretreated urine samples to evaluate resistance
to chemical attack and corrosion. Thirteen
(13) samples of various metal alloys were
exposed to the two urine pretreatment formulas
for as long as 140 days. The samples were
coupons, sized 2.5 cm X 7.6 cm X 0.32 cm, except
for the 316L stainless steel welded tubing, the
21-6-9 stainless steel tubing, and the 440CX
stainless steel bar stock. The samples were
half immersed on end in separate beakers con-
taining the Biopal II and the Oxone pretreated
urine and kept at 37.8°C (100°F). The beakers
were loosely covered to allow a humidified
atmosphere. Photographs were taken before and
after the tests. The results are listed in
Table 6.
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Basically, the wastewater, pretreated and stored
in the pretreat tank, is drawn into a constant
volume recycle loop where it is heated to 65.6°C
(150°F) by a heat exchanger in contact with the
hot side of the thermoelectric heat pump. In
the hollow fiber membrane evaporator, water
diffuses through the walls of the hollow fiber
tubes and evaporates. The water vapor is
condensed on a chilled porous plate surface in
thermal contact with the cold side of the
thermoelectric heat pump. The condensate is
then drawn into an accumulator where it is
collected prior to delivery to a posttreatment
module. A more detailed description of the
TIMES system is presented in Reference 6.
The TIMES water recovery subsystem has been
operated for over 2700 hours on both urine and a
urine/washwater mixture. Most of this testing
was done with urine pretreated with the HSD
(chromium trioxide/sulfuric acid) formula.
Although the HSD formula was effective in fixing
free ammonia and disinfecting the urine solu-
tion, it had contributed to some fouling in the
hollow fiber membrane tubes and solids deposi-
tion elsewhere in the subsystem. The deposits
consisted primarily of Cr(OH)3 compound. It
forms in the chromium pretreated urine solution
when the pH exceeds 3.5. In the TIMES system,
as the urine in the recycle loop becomes concen-
trated, ammonia accumulation increases and
causes an increase in pH as it neutralizes the
pretreatment acid charge. This results in the
formation of the Cr(0H)3 precipitate.
Use of the Oxone/sulfuric acid pretreatment
did not exhibit the same chemical equilibrium
behavior and, as a result, did not contribute
precipitates to the recycle fluid and presented
no indication of membrane fouling. The only
change in the urine recycle fluid as it was
concentrated was a shift in color from yellow to
clear amber. The fluid-contacting materials in
the TIMES subsystem are AMS4901 titanium,
AISI347 stainless steel, Viton-A, Viton-GF, and
polysulfone. During the 600 hours of testing
with the Oxone pretreatment, there was no
indication of the materials incompatibility with
the Oxone/sulfuric acid pretreated wastewater.
In subsequent tests with urine/washwater, a
precipitate did form when one of the detergents
{BIOSOFT HD-100) was used in the washing cycle.
This is believed to be a reaction product with
the Oxone. Further investigations into this
phenomenon are planned.
While the TIMES testing was underway,
product water samples were collected and fur-
nished to Spectrix Corporation for identifica-
tion and quantification of organics. A good
urine pretreatment agent should minimize the
amount of organic contaminant carryover into the
product water. Samples were obtained during the
testing with chromium trioxide/sulfuric acid
pretreated urine and compared with samples
obtained during testing with the Oxone/sulfuric
acid pretreated urine. The samples were taken
of untreated condensate to allow a comparison
without the effects of posttreatment. The
identification of the organic contaminants are
shown in Table 7. This analysis, unfortunately,
did not measure formic acid and acetic acid,
major organic contaminants in both products.
Although the results appear to indicate that the
Oxone pretreatment produces fewer organic
contaminants, additional work is needed before
definite conclusions can be drawn. It is
believed that some of the organic contaminants
from both of these pretreated urine products are
caused by partial oxidation of some of the urine
organics, resulting in smaller, lower molecular-
weight species, which are more volatile and can
carry over into the product water. A properly
designed posttreatment system should be effec-
tive in polishing this recovered water to a
purity acceptable for personal consumption and
hygiene.
FOAMING TEST - In preparation for using the
Oxone agent in the VCD subsystem, tests were
performed to evaluate the foaming characteris-
tics of the pretreated urine. Liquid/vapor
separation is maintained in the VCD by arti-
ficial gravity produced by rotating cylindrical
evaporator and condenser surfaces. If the
pretreated urine mixture foams extensively on
the evaporator surface, some could be mechan-
ically transported over into the condensor,
contaminating the product water. To evaluate
the foaming tendencies, 260 ml of pretreated
urine and 155 ml of water (representing the
urinal flush water) was placed into a 1 liter
Erlenmyer vacuum flask. Initial tests indicate
that under low pressure the Oxone pretreated
urine did foam excessively, so the tests were
repeated with the addition of 0.5 mg of antifoam
per cc of urine (the same amount of antifoam as
in Biopal I and II formulations). For compar-
ison purposes, the foaming tests were conductd
with the Biopal I, Biopal II, chromium trioxide,
Oxone with antifoam, and Oxone without antifoam.
A sample was also tested with no pretreatment.
One should remember that both Biopal formulas do
contain an antifoaming agent. Each of the
vacuum flasks was depressurized to approximately
50 mmHg and observed for one minute. Then the
mixture was agitated in a swirling action by
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movement of the vacuum flask and the foaming
characteristics were again observed. The test
was repeated with the same urine samples at
intervals of 24 hours and 8 days to determine if
storage at room temperature would have any
affect on foaming characteristics. Results of
this testing are described in Table 8.
The results indicate that, initially, the
Oxone pretreated urine, without antifoam, does
foam excessively when depressurized. The
foaming is believed to be due to reaction of the
Oxone with urine constituents and formation of
dissolved reaction products. With the reduction
in pressure, some of the reaction products
evolve, causing the excessive foaming. After 24
hours, the foaming had decreased significantly,
at which time it was no worse than the other
pretreated samples. The addition of the anti-
foaming agent controlled the foaming satisfac-
torily and may be necessary for successful use
in the VCD. Alternatively, exposure of the
pretreated urine to low pressure before intro-
duction to the VCD might eliminate the foam
potential and negate the need for the antifoam
agent.
CONCLUSIONS
These studies indicate that a pretreatment
formula based on Oxone (potassium monopersul-
fate) appears to have distinct advantages over
other urine pretreatment agents. Urine, treated
with Oxone and sulfuric acid was stabilized
effectively for a long period of time with less
solids formation than samples with other pre-
treatment. The Oxone agent was found to be very
effective in maintaining disinfection. The
offgassing products of the Oxone pretreated
urine were fewer and of a less toxic nature than
from the Biopal pretreated urine. The Oxone
also is more compatible with various metal
alloys than the Biopal. During testing in the
TIMES water recovery subsystem, the Oxone
formula produced fewer solids and resulted in
product water with a lower number of contamin-
ants. The foam test indicated that addition of
a defoaming agent may be desirable for use in
the Vapor Compression Distillation Subsystem.
Although the Oxone formula does appear to
have significant advantages, further work needs
to be done before its spacecraft applicability
is determined. In addition, extensive develop-
ment work is needed on recovered water post-
treatment to consistently produce water which is
acceptable for consumption and personal hygiene.
Long term testing of complete water recovery
systems including pretreatment, distillation,
and recovered water posttreatment is needed to
verify the technology readiness for regenerative
water systems for space station applications.
ACKNOWLEDGEMENTS
Acknowledgements are given to the personnel
of the Spectrix Corporation, the JSC Toxicology
Laboratory, the JSC Microbiology Laboratory, and
the Crew Systems Division ECS Chemistry Labora-
tory for their analysis and test support.
Acknowledgement is also extended to the urine
donors of Crew Systems Division and Hamilton
Standard Division.
REFERENCES
1. Putnam, D. F., "Chemical Aspects of Urine
Distillation," Paper No. 65-AV-24 presented
at the American Society of Mechanical
Engineers, Aviation and Space Conference,
Los Angeles, CA March 1965.
2. Bambenek, R.A., Nuccio, P.P., Hurley, T.L.,
and Jasionowski, "Upgrading and Extended
Testing of the MSC Integrated Water and
Waste Management Hardware," Final Report
NAS9-9191, May 1972.
3. Johnson, K.L., "Development of a Preproto-
type Vapor Compression Distillation Water
Recovery Subsystem, "Final Report NAS9-
15136, November 1978.
4. Ellis, G.S., Wynveen, R.A., and Schubert,
F.H., "Preprototype Vapor Compression
Distillation Subsystem," Final Report NAS9-
15267, August 1979.
5. Flammability, Odor and Offgassing Require-
ments and Test Procedures for Materials in
Environments that Support Combustion, NHB
8060.1B, NASA, September 1981.
6. Roebelen, G.J. Jr., Dehner, G.F., and
Winkler, H.E., "Thermoelectric Integrated
Membrane Evaporation Water Recovery Tech-
nology," SAE Paper No. 820849, presented at
the Intersociety Conference on Environ-
mental Systems, San Diego, CA, July 1982.