Embed Size (px)
Citation preview
AD-A125 29 A RAPID SAFE DRINKING WATER SUPPLY PRODUCTION METHOD 1/1(U) LOS ALANOS TECHNICAL ASSOCIATES INC NM
GRAN ET AL. 24 OCT 82 DAAK78-82-C-6045UNCLASSIFIED .F/G 13/2 NLEIIIEIIIIIIEI
mlllmlllllllEllllllllE-ElIEhhhhhhhhhhhhIllllhhlllhllIIllIIhhlIIhllhIElllllIIIIIIIE
"-. .
I I L4=- Ilu &6
w4,
,a -- , 2
IN S *jo' E20o
1.8
* 125 fL3A .6,
MICROCOPY RESOLUTION TEST CHART
NATIONAL BUREAU OF STANDARDS-1963-A
_-.5'
',oL-*-"- -° ." -*" .".'" .*- "- .' , .'" °' " ,". ." ",%-"- -H "-
7 7 7-7 77
S-4
Report DAAK-70-82-C-0045
A RAPID, SAFE DRINKING WATER SUPPLY PRODUCTION METHOD
:, '> Helen F. GramMartin E. Muller
' Ann M. Pendergrass
Los Alamos Technical Associates, Inc.Los Alamos, New Mexico 87544
* I. J. WilkScience Services
- Stanford, California 94305
24 October 1982Final Technical Report
Distribution of this documentis unlimited. 1983
Prepared forU.S. Army Mobility Equipment Research and Development CommandDRDME-GSFort Belvoir, Virginia 22060
* 0
C.
-- --- - - --...-j-*- . . .
".C..
or 83 O a
KIL-8Th-647A* _______________________31 January 1973
890u0m0, CLAINIICASOU @U T~OO *Aft Most. Onc Eomm______________
A Rap Safe NTTO Drikin Wate Supply F 5
Marti E.Muler AAK70-2-C004
*~~~~ia Lohnca AResTchia"sscae
7,. 6.T~as~n CONTRAC OAil ANDN AMetSIt E
UarS. Arm Mobilit qipr& Co adA24 October 1982
&nn MUnclassified9. ESTUISUTIN STR9ATIONT N AND ADDES V RAI9"ft..'j9r S
Apove or pubnic relecasedstrbto niie
ISI. COPLNTRN OIESNA ADADESi.8101DT
. WS ArMobPee@ it Equ.w- R&tsDp Cand 24f Ocoer18
DEletrlsis.0"911o AE
PurifyUPotableiWate
lytically inr weaubl slutions uistiing cunltsefd-2
vl ts aOO Cm nd rveo 2-8 o amps nd ambient tyee atuesusngnlti
plnated elrde. heootye ueenite electro- hm
of water on a continuous basis. One volume of electrulyzed
K OS , ~ 1473 LOIWN OF INOV05 ISOSOLETE SECURITY CLASSFICATI0ON VOTIS PAGE (5. e ...
MIL-STD-847A31 January 1973
r*cUUMV LAM aIFICATI he sIr THIS PAglhOw aD&U.0
solution sterilized and deodorized 40 volumes of sewage-contaminated surface stream water in about 10 minutesat a production rate of (600 gal/hr. (2200 1/hr.). Theunit is compact (20" cube) and portable, and can renlacechlorination as a more rapid and thorough disinfectionprocess.
Item 7.
I. J. WilkScience Services,Stanford, CA 94305
" C U P'.Y CM P SC *?S S o f VM S wA oaU M M S m. d
1.0 SUMMARY
'-The electrolytic generation of' ozone and chlorine-hypochlorite (andperhaps free radicals) in weak electrolyte to kill microorganisms has been
investigated. A dilute NaCI solution was passed between novel platinumelectrode plates which carried a current of 5-25 volts and 2-8 amps. Theamount of ozone generated in the anode stream was found' to be directly
related to the applied voltage and to the electrolyte concentration. Theprototype unit developed for these experiments is capable of electrolyzing1 t/min of water on a continuous basis. One volume of electrolyzed solution
(produced at 10 volts, 3.5 amps) sterilized and deodorized 40 volumes of* surface stream water contaminated with raw sewage. Conservative estimates
are that 18,000 5 (4,800 gallons) of water contaminated with microorganismscould be sterilized in an 8-hour day using 0.035 kw. The unit is compact(20' cube) and portable, with a pump as the only moving part. The unitgenerates ozone directly in water at ambient temperatures rather than byusing oxygen, an air supply, or hazardous chemicals such as chlorine gas.Such a, system could replace chlorination as a more rapid and thorough
secondary treatment process.
1)7
1. - C L
%
F 2.0 PREFACE
2.1 Authorization
This project was authorized under Contract No. DAAK 70-82-C-0045
pursuant to the DESAT program of the Department of Defense.
2.2 Relationship of Work to Overall Project
The electrolysis unit developed and tested under this contract to destroy
bacterial and chemical contaminants can be placed downstream of the reverse
osmosis elements in the reverse osmosis water purification unit (ROWPU) now
being field tested to provide safe drinking water for troops. It can also be
developed as a stand-alone unit to provide safe drinking water, free from
nuclear, biological, and chemical warfare agents for troops and individual
soldiers.
2.3 Contributors
The contributors to this project are:
H. F. Gram
M. E. Muller
A. M. Pendergrass, PhD
I. J. Wilk, PhD
2.4 Copyright Permission
No copyrighted material was used in work performed under this contract.
The novel platinum *lectrodes, used with the permission of the inventor,
Mr. C. D. Themy, are covered by the following patents:
3,443,055 Laminated Metal Electrodes and Method for Producing
the Same.
2. . . . . . . . .
, A , . .A ,.. - P 0,,' ". ' .. * ... , J.,' % . .. ". '- "- . -. .. - - -,. . •. - ! . i .-
-Los Alamos bchrical Assocites, hac.
Ross M. Gwynn, 916 Donnajo Way 95825, andTim Themy, 7025 Uranus Parkway 95823, both ofSacramento, Calif.Filed Jan. 14, 1966, Ser. No. 520,596Patented May 6, 1969.
3,547,600 Composite Electrode Having a Base of Titanium or"" Columbium, an Intermediate Layer of Tantalum or
Columbium, and an Outer Layer of Platinum GroupMetals.Ross M. Gwynn and Tim Themy, Carmichael, Calif.,
assignors, by mesne assignments, to KDI Chloro GuardCorporation, a Corporation of Delaware.
Filed May 28, 1968, Ser. No. 732, 510
Patented December 15, 1970
4,236,992 High Voltage Electrolyte Cell
Constantinos D. Themy, 4984 S., 360 West, Murray,
Utah, 84106.Filed August 6, 1979, AppI. No. 64,073
Patented December 2, 1980.
I,3
* 3l
.............
s.
;3.0
3.0 TABLE OF CONTENTS
Page
1.0 Summary 1
2.0 Preface 2
2.1 Authorization 22.2 Relationship of Work to Overall Project 22.3 Contributors 22.4 Copyright Permission 2
3.0 Table of Contents 4
4.0 Report 5
4.1 Introduction 54.2 Investigation 6
4.2.1 Static System 64.2.2 Laboratory Scale Flow-Through System 84.2.3 Microbiological Tests 104.2.4 System Design Modifications 154.2.5 Construction of Prototype Electrolysis Unit 174.2.6 Ozone Generation Tests 234.2.7 Microbiological Tests 274.2.8 Potential for Detoxification of Chemical Agents 32
" 4.3 Discussion 33
4.3.1 Historical Perspective 334.3.2 Unit Development and Testing 35
4.4 Conclusions 39
4.5 Recommendations 40
5.0 References 41
Appendix A - Ozone Determination Method 42
Appendix B - Computerized Literature Survey 44
Distribution List 93
4
4.0 REPORT
4.1 Introduction
Ozone has long been used as a potable water treatment method because itis effective ins killing bacteria, viruses and other microorganisms; it increasessettling; removes tastes, odors, and colors; oxidizes sulfides, cyanides, and
* algae; and oxidizes organic materials. However, standard ozone generation*techniques currently in use are not amenable to field conditions. In contrast
the ozone generation unit developed under this contract is small and portable,with low power consumption. Ozone is generated by electrolysis directly inwater, which eliminates gas to water transfer problems and minimizes hazardsof handling harmful chemicals such as chlorine. The unit can produce large
* amounts of excellent quality water in the field.
Under this contract, a fast, efficient, and safe process for waterpu rif ication/decontami nation using novel platinum electrodes in a portable unitsuitable for field use was to be developed and tested. The concept ofgenerating ozone directly in water was,. to be verified. A prototype
* electrolysis unit was to be built, capable of producing essentially steriledrinking water at a rate of 1,000 k/day. This has been accomplished.
The tasks specified in the scope of work are
* establish the optimum efficiency of microorganism kills and thecorresponding reduction in size, weight, and power consumption ofthe prototype unit, Task 1;
* develop a base unit capable of producing about 1000 e/day of pure-drinking water, Task 2;
* conduct a literature search to identify potential chemical warfareagents and the detoxification effects of oxidation- ozonolysis andhydrolysis on compounds of this type, Task 3;
5
* conduct preliminary laboratory studies to determine the feasibility of
the unit to produce decontaminated as well as sterilized water,
Task 4.
This electrolytic ozone generation unit could be incorporated into the
ROWPU unit downstream from the reverse osmosis elements. Bacteriological
and chemical contaminants would be detoxified by the electrolytic unit.
Alternatively, fresh water which did not require desalination could be treated
directly with the electrolytic unit to destroy biological and chemical
contaminants thereby doubling the output of the ROWPU. The addition of an
ion-exchange column would remove radioactive contaminants.
4.2 Investigation
4.2.1 Static System
Preliminary tests were conducted to determine the conditions under which
ozone and chlorine-hypochlorite could be generated in water electrolytically.
Electrodes of 4 cm x 6 cm dimensions were placed 0.5 cm apart in a
cylindrical cell 11 cm high by 6.5 cm in diameter. Tap water solutions of 3
and 30 g NaCI/ were placed in the cell. Direct current at a series of
increasing voltages and amperages was applied across the electrodes for
2 minutes. Total chloride and ozone in the electrolyzed solutions were
measured by amperometric titration with thiosulfateI . Two samples were
obtained. The first sample, adjusted to pH 4 with H2 so 4 , was then titrated
against standard thiosulfate solution to measure total chloride (HOCI OC).
The second sample was adjusted to pH 11.5 and allowed to react for 2 minutes
to decompose 03. This sample was next adjusted to pH 4 with H2 SO4 , and
then was titrated in the same manner to measure 03 + total chloride. The
2difference in the 2 samples is a measure of 03 concentration
1. Greenbure, A. G., J. J. Connors, D. Jenkins, and M. A. H. Franson,eds. "Standard Methods for the Examination of Water and Wastewater,"
. 15th ed. Amer. Pub. Health Assn., 1980.
2. Wilk, I. J., personal communications with H. Gram and unpublished work,1969 - 1982.
6
. S.. .. S - S S - .]
.7
Both ozone and chlorine-hypochlorite concentrations are directly relatedto the applied voltage (Tables 4-1 and 4-2). At a comparable voltage, thehigher concentration of electrolyte allows more current to flow, and moreozone and chlorine-hypochlorite are formed.
TABLE 4-1
OZONE GENERATION IN 3 g/t NaCI SOLUTION(Tap water, pH adjusted to 7.05, electrolyzed for 2 minutes)
TemPin TemPou t PH pH Cl 2 03Volts Amps (°C) (oC) in out (mg/) (mg/2)
3 0.2 23 23 7.05 7.05 10.5 05 0.9 23 23.5 7.05 7.85 18.0 2
10 3.1 23 24 7.05 8.05 83.0 1
*C12 and 03 were measured by titration as described in the text.
TABLE 4-2
OZONE GENERATION IN 30 g/Q NaCI SOLUTION(Tap water, pH adjusted to 7.2, electrolyzed for 2 minutes)
*" •
Tempin Tempo ut pH pH Cl 2 03Volts Amps (oc) (oc) n out (mg/0) (mg/)
3 0.5 23 24 7.2 8.4 55 46.8 10.0 23 25 7.2 10.4 920 0
*Ci and 03 were measured by titration as described in the text.
7
Low ozone concentrations measured at high voltages were thought to be
due to excess OH" generated at the cathode which decomposed the ozone. 3
On a thermodynamic basis, chloride ions react with ozone to form chlorine but
the reaction is limited by unfavorable kinetics. Even in acidic solutions, the
rate of reaction is so slow that it is of no practical significance. 4
I'sing the small static cell, sufficient oxide is generated by a 10 volt,
3 amp current per volume of 3 g/e NaCI solution (Table 4-1) to disinfect 8 to
10 volumes of water, with a slight increase in salt concentration. When 30 g
NaCl/e (sea water) was electrolyzed using 6.8 volts, 10 amps, approximately
30 volumes of water could be treated based on the quantity of
chlorine/hypochlorite formed (Table 4-2).
4.2.2 Laboratory Scale Flow-Through System
In order to disinfect large quantities of water, a continuous system is
more efficient than a batch process. Electrolytic experiments were carried
out to determine feasible operating parameters of a flow-through system. As
in the static system, electrodes of 4 cm x 6 cm, spaced 0.5 cm apart wereenclt-ed in a housing. Tap water containing 3.0 g NaCI/A was adjusted to
pH 7.05 and passed through the electrolytic cell at rates of 0.2 and 1 E/min,
at increasing voltages and amperages.
Generally, the higher the applied voltage/amperage, the greater the
increase in temperature of the treated water (Table 4-3). Increased
temperature increases the decomposition rate of ozone4 , which may account for
3. Venosa, A. D., Ozone as a Water and Wastewater Disinfectant: a Litera-ture Review in "Ozone in Water and Wastewater Treatment." F. L.
a Evans III, ed. Ann Arbor Science Publishers, Inc. 1972.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Technol-ogy," Ozone, Vol. 16, 3rd ed., John Wiley , Sons, NY, 1981.
8
TABLE 4-3
OZONE GENERATION IN FLOW-THROUGH SYSTEM(Tap water containing 3.0 g/t NaCI)
Flow Rate Tempin Tempout C12 0 3(a/min) Volts Amps (OC) (oC) PHin PHout (mg/) (mg/ )
0.2 5 0.6 23 24.0 7.05 7.8 16.0 1.510 2.9 23 24.0 7.05 8.0 45.0 2.015 5.9 23 26.0 7.05 8.35 110.0 0.0
1.0 15 5.2 22 22.0 8.4 8.8 25.5 2.725 10.0 22 23.5 8.4 9.23 42.5 5.4
failure to measure residual ozone generated at 15 volts and 0.2 i/min flow.
Increased chlorine concentration indicates increased electrolytic activity. If
ozone generation per unit time is a function of voltage and electrolyte
concentration, a slower flow rate through the cell should produce greater
ozone concentration in the outflow stream. However, in an experiment to
, demonstrate this, the ozone concentration in electrolyzed solution was not
. positively affected by the slower flow rate (Table 4-3). This may be due
* again to destruction of ozone within the electrolytic cell by OH generated at
the cathode. More rapid flow through the cell would decrease the contact
time and preserve more ozone in the outflowing stream.
These tests establish that both ozone and chlorine-hypochlorite in
measurable quantities can be generated electrolytically in dilute NaCI solutions
at a flow rate of 1 k/min, and a current of 5 to 25 volts. As shown in
* Table 4-3, the ozone and chlorine-hypochlorite produced are related directly
to voltage, amperage, and concentration of electrolyte in the flow-through
system, as in the static system. These results complete the part of Task 1
relating to experimental ozone generation. The completion of the remainder of
Task 1 is discussed in Subsection 4.2.3.
69
4.2.3 Microbiological Tests
The effectiveness of electrolyzed solutions to kill Escherichia coli was
tested. For these determinations, 760 ml of tap water spiked with E. coli to
a concentration of 106 cells/ml was mixed with 20 ml samples of tap water
which had been passed through the electrolytic cell at a range of voltages
from 5 to 25 volts, 0.75 to 9.5 amps. This is a 1/38 dilution of treated to
untreated water. Samples were collected in sterile bottles containing a small
amount of Na 2 S 2 0 3 . Coliform counts were carried out by membrane filtration
using ENDO broth, 3 dilutions per sample time, following 909A Membrane
Filter Procedure. 1
The original E. coli count of 106 cells/ml is considered to be a
worst-case contamination of a water source. The dynamics of coliform kill,
Figure 4-1, show that destruction of bacteria is largely accomplished during
thf first 5 minutes following introduction of the electrolyzed solution.
Essentially sterile water was produced in a batch process within 10 minutes
by treating 38 volumes of heavily contaminated water with one volume of 3 g/t
NaCI salt solution electrolyzed at 25 volts, 9.5 amps, produced at a rate of
1 /min. There was no further significant reduction in bacterial population
after 10 minutes. On this basis, 2280 e (600 gal) of water could be sterilized
per hour, or 54,720 k/24-hour day (14,400 gal). The increase in NaCI
concentration of the treated water would be about 80 mg/e. If less heavily
contaminated water were treated, a reduction in E. coli of 104 /ml could be
" .achieved within 5 minutes using water treated at 15-20 volts, 4-10 amps. The
amount of ozone required for sterilization depends upon the bacterial
population and quantity of organic material in the water. 4 , 5
1. Greenberg, A. E., J. J. Connors, D. Jenkins, and M.A.H. Franson,eds., "Standard Methods for the Examination of Water and Wastewater."15th ed. Amer. Pub. Health Assn. 1980.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Technol-ogy," Ozone, Vol. 16, 3rd ed., John Wiley & Sons, NY, 1981.
5. Kinman, R. N. Ozone in Water Disinfection in "Ozone in Water andWastewater Treatment," F. L. Evans III, ed. Ann Arbor SciencePublishers, Inc. 1972.
10
T40 ffig TAP WATO COUTAMTW~
-
~w "I L AuI Wh s (aLLSIMI~
8 or NOWIA.iis FLOW OATa
66..
400
2.0
20vY.
0 1
fiure 4-1 Dynamics Of I~ ~ 2n OUin
r A test of water sterilization was run using 30 9 NaCI/1 in tap water as
the electrolyte solution because this approximates sea water, a source which
could be readily available. Water contaminated with 106 E. coli/ml was
sterilized to less than 2 bacteria per ml within 30 minutes by treating
38 volumes of contaminated water with 1 volume of 30 g NaCI/Z solution
electrolyzed at 6.8 volts, 9.5 amps, flowing at 1 Q/min. On this basis, about
3 times as much water could be sterilized per day as using 3 g NaCI/9, which
is about 150,000 liters. The added salt increased total dissolved solids (TDS)
concentration by about 250 mg/R. The New Mexico water quality standard,
which is an aesthetic limit for TDS, is 1,000 mg/k. The Army long-term
quality standard for TDS is 1500 mg/e. 6
An experiment was conducted to test the effectiveness of dilute
hypochlorite solution compared with the ozone/chlorine-hypochlorite solutions
generated electrolytically to kill microorganisms. In these tests, one volume
of oxidant solution was mixed with 38 volumes of tap water contaminated with
106 E. coli/ml. Concentrations of coliform bacteria were measured over a
30 minute period. Total kill was produced in 10 minutes by the 3 g NaCI/1
solution electrolyzed at 25 volts 9.5 amps, the 30 g NaCI/A solution
electrolyzed at 6.8 volts 9.5 amps, and the Ca(OCI) 2 solution. However,
after 1 minute, both of the ozone/chlorine-hypochlorite solutions had killed
slightly more bacteria than the Ca(OCI) 2 solution (Table 4-4). There may bea synergistic effect using the ozone/chlorine-hypochlorite solution compared to
using hypochlorite alone. Ozone is known to act faster than chlorine in
killing microorganisms. 4 This is suggested by the slightly faster kill rate
obtained from the electrolyzed 30 g NaClh/ solution compared to hypochlorite
alone. Both solutions have a comparable total chloride concentration.
6. Department of the Army Technical Bulletin R B Med 229, "Sanitary Con-trol and Surveillance of Water Supplies at Fixed and Field Installations,"U.S. Government Printing Office, 1975.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Technol-ogy," Ozone, Vol. 16, 3rd ed., John Wiley , Sons, NY, 1981.
12
TABLE 4-4
COMPARISON OF BACTERIAL KILL BYHYPOCHLORITE AND ELECTROLYZED SOLUTIONS
(One Volume of Solution Added to 38 VolumesTap Water Contaminated with E. coli)
Total Initial E. coli ConcentrationSalt Conc Cl 2 Oxidant (Cells/me)
Solution (g/k) (mg/R) (mg/1) Initial 1 min 5 min 10 min
Ca (OCI) 2 9.4 x 10 47 1.2 106 1.7 x 105 <1 <1
* NaCI
25 v, 9.5 a 3.0 150 1.2 106 9.3x 104 1.6 x 10 <1
NaCI
6.8 v, 9.5 a 30.0 44 3.9 106 1.5 x 104 <1 <1
Dilute acid solutions were electrolyzed and the effluent tested for kill of
E. colt, in the same manner as the NaCI solutions. Perchloric acid (0.01N)* and sulfuric acid (0.01 and 0.1N) were electrolyzed at 11 to 42 volts and
6.8 to 11 amps. One volume of electrolytically-generated oxidant solution was. mixed with 38 volumes of tap water contaminated with 10 E. coli/ml.
Concentrations of coliform bacteria were measured over a 30 minute period.
The reduction in bacterial population (Table 4-5) was very small despiteShigher applied current (Table 4-4), which demonstrates that acid solutions*are not nearly as effective as salt solutions in water for electrolytic
- treatment.
A second type of biological agent, L egionella pneumophila, the
" Legionnaires' Disease agent, was tested for the efficiency of kill with
electrolytically produced oxidant solution. Solutions containing 985 ml of cell
suspension were treated with solutions produced from 3 g9/ NaCI in tap waterelectrolyzed at 20 volts, 7 amps. Electrolyzed solution obtained by catheter
*i from the anode area was added to form total oxidant doses of 0.75 mg! and
0.50 mg/k in the L. pqneumophila suspensions. The introduced solution
j! 13
TABLE 4-5
EFFECTIVENESS OF ELECTROLYZED DILUTE ACID SOLUTIONSIN ACHIEVING BACTERIAL KILL
(One Volume of Solution Added to 38 Volumes of Tap WaterContaminated with E. coli)
Acid Initial E. coli ConcentrationConc Oxidant (Cells/ml)
Solution (N) Volts Amps (mg/L) pH initial 1 min 5 min 10 min
H so4 0.01 42 7.5 2.4 0.6 2 x 106 2~ x 1 6 2 -0 10io
H2SO 0.1 11 11 1.7 0.2 3, 106 2 - 106 1 - 106 3 , 10'2 4
HCIO4 0.01 42 6.8 2.3 0.3 2 106 2 - 106 7 . 105 4, 105
contained 1 mg O3/e and 33 mg Cl 2 /k. For comparison, similar tests
made using solutions of 0.75 mg/e CIO 2 and 0.67 mg/e HOCI.
Ozone-hypochlorite is effective against L. pneumophila at the doses
tested, 0.50 and 0.75 mg/t (Table 4-6). There is less kill at the early
sample times than was noted with E. coti, indicating that L. pneumophila may
be more resistant. Experience has shown it to be difficult to kill and
resistant to chlorine concentrations in drinking water. The 0.75 mg/t
ozone-hypochlorite solution was the most effective solution tested, superior to
0.75 mg/1 CIO2 and 0.67 mg/e HOCI. Again, a synergistic effect of ozone-
hypochlorite is suggested by the greater kill at similar total oxidant
concentrations.
TABLE 4-6
r EFFECTIVENESS OF OXIDANT SOLUTIONS INr LEGIONELLA PNEUMOPHILA KILL1'.
L. pnoumophila Concentration: CoIls/mkSolution Total Oxidant Initial 2 min S min 15 min
O3 /HOCI 0.75 mg/t 10F 1.9 -1o 1.5. 104 3.0 1"l
O3 /HOCl 0.50 mg/1 107 3.0 - 106 3.1 - 105 2.5 - le
CIO 2 0.75 mg/t 107 2.0. I06 1.0. 103 1.0 103
OCl 0.67 mg/t 10 8.0. 106 6.0 106 1.0 106
14
__.
.7
These tests show that severely contaminated water can be sterilized with-
in 5 minutes by mixing 38 volumes with one volume of electrolytically treated
water. Either 3 g NaCI/ solution trhated with 25 volts at 9.5 amps or 30 g
NaCIA solution treated with 6.8 volts, at 9.5 amps, produced at a rate of
1 t/min, will kill virtually all coliform bacteria. At this production rate,
56,000 liters (14,800 gallons) of water per day could be sterilized. Less
severely contaminated water could be sterilized at lower power requirements.
The tests establish the voltage/amperage and salt concentration require-
ments for optimum kill of a worst-case microorganism contaminated water,
completing Task 1.
4.2.4 System Design Modifications
The standard electrodes used in these early experiments were platinum
foil bonded to a titanium substrate (Patent No. 3,443,055). An improved
* electrode was subsequently obtained for testing (Patent No. 3,547,600). In
the improved electrode, the platinum foil is bonded to the titanium through an
intermediate layer of tantalum. Preliminary tests comparing the two
(Table 4-7) indicate that the chlorine generating efficiency of the improvedelectrode is 2.8 times that of the original electrode. The reason for superior
performance is not known but may be due to better bonding and increased
current flow. The improved type of electrodes formed as flat plates were
incorporated into the prototype electrolysis unit built subsequently for
*" Task 2.
TABLE 4-7
i oCOMPARISON OF STANDARD AND IMPROVED ELECTRODES
Electrode
AreaS out C 2 03Electrode Volts Amps (°C) (oC) PH in out (m/Q) (mq/) (cm )
* Original 5 0.5 23 23 7.05 7.6 3.0 0 20
Improved 5 0.6 23 23 7.05 7.9 8.3 0 24
15
Tests of longevity have been conducted on the standard electrodes. A
1200 hour test in which 100 volts at 10-20 amps was passed between elec-
trodes resulted in a negligible loss of the electrode material. A minimum
operating life expectancy of 6 years was estimated from this test. On a
commercial scale, a unit installed to purify a municipal water supply in Neo
Pendeli, Greece, was operated for 6 hours per day at 20 volts and
35-40 amps. Due to extreme hardness of the water, the electrodes requried
cleaning weekly. The electrodes were 10.16 cm long, 5.08 cm wide. Thisexperimental installation was operated for 6 months, or 1100 hours of oper-
ation. A similar installation in Zakynthos, Greece, was operated for more
than 5 years, 14 hours per day, at 20 volts and 33-40 amperes. The elec-
trodes, 10.16 cm x 5.08 cm, were acid-washed twice a week because of the
hardness of the water. This unit was first serviced 3- years after instal-
lation. Assuming that the electrodes were replaced at that time, the electrode
operating life would have been 18,000 hours. 2
The cost of the commercial electrodes, 10.16 cm x 5.08 cm, is not known
at this time. The cost of electrodes used in the prototype unit, 4.5 cm x
5.5 cm, is about $250.
All foregoing tests suggested that the ozone (measured by Na2 S2 0 3
titration) was being destroyed within the electrolytic cell by OH- produced at
the cathode. This is reported in other work 7 , and the small distance
(0.5 cm) between electrodes supports this idea. To avoid or reduce mixing
of products formed at the separate electrodes, a semipermeable membrane,Dupont Nafion 315, was inserted between the electrodes. Samples of the
2. Wilk, I. J., Consultant, personal communications with H. Gram andunpublished work, 1969-1982.
7. Farooq, S., E. S. K. Chian, R. S. Englebrecht, "Basic Concepts in
Disinfection with Ozone" Journal WPCF, August 1977, pp. 1818-1831.
16
. .
were removed from the anode side of the cell with a catheter for analysis. Inboth flowing and stationary systems, the Interposition of a membrane betweenthe electrodes resulted in significally higher ozone concentration in the
-' electrolyzed water (Table 4-8).
TABLE 4-8
EFFECT OF INTER-ELECTRODE MEMBRANEON MEASURABLE OZONE AND CHLORINE CONCENTRATIONS
Cl 2 03Solution Flow Rate Membrane Volts Amps (mg/k) (mg/k)
3 g NaCI/Z 1 a/min 25.0 9.0 19.3 7.2- 25.0 10.0 42.5 5.4
30 g NaCI/2 stationary 10.0 11.4 370.0 62.5- 6.8 10.0 920.0 0
The membrane concept was incorporated in the prototype electrolysis
unit. The substitution of better cell design and electrode components during
the design of the working model resulted in a superior piece of equipment.
The working model is considered to incorporate the latest information available
from the preliminary studies.
4.2.5 Prototype Electrolysis Unit
A prototype electrolysis unit which incorporates the improved electrodes
and interposed membrane was constructed.
Process Description
A schematic of the electrolytic water purification system is shown inFigure 4-2. In this system raw water is mixed with an electrolyzed salt
. solution to destroy impurit by reaction with ozone, hypochlorite, and free
radicals. These chemical secies are generated in the salt solution as it isl a passed between the two electrodes of the electrolysis unit. The quantities of
ozone and hypochlorite that are thus generated are related to the voltage and
, amperage applied to the electrodes.
17
K. u
'41, L
IC 4
z0
0 C 0
0mc U
I.ILa0
49U
Figue 4 Th* rottypeEletrolsisUni
The salt solution is produced by contacting NaCI crystals with raw water
to produce a saturated solution. The solution is then diluted with raw water
to a predetermined concentration. Complete mixing of the saturated salt
solution with raw water is assured by the use of a static mixer.
The electrolyte solution is passed between two novel electrodes at a flow
rate of 1 liter per minute. Electrolysis produces ozone and chlorine-
hypochlorite in situ. The amount of oxidant formed is sufficient to purify up
to 60 volumes of raw water per volume of electrolyzed solution. The
electrolyzed solution and raw water are mixed in a static mixer to maximize
contact of impurities with oxidant. The water is stored in a catch tank after
treatment.
The anode and cathode outflow streams are kept separate in order to
analyze the anode stream. Early tests showed a decrease in ozone measured
when the two streams were allowed to mix, probably due to the decomposition
of ozone by OH'. Under field conditions it may be desirable to reserve the
cathode stream until sterilization of the water has taken place, then add it to
the treated water to raise the pH and obtain decomposition of chemical agents
by alkaline hydrolysis.
The key element of the electrolysis system is the electrolytic cell
(Figure 4-3). The overall length of the unit is 17.75 cm (7 in.); the height
is 10.8 cm (4.25 in.). Electrodes formed as flat plates are oriented along the
sides of the cell. The distance between electrodes is 0.5 cm (0.2 in.). Total
volume of the cell is 13.1 ml. The membrane, Dupont Nafion 315, is oriented
as nearly as possible down the center of the cell. Both electrodes are the
improved titanium-tantalum-platinum type, but only the anode needs to be this
type. Based on the size of the electrode cell, this prototype unit is
portable, as specified in Task 2.
The volume of the system from the electrode to the static mixer where
untreated and electrolyzed solution are mixed is 33 ml. At f flow rate of
1 t/min, residence time of electrolytical.ly treated water from entering the cell
to mixing is less than 3 seconds.
19
MI
* Figure 4-3. The Eiectrode Cell
20
The volume of the static mixer and piping to the storage (receiving)
tank Is about 1 1. At an electrolyzed solution/raw water ratio of 1/40 and an* -electrolyzed water production rate of' 1 I/min, the residence time between
entering the mixer and collection in the tank is about 1.5 seconds.
The prototype unit utilizes a variable power supply. This can be
reduced in size for a field unit which need only produce a single voltage.Specifically, tests were made to determine whether voltage available from an
automobile battery, 10-12 volts, would generate sufficient ozone to killmicroorganisms, which it did, as discussed in Subsection 4.2.7.
Components, Parts, and Materials
Storage Tanks
Storage for the raw water and the treated water is in plastic containers*large enough (150 gal) to allow several minutes of continuous operation of the
electrolyzer. Plastic is used to avoid the potential problem of introducing*corrosion products into the water. The storage tanks would not be an* integral part of a prototype unit.
Pumps
Two pumps are required to move the water and electrolyte solution
through the system. Water is pumped to the NaCI bed and peristaltic pump.* Peristaltic pumps operate by squeezing a flexible tubing and thus forcing the
liquid ahead of the squeeze point. The peristaltic pump has variable speedconitrols to allow adjustment of the flow rate. Additionally, control valves atthe rotometers provide accurate flow control. The raw water is moved with a
.4centrifugal pump. This pump is capable of moving up to 10 gallons per
minute of raw water.
NaCI Bed
The NaCI bed is a plastic container filled with NaCI crystals. Raw water
enters through the top of the container and is directed to the bottom by aninternal pipe. Saturated salt solution exits the top of the container.
* 21
Static Mixers
The static mixers are plastic pipes equipped with Ross plastic static
mixer elements. These elements provide positive mixing of the solutions but
have no moving parts.
Rotometers
The outlet from each pump is connected to plastic, floating-ball-type
rotometers to measure flow rates. Control valves are an integral part of therotometers.
Electrolytic Cell
The electrolytic cell consists of a pair of platinum coated electrodesfitted in an acrylic container. The container holds the electrodes at a 0.5-cmspacing and directs electrolyte flow between them. The ends of the containerare fitted with plastic tubing connectors to allow connection to the pipingsystem. A membrane, Dupont Nafion 315 is permanently fixed between theelectrodes. Division of flow to the two chambers around the membrane iscontrolled by a rotometer and control valve in the stream exiting the cathode.
Piping and Valves
* *All piping and valves throughout the system are plastic, either teflon,
PVC or tygon.
Power Supply
The power supply is capable of converting 115 vac, 60 hz power to
0-60 vdc. It has an amperage rating of 20 amps. The lab power supply maybe different from that used in a prototype unit, and is much larger than what
would be required by a field unit.
22
4.2.6 Ozone Generation Tests
Ozone was generated by the prototype unit using salt concentration,voltage, and flow rate parameters established in Task 1. Ozone was measured
in the anode stream, using the more sensitive method of indigo dye
bleaching. This method is detailed in Appendix A. Indigo trisulfonate
which has an absorbance maximum at 600 nm, is rapidly and stoichiometrically
oxidized by ozone to isatin sulfonic acid, colorless at that wavelength. Ozone
was then measured by the disappearance of dye. Chlorine causes a slow
decoloration of the dye within 1 Interference by chlorine was minimized* by promptly measuring the color disappearance, in solution acidified to pH 2
with H2SO4 . The ozone measurements are relative in that the method was not
standardized against known ozone concentrations. Total chlorides were
measured using a HACH colormetric procedure. This method utilizes
prepackaged reagents and a visual color comparison against a standard color
wheel. It is considered indicative only.
Ozone generated by the prototype unit was related directly toconcentration of salt in the solution passing through the cell and to the
applied voltage. Tests over the range of 2 to 25 volts, 0.1 to 3.5 amps,
were carried out on 3 g NaCI/Q solution (Figure 4-4) and 5 to 20 volts, 0.75
to 7.5 amps, on 30 g NaCl/Z solution (Figure 4-5). The ozone generation in30 g NaCI/e is about 12 times that in 3 g NaCl/k at the same voltage.
Increasing the voltage beyond 25 volts was shown not to be necessary.
Another determination of the effect of salt concentration on ozonegeneration was made over the range 0.625 to 30 g NaCl/i (Figure 4-6).
Again, there is a strong linear relationship, and a great deal of ozone can
be produced at high salt concentrations, as much as 163 mg/9 in 30 g NaCI/
solutions, electrolyzed at 10 volts, 3.5 amps.
8. Bader, H. and J. Hoigne, "Determination of Ozone in Water by theIndigo Method," Water Research, Vol. 15, pp. 449-456, 1981.
23
* .*
175
150i A I MIN FLOW RATE
125
*Z 100
Z
Z 70
25
00
K5 10 15 20 25 30
VOLTS
42
I1OW0
m/1 30. gI.L, Ned
I A MIN FLOW RATE
aMo
400
200
0
5 10 15 20
VOLTS
*Figure 4-5. Ozone Generation -Voltage Relationship in 30 9 NaCl'k Solution
'25
,'.-
170
1601 J, MIN FLOW RATE
150 -10 VOLTS D. C.
140
130
120
* 110
*z 100
m 90
00
60
50
40
30
20
10.
0 0 210 1 10
NaCI - 911
Figure 4-6. Ozone Generation Relationship to Salt Concentration
26
An attempt was made to measure ozone generated at flow rates less than
1 /min. The range sampled was 0.2 to 1.2 /min. As in earlier tests, the
ozone concentration in the anode stream was nearly independent of flow rate.
The reason for this is not known, but it may be an electrode surface satura-
tion phenomenon, although the low power level (10 volts) was selected in an
effort to avoid this phenomenon.
These ozone generation tests performed using the prototype unit
complete Task 2.
4.2.7 Microbiological Tests
Sterilization tests were run on surface stream water contaminated with E.
coli as a demonstration of electrolytic water pui-ification. For this series of
tests, water was collected from Frijoles Creek in Bandelier National Monument.
A worst-case situation was established by spiking the water with raw sewage
inflow to the Bayo Canyon treatment plant in Los Alamos County, N.M. toprovide an E. coli population of 105 - 106/100 ml. Ozone/chlorine-hypo-
chlorite solution was generated by passing water of 3 and 30 g NaCI/k
through the prototype electrolysis unit at 1 k/min. Volumes of the anode
stream which correspond to 1/20, 1/40, and 1/60 ratio of electrolyzed (anode
+ cathode stream) to untreated water were added to the contaminated water.
This was stirred intermittantly and samples were removed to determine the
microorganism population at 5-minute, 10-minute, 2-hour, (30 g NaCI/k
solution only), and 24-hour intervals. The cathode stream was added to the
treated water after 2 hours and the solution was allowed to stand covered for
24 hours to determine whether the treated water was sufficiently sterile to
prevent the regrowth of coliform bacteria. The membrane filter technique 1
was used to determine bacterial population. Filters were incubated with m FC
medium at 440 C to make the test specific for fecal coliform.
1. Greenburg, A. E., J. J. Conners, D. Jenkins, and M. A. H. Franson,eds., "Standard Methods for the Examination of Water and Wastewater,"15th ed., Amer. Pub. Health Ass'n., 1980.
27
The 30 g NaCl/e solution electrolyzed at 10 volts, 3.5 amps contained
163 mg/I 03 and about 200 mg/e Cl 2 At 1/20 dilution, water was sterilized
within 10 minutes. At 1/40 dilution, 2 hours were required for sterilization.
At 1/60 dilution, after 2 hours the water did not meet federal drinking water
standards for coliform bacteria. The Federal standard for drinking water is
one coliform/100 ml. After 24 hours, the 1/20 and 1/40 dilutions were still
essentially sterile and the 1/60 dilution nearly so (Table 4-9). The 1/20
dilution met the federal standard; the 1/40 dilution contained 2 coliform
cells/100 ml; and the 1/60 dilution contained 9 coliform cells/100 ml.
The 3 gr NaCI/Q solution electrolyzed at 25 volts, 2.5 amps, contained
100 mg/A 03 and about 22 mgiZ Cl 2 . At 1/20, 1/40, and 1/60 dilutions water
contained about 105 coliform cells/100 ml after 10 minutes, and did not
approach the drinking water standard. After standing 24 hours, the odor
was gone, the turbidity had decreased, but water still contained too manycoliform cells to be safe for drinking. The large quantity of dissolved and
suspended organic material present probably depleted the ozone concentration
too far for effective bacterial kill. A prefilter would alleviate this problem if
suspended material is the substantial contributor to ozone demand.
The treatment of raw water with electrolyzed solution appeared to
improve other parameters of water quality. The untreated water was slightly
turbid, slightly tinted, and had a strong sewage odor. After standing for
24 hours in closed containers, the water no longer appeared turbid althoughthe tint remained. The sewage smell was no longer detectable in even the
water that had been treated with the most dilute electrolyzed solution. Thus,
water treated electroytically would be aesthetically acceptable for consumption,
which could be important under field conditions. No residual ozone wasmeasured in samples which had stood covered for 24 hours. The pH was
7.72-7.75 compared with 8.05 for tap water.
The final experiment was a flow-through test of the entire prototype
electrolysis unit. The tank which corresponds to raw water intake- (Figure 4-1) was filled with 110 gallons of turbid Frijoles Creek water spiked
28
i~~i- " * ' ' . . - . ' * - .- - . . . . .. .. .. ..-. . ...- ,- -...- . . , . . .
TABLE 4-9
DYNAMICS OF 'E. COLI KILL:30 g NaCI/I ELECTROLYZED SOLUTION
Dilution Factor E. coli Concentration(Volume Electrolyzed/Untreated) Time (cells/100 ml)
1/20 0 2 x 1055 rain 1 x 102
10 min 3
120 min -1
24 hr 1
1/40 0 2 x 1055 min 1 - 10 3
10 min 2 x 102
120 min -1
24 hr 2
1/60 0 2 x 105
5 min 5 104
10 min TNTC*
120 min 8
24 hr 9
Unspiked water 3 101
Federal standard for drinking water 1
* Too numerous to count at dilutions prepared.
-
with Bayo Canyon raw sewage inflow to provide an E. coli population of
4 10 5/100 me. A portion of this water was combined with supernatant from
the salt bed to form a solution containing 30 g/e NaCI. This was pumped
through the electrolysis cell at a rate of 1 R/min. The cell was operated at a
29
current flow of 20 volts, 7.5 amps and 10 volts, 3.5 and 4 amps. The anode
stream was mixed with raw water at a production rate of 300 and 600 gallons(1135 and 2270 e) per hour. About 30 gallons of water was produced. The
treated water was collected and samples were removed to determine themicroorganism population at 5-, 10-, and 30-minute intervals after treatment.
1The membrane filter technique was used. Filters were incubated with m FCmedium at 440 C to make the test specific for fecal coliform. Because of
equipment malfunction, ozone and chloride measurements were not made.
At a production rate of 600 gal/hr (2270 k/hr) and 10 volts, 3.5 amps
current, the dilution factor of electrolytically treated water to raw water was
1/40. As shown in Table 4-9, the bacterial kill was substantial within
5 minutes and the water was sterile within 30 minutes.
At the same 600 gal/hr (2270 Q/hr) production rate but 20 volts,
7.5 amps current, water was nearly sterile within 5 minutes and sterile within
30 minutes, as shown in Table 4-9. The higher current applied was shown in
previous experiments to generate more ozone and chlorine-hypochlorite. This
increased ozone satisfied the ozone demand due to organic material in the
Frijoles Creek water more rapidly, which may account for the more rapid rate
of bacterial kill.
At a production rate of 300 gal/hr (1135 i/hr) and 10 volts, 4 amps, the
dilution factor of electrolytically treated water to raw water was 1/20. As
shown in Figure 4-9, the water was sterilized within 10 minutes. The smaller
dilution factor, or higher concentration of oxidant contacting organic material
and bacterial population, should account for the more rapid rate of bacterial
kill.
1. Greenberg, A. E., J. J. Connors, D. Jenkins, and M. A. H. Franson,eds., "Standard Methods for the Examination of Water and Wastewater,"15th ed., Amer. Pub. Health Assn., 1980.
30
After 30 minutes, the odor of the sewage-spiked water had dissipated.
* After 24 hours, the water appeared less turbid. However, the extent of
settling was not determined.
The single-cell electrolysis unit operating at 20 volts, 7.5 amps, pro-
* duced sterile water from turbid surface water heavily contaminated with
coliform bacteria. Water was produced at a rate of 600 gal/hr (2270 £/hr)
which corresponds to 18,000 e/8 hr (4,800 gal/8 hr) or 54,500 /24 hr
(14,400 gal/24 hr).
These experiments complete Task 4.
TABLE 4-9
PROTOTYPE UNIT TEST OF E. COLI KILL
E. coli ConcentrationOperating Parameters* Time (cells/100 ml)
600 gal/hr 0 4 x 105
10 volts, 3.5 amps 5 min 2 x 102
1/40 dilution factor 10 min 3 , 101
30 min <1
600 gal/hr 0 4 x 105
20 volts, 7.5 amps 5 min 3 101
1/40 dilution factor 10 min 8 101
30 min 1
300 gal/hr 0 4 105
10 volts, 4 amps 5 min 5 1011/20 dilution factor 10 min <1
30 min <1
Federal standard for drinking water 1
4 *Electrode cell flow rate 1 I/min (constant)
31
4.2.8 Potential for Detoxification of Chemical Warfare Agents
A literature survey was conducted to determine the types of compounds
used as chemical warfare agents that are susceptible to decomposition by
oxidation-ozonolysis and/or hydrolysis in acidic or basic solutions. If such
agents contaminate drinking water, they could be detoxified by treating the
water with ozone or by substantially changing the pH of the water. Ozone is
known to readily oxidize a range of phenolic compounds, detergents,
-. pesticides, chemical manufacturing wastes, aromatic compounds, and proteins.
Some chlorinated hydrocarbons are not readily oxidized, however. 4
A computerized literature search of chemical warfare agents was
conducted. The printout is attached as Appendix B.
The following compounds 9 ' 10 should be subject to alkaline hydrolysis
and/or oxidation-ozonolysis
Phosgene PD(Phenyldichloroarsine)Tabun ED (Ethylenedichloroarsine)Sarin CNLSoman MD (Methydichloroarsine)VX (Nerve agent) BZ (Incapacitating agent)CN (Cyanogen) DA (Diphenylchloroarsine)HCN (Hydrogen cyanide) DM (Adamsite)Mustards DC (Diphenylcyanoarsine)Lewisite
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Tech-nology," Ozone, Vol. 16, 3rd ed., John Wiley F, Sons, NY, 1981.
9. Department of the Army, "Military Chemistry and Chemical Compounds,"Field Manual, FM 3-9, October, 1975.
10. Hoskin, F. G. G. and A. H. Roush, "Hydrolysis of Nerve Gas bySquid-Type Diisopropyl Phosphorofluoridate Hydrolyzing Enzyme onAgarose Resin," Science, Vol. 215 (5), pp. 1255-1257, 1982.
32
The prototype electrolytic unit is capable of generating water which
contains about 800 mg 0 3 / at a rate of 30 1/hour effluent from the anode.
The anode stream is about pH 4 and the cathode stream is about pH 10,
, depending upon applied voltage. Thus, this unit produces conditions under
*. which many, chemical warfare agents could be decomposed.
Detoxification studies of selected chemical agents can be undertaken in
Phase II.
The literature search completes Task 3.
4.3 Discussion
4.3.1 Historical Perspective
Ozone has long been used in treatment of potable water because it kills
bacteria and viruses, removes tastes, odors and colors by oxidizing dissolved
and suspended organic materials, and oxidizes a range of sulfides and
cyanides. 3,7,11
As a bactericidal agent, ozone acts rapidly to lyse or rupture the cell
walls. In contrast, chlorine kills by diffusing through the cell walls and
* inactivating the enzyme systems. Disinfection of E. coli with ozone is
. 3. Venosa, A. D., Ozone as a Water and Wastewater Disinfectant: a Lit-erature Review in "Ozone in Water and Wastewater Treatment," F. L.Evans Ill, ad., Ann Arbor Science Publishers, Inc., 1971.
7. Farooq, S., E. S. K. Chian, R. S. Englebrecht, "Basic Concepts inDisinfiction with Ozone," Journal WPCF, August 1977, pp. 1818-1831.
11. Hill, A. G. and R. G. Rice, Historical Background, Properties andApplications in "Handbook of Ozone Technology and Applications,"
Vol. 1, Ann Arbor Science, 1982.
"4
i 33
3,125 times faster than with chlorine. 4 Ozone is known to be effective
against a range of microorganisms at very low concentrations (Table 4-10)
once the ozone demand due to dissolved organic material has been satisfied.
The prototype unit is capable of generating water containing a
tremendous excess of dissolved ozone over that required to kill any
microorganism listed in Table 4-10. The particular advantage of this
TABLE 4-10
LETHALITY OF OZONE ON MICROORGANISMS
Ozone Concentration in mg/kOrganism for 990. Destruction in 10 min
Escherichia coli 0.001Streptococcus fecalis 0.0015Microbacterium tuberculosum 0.005Polio virus 0.01Bacillus megatherium (spores) 0.1Endamoeba h istolytica 0.03(Source: Reference 4)
system is that ozone is generated directly in water, eliminating the slow
gas-to-liquid transport step which is a part of silent discharge ozonolysis.
Approximately 600-800 mg/t of dissolved ozone has been produced at
15-20 volts. At 10 volts, the equivalent of an automobile battery, watercontaining 160 mg 0 3 / was produced (Figure 4-7). At the pH of the anode
effluent stream (pH 4), ozone decomposition is very slow. Surface waters can
contain considerable concentrations of dissolved organic material, which exert
ozone demand that will reduce the amount of ozone available to killmicroorganisms. However, the large amount of ozone which can be produced
indicates that sufficient ozone will be available to sterilize water even under
severe conditions.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Tech-nology," Ozone, Vol. 16, 3rd ed., John Wiley F, Sons, NY, 1981.
34
Ozone is a more satisfactory disinfection agent than several chlorine
species (Table 4-11). In this study, hypochlorite performed better only on
virus. To chlorinate water directly -Under field conditions, chlorine agents
which are hazardous must be transported. By contrast, the electrolytic unit
'- produces ozone and hypochlorite in water on demand with very low power
requirements. Thus the biohazards of gaseous ozone and chlorine are
avoided. Ozone in water of normal pH at ambient temperatures has a half-life
of 20-40 minutes, and decomposes to oxygen.
TABLE 4-11
COMPARATIVE DISINFECTION EFFICIENCY AT 50 C
Enteril Organism Amoebic
Disinfectant Bacteria Virus Spores Cysts
03 500 0.5 2 0.5
Cl2 (as HOCI) 20 1.0 0.05 0.05
Cl2 (as OCI) 0.2 <0.02 sO.0005 0.0005
Cl2 (as HN 2CI) 0.1 0.005 0.002 0.02
* (Source: Reference 4)
4.3.2 Unit Development and Testing
Experiments conducted under Task 1 showed that chlorine-hypochlorite
concentration increased as voltage and salt concentration increased but that
. ozone levels were low. The apparatus was modified by enclosing theelectrodes in a flow-through chamber and by placing a membrane between the
electrodes to test whether more ozone could be recovered by isolating .Ie
I anode from the cathode stream. This proved to be the case. Much higher
concentrations of ozone were then measured in the anode effluent from the
electrolytic cell.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Technol-ogy," Ozone, Vol. 16, 3rd ed., John Wiley F, Sons, NY, 1981.
35
A prototype electrolysis unit was constructed using PVC or CPVC
materials to avoid material degradation by ozone. The unit incorporated the
improved platinum-titanium-tantalum electrodes and a Dupont Nafion 315
semipermiable membrane placed between the electrodes. The flow-through
system is capable of treating water at 1 Q/min flow rate over a 0-30 volt
range. The unit was tested over a NaCI concentration range of 0.6 to 30 g/e
as described in Subsection 4.2.6. The unit performed extremely well;
virtually the only problem encountered was the destruction of the bonding
material used in making the cell by ozone. Improved cell design is a goal of
Phase II of this project. Basically, the unit is extremely sturdy. There are
no moving parts, except for the pump, which could be replaced by gravity
flow under many conditions.
Ozone-hypochlorite solutions were produced over a range of 5-25 volts,
0.1 to 9.5 amps, at 1 e/min flow rate. The progress and extent of E. coli
kill was studied as described in Subsection 4.2.2. Sterilization of
contaminated water took place during the first 5-10 minutes of treatment.
One volume of tap water containing 3 g NaCI/k electrolyzed at 25 volts,
9.5 amps sterilized 38 volumes of contaiminated water. Tap water containing
30 g NaCI/e, electrolyzed at 6.8 volts, 9.5 amps produced similar results.
Comparable bacterial kills were found for 47 mg/e Ca(OCI) 2 solution.
Ozone-hypochlorite solution of 0.75 mg/i was very effective in killing L.
pneumophila, the causative agent of Legionnaires' Disease, as discussed inSubsection 4.2.2.
To investigate bacterial kill under simulated severe field conditions,
surface water from Frijoles Creek collected in Bandelier National Monument
was spiked with raw sewage inflow to the Bayo Canyon treatment plant in Los
Alamos County, N.M. to a fecal coliform count of 4 x 105/100 ml. This water
contained considerable organic material. Based on the rate of bacterial kill,
sterile water was produced in 30 minutes using a solution containing 30 g
NaCI/Z electrolyzed at 20 volts, 7.5 amps, produced at I i/min and diluted
1/40 with raw water. Production rate was 2,270 i/hr (600 gal/hr). The
sewage odor had disappeared, although some tint remained.
36
The design goal, specified in the Phase I proposal, was a unit capable of
producing 1,000 1 of drinkable water per day. The working model exceeds
this specification by 18-fold using very realistic operating conditions. The
electric current required to meet this 2,270 Z/hr sterile water production
rate, 20 volts at 7.5 amps or 0.15 kwh, could be provided by a small, self-
. contained gasol'ne powered generator.
The electrolytic unit constructed provides ozone- hypoch lorite solution
. capable of killing microorganisms. Dissolved and suspended organics in the
raw water are also destroyed. The anode stream is pH 4 and the cathode
stream pH 10. These conditions can be used to detoxify many chemical
. agents by hydrolysis under alkaline or acid conditions.
The microorganism kill documented in these experiments cannot be
assigned either to ozone or to chlorine-hypochlorite, since both are generated
electrolytically in the NaCI solution. Ozone is known to be a more efficient
agent against microorganisms than chlorine. 4 The electrolytically generated
oxidant solution was more effective than hypochlorite alone against E. coli
(Table 4-4). The extreme effectiveness of the electrolyzed solution in
treating contaminated water indicates a synergistic effect. The electrolytically
generated oxidizing solution kills faster than more conventional methods of
water treatment, and uses only water and NaCI, which eliminates the need for
handling chlorine, a hazardous material. The method achieves complete
microorganism kill and is safer for personnel engaged in water treatment.
The electrolytic unit represents a significant advance in ozonolysis
because the ozone is generated directly in dilute electrolyte solution at
ambient temperatures. Ozone generators generally in use for water treatment
rely upon ozone generated as a gas which is then mixed with water. The
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Tech-nology," Ozone, Vol. 16, 3rd ed., John Wiley , Sons, NY, 1981.
37'I
ozone must diffuse from the gaseous state into the water before effective
treatment can take place. 7 , 11 The diffusion step is rate-limiting, and the
process is inefficient. The anode temperature must be very low (-20 ° to
-60°C) in order to achieve improved current efficiency.12 Another method of
enhancing current efficiency is to use tetrafluoboric acid (HBF 4 ) as an
12electrolyte 2 , but this cannot be used in processing water for human
consumption.
By contrast, the electrolytic unit operates at ambient temperatures. The
only process which is temperature-sensitive is the saturation of NaCI in
water, but this varies only about 10., over the temperature range 0' to
100°C, and should not pose an operational problem. After dilution, the TDS
content of treated water will be increased by about 750 mg/Q (750 ppm),
which is within DOA treated water quality standards. Gaseous ozone is13hazardous and toxic, however, dissolved ozone breaks down to oxygen,
apparently without forming toxic compounds. 4
7. Farooq, S., E. S. K. Chian, R. S. Englebrecht, "Basic Concepts inDisinfection with Ozone," Journal WPCF, August 1977, pp. 1818-1831.
11. Hill, A. G. and R. G. Rice, Historical Background, Properties, andApplications in "Handbook of Ozone Technology and Applications," Vol 1,Ann Arbor Science, 1982.
12. Foller, P. C., Status of Research on Ozone Generation by Electrolysis,
In "Handbook of Ozone Technology and Applications," Vol. 1, R. G.
Rice and A. Netzer, eds., Ann Arbor Science, 1982.
6. Department of the Army Technical Bulletin RB MED 229, "Sanitary Con-
trol and Surveillance of Water Supplies at Fixed and Field Installations,"
U.S. Government Printing Office, 1975.
13. Nieto, J. A., R. P. C. Salvi, and A. Gutierrez, "Ozone Hazards in
.- Plant Operation," Health Physics (42:6) pp. 865-868, 1982.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of Chemical Tech-
nology," Ozone, Vol. 16, 3rd ed., John Wiley , Sons, NY, 1981.
38
This unit generates both 03 and Cl 2 at the anode. As noted earlier by
Szabo, 14 Cl 2 causes 03 to decompose to a variety of products including CIO
and C1IO 2 , which are bactericidal agents. Measurements of the concentrations
of all individual species have not yet been made, but preliminary work
* indicates an initial large excess of 03 over total chloride (Subsection 4.2.7).
The bacterial kills noted may be due to a synergistic effect of the several
. species present, but cannot be ascribed at this time to any specific one.
As far as we are aware, no portable unit is presently marketed which
generates ozone in situ, at ambient temperatures, for treating potable water.
The electrode inventor, C. Themy, manufactures units for specific water
treatment problems. Units such as Chloropac, marketed by Englehard
Industries of Union, New Jersey, generate NaOCI in water.
4.4 Conclusions
Contaminated water can be sterilized by treating it with an electrolytic
process which generates ozone and chlorine-hypochlorite in dilute NaCI
solution. Novel platinum electrodes are used to form the oxidants in water as
the salt solution flows between them. In a pilot plant scale demonstration,
electrolyzed solution mixed with 40 volumes of contaminated water produced
sterile, deodorized water containing an increase of 0.75 g NaCI/Q at a
*minimum rate of 18,000 e (4,800 gal)/8 hr. Water was sterile within 30 min.
The power requirement was 0.15 kw. The only moving part in the appartus
is the pump, which could be replaced by gravity flow if necessary. The
*electrolytic cell is 17.75 cm x 10.8 cm (7 in x 4.25 in). Power requirements
r for the unit could be supplied by a gasoline-powered generator.
14. Szabo, Z. G., "Some Remarks on the Decomposition of Ozone Catalyzedby Chorine," C.A. 45:3 (8386), 1951.
39
* -- *-------
4.5 Recommendations
This study indicates that it would be feasible to develop a portable
electrolytic unit to sterilize and detoxify water under field conditions. The* next phase of developmental work should focus on:
I Improving the electrolytic cell design,I.
* Continuing tests to define the range of field operating conditions,
P * Testing destruction of chemical agents,
•.-Testing destruction of other biological warfare agents,
.* Incorporating an ion exchange unit to remove nuclear warfare
agents,
*" Proving the unit by 2,000 hours of continuous operation, and
* .Building a prototype multicell electrolysis unit capable of generating
55,000 gallons of sterile, decontaminated water per day.
0.
% 40
5.0 REFERENCES
1. Greenberg, A. E., J. J. Connors.,, D. Jenkins, and M.A.H. Franson,eds., "Standard Methods for the Examination of Water and Wastewater."15th ed. Amer. Pub. Health Assn. 1980.
2. Wilk, I. J., Consultant, personal communications with H. Gram andunpublished work, 1969 - 1982.
3. Venosa, A. D., Ozone as a Water and Wastewater Disinfectant: aLiterature Review in "Ozone in Water and Wastewater Treatment." F. L.Evans III, ed. Ann Arbor Science Publishers, Inc. 1972.
4. Grayson, M., ed., In: "Kirk-Othmer Encyclopedia of ChemicalTechnology," Ozone, Vol. 16, 3rd ed., John Wiley & Sons, NY, 1981.
• 5. Kinman, R. N. Ozone in Water Disinfection in "Ozone in Water andWastewater Treatment," F. L. Evans Ill, ed. Ann Arbor SciencePublishers, Inc. 1972.
6. Department of the Army Technical Bulletin R B Med 229, "SanitaryControl and Surveillance of Water Supplies at Fixed and FieldInstallations," U.S. Government Printing Office, 1975.
7. Faroog, S; E.S.K. Chian, R. S. Englebrecht, "Basic Concepts inDisinfection with Ozone," Journal WPCF Aug. 1977, pp. 1818-1831.
8. Bader, H. and J. Hoigne, "Determination of Ozone in Water by theIndigo Method," Water Research, Vol. 15, pp. 449-456, 1981.
9. Department of the Army, "Military Chemistry and Chemical Compounds,"Field Manual, FM 3-9, October, 1975.
10. Hoskin, F. G. G. and A. H. Roush, "Hydrolysis of Nerve Gas bySquid-Type Diisopropyl Phosphorofluoridate Hydrolyzing Enzyme onAgarose Resin," Science, Vol. 215 (5), pp. 1255-1257, 1982.
11. Hill, A. G., and R. G. Rice. Historical Background, Properties, andApplications in "Handbook of Ozone Technology and Applications" Vol. 1,R. G. Rce and A. Netzer, eds., Ann Arbor Science, 1982.
* 12. Foller, D. C., Status of Research on Ozone Generation by Electrolysis,In "Handbook of Ozone Technology and Applications" Vol. 1, R. G. Riceand A. Netzer, eds., Ann Arbor Science, 1982.
13. Nieto, J. A., R. P. C. Salvi, A. Gutierrez, "Ozone Hazards in a-Plant
Operation," Health Physics (42:6) pp. 865-868, 1982.
14. Szabo, Z. G., "Some Remarks on the Decomposition of Ozone Catalyzedby Chlorine," C.A. 45:3 (8386), 1951.
41
--------------------------- o-...'---
Los Alamos Technical Associates, In
APPENDIX A
OZONE DETERMINATION METHOD
Introduction
At a pH below 3.0, indigo trisulfonate is bleached rapidly and
stoichiometrically by ozone. The loss of color due to the ozonolysis of indigo
then is determined photometrically and related to the concentration of ozone
present. The maximum absorbance of the dye is at 600 mm with a molar
absorptivity of 2.0 x 104 /mol-cm. The precision of the measurement is
affected by the initial concentration of indigo dye present, since it is a
bleaching method. Detection at the 3-i'g/e concentration level is possible,
however. The method is subject to fewer interferences than most colorimetric
and all iodometric procedures. At pH 2, chlorite, chlorate, hydrogen
peroxide, and manganese(ll) do not interfere. Some other interferences can
be corrected for by adding malonic acid. 8
Experimental Proceedure
The indigo reagent, potassium indigo trisulfonate (FW 616.74), was
prepared by dissolving 0.66 gr e (1.1 mu) in distilled HOH. This standard
dye reagent was stored at 0 0C.
The analytical method is based upon decrease in absorbance due to
ozone, and represents a relative measure of ozone concentration because the
method was not standardized against a known concentration of ozone.
An aliquot (0.1 to 2.5 ml) of solution to be tested for ozone
concentration was placed in a 1-cm path spectrophotometer tube. The volumej7 was adjusted to 2.5 ml with distilled water. Concentrated sulfuric acid
(0.1 ml) was added to bring the solution below pH 3. The indigo dye
solution (0.1 ml) was added. The tubes were inverted several times. A
blank was prepared using glass distilled water.
8. Bader, H. and J. Hoigne, "Determination of Ozone in Water by theIndigo Method," Water Research, Vol. 15, pp. 449-456, 1981.
v 42
", The absorbance of solutions was read within 10 minutes at 600 nm on aBausch and Lomb Spectronic 21 spectrophotometer. Ozone was considered to
be equal in moles to the amount of -dye destroyed, or blank minus test
solution.
4
I4
APPENDIX B
Computerized Literature Survey
44
0 4 - ',6 . Kos ;zjE
in I5- *Ct Az a
bi S0 -9 1C.
- L;1 30 ota
a.W ao-
U :t ._~
zwC -w1A! -- *.1
C~ aCC w2..
O a rZu-C 180 Zaz-s -"----v N -a 3-tC-
a.4 .-a
..-rr 4L t641s
_ CCC - CISI 3 45
* c4 ,~4 ft* ~ ~ 4 at ~a .0
4z 0- B.4 1
N NZo I- AM34
a l. i1
400
Cc 0 444 4 N -
- O C 0 4 0 1 - 4 0c : : ~
AU -.
-4:~El 40 -0- . .. '
-W- I - Ei4 4 U
-. ~14 Ow h. Y0
00:;-! law .. 4.'-2 - 0
VI~~ its.4~
4B4C wj w-- 4 1
OR w* Eva4- L-4~ .!a -oVY -4 43 10A w
4A -c ww
4a I1U 4a
%A-. 1 1~ -. .10V I-
~~~ w 0' i s£.44
Iwo *oMI I'm T4
e~ -1
'C~'4A.B ~ 0 -446
.~. .*'' .* . S
3 L1
3..
C 0s- r a
-a-~~ ~ 6m f~U .
r "s CC
aau at - 4 2 1-O% -c o woJ
a-3 ft 4wlv~~E Ksa
31 af C - c -r .. : 5c
U - CN N C
34 ;61.C
b C 0
Ra ta: %ata
US 0CC j C 't bC-:9I 4 l~aC.
a- -a UC ca- U~ q f- -ua~aP N at .-s-rbb..R C 62 ia L
ES C asC I s C - a
-a C -0 aau:--SCLbv *a
w Iti lea.C I ICb
F . fin H S
1.1-s.a ~ 47
omos.....4 z: I
-0 .. . . . 0 =2 (Z 4 L
0-. -1 I vIQ :2-Z 04 U'*OC24 O
- 0 -i. 4i 44 - U 39U
. 04 0 4jCc C in z-oc -0 a z '0 24 -4 2
20 0-44 C2 -*.DZ
o ~ 3 -a(i -... 00 2
!r 1 - 2.440 x - U 4.. 0
3- Z. c W v
Z- vi zz-04N4 J4 00
N'_i-i- - -02.-- W N 04
o 0 o.. U V 0. CL -- 4 e..0.4- IL..4 ~
£ ~ ~ ~ 0 a .U U
n '. 004 -- ' -tau2 vi-J .(
31- W ' g -- ';;a - a .44-c _ inK 0
S 0 4! 'l 50 'l N!. ~
0! 04 " 40, aUv a Z; . 3103,
Ox4 Zu o i4 Z =0 - a.
2... 4 .0~U-4 2 P. 240~... Z.43 . 4-.4 0 .1 - .4Z2U.-.
4004- 4 0 HA
d la 1 42, W ., -20 404 0 06- ~ ~ ~ ~ ~ ~ ~ * ui I' 2 044 4~4 0 0 vi .- in-inc
*~~ lU.; -.. 4v 40- iK .. ~ iIowa Z... Ilev a 1 4 40
4Z 0.( 04
inm 403,I
4
4...4v 4Z4LN-'vi. ~ V .S- .4--,a~i4.i0ih 4i~0 avif C ZU 44ll mu a f I~.Jh Pl0. .. U v e .
Y04 4 . W 4 - U 0 4 w Uvi 4 424~ - 056 * 40-'i O 4 *. 4nnO.4! 0 malO lvig-g i40 2 04 1
P -vi U..W4 -20 *- . 3 4 42 - 4 I 4 4
"'4 9 !~44 * "' - 9
48 i~' .~ i
~.............
a 49 6 Z I , aU' c L-E~~~~ -a0f o U
. 1.: _ & 343-U0 5. AmI.d 4-4 0 ; 0-4 W.. Q .- 2
0=1 Im 4 4 44. & 4
494
*1v U' ' INtc
14-- U zi! -.. A n4 0-
a tg-U be ~Z 44 14d.U 4z V 1
2 N- 3.
a 1k .f 2U'.. a- a Q 4
U'.-.Zr Z L3 3U') rzW . t - ~ ~ N
.43 4 40 4.. 4... 02- 1&- lit's* 4 ~ -4
U -3 .320 - N4~ -U4E 00
4.;X 1 9-m &0-444.... f
~f iliat ~ -, 343 34
% C .1 4 1 a I....
, .. --.J c~-
C 04 *. 14 .C-..0~ . £ 4 -toVin
OM4'444:0-~-
49.C
31 * 04
g z.
-l s l -a1 .;;5 I
V, -04 3;Bu W S
50
IV,
'CC
C. I
c~c. le 0 -
-C 2c- 9C Ir. -
V LC C 0 L
-&~ -0 r
r3 0 1 a, 1I. R.. C g. VW
0-.33 - -.- i
L , 1 C- - &3U 0
OC IL v. -
tvv r-- V cc
1 36( CC.~ C CC
LC (3 0-I :U 11CC
-- c
-C LMU wC Cx w-CO C. 3CC -
40 z
o L3(- Ul C 1
- ~ ~~ ~ - Cc I4( - U --
- 0 (3LV~~~~ v v0(U3
C.~~~~~ cC 33 - O3se I
G L 2lI C5'~ ~ -Z >-0- LI ~ C ~ 4C
.0 u3
ILS 000- ~ P
- E.0 E, 3 -
- LaZ)-
C: L
L; 0
. C . E
CC 0o . 0
*4 C.
. >. D V
a.~ to to000 42 Zo 0M
411. 'o. -
ec~~~ C C0-f C to ~ 1
00 C. I 00aw. 3tCC - to *
- 000: 00 Co. L
C'.~O - CL~.0
IL U.C-0z0 CU t3i 00 -041
0Ua 4 aCo > CC 00 6- 1 0
C ~ ~~ 4101 a. C0- 4-to a..a-
I ~ ~ 1 -0 :- A~ a .u. -
I. I -*4- 1
u 0. -0CCLL Li
6f04U.8 --3-0
:52 ~ -52
- C -- - C~ C D r r - - r - -fy i r'. -
I 0
r- tLi S. ;!:kI1, i.s14,+ --w i c- I r- - -- s.
"' - o k TI -
C 4 S.€
" ,L; v 'A; e~
C .---I,- &..S.I - .4j .o, e U
• G - • " I - -F ;- l
* c
a y a--.
.o- . - r,, . ... - .cur
Cc -, . t. 6 r
-24-. W .rc a'n• - LL - L ' -0
-ir-s +- - c ,e ,+-- me U' . .L-
31 61
SC - '. ' -C "" ' :-
-IL L~y - -a..
_.v
E r. -V
a0 I,* V- W LV W ~ > L;
C~ L -
cc- It; !trio
0~t-> It63 y r I
4tC -i Qu O i 05£ C a §
- in arSV . S5 1C C ~ ~ C LL i
C. -- :;o 1
~!cc,~ CO -' r ~ --
u 1U S CU - 0 -- c .. 1 t a,-
*~ C ' U - Ucv-! -Cc Fri r- - Cus
3 ~ ~ ~ e 0 !- LOS. uI0 r e;Ft c 2
a10 3 j SU o -
53.UU- -- C
L; -C L.. 4! 1 3 M
- C I- Ir.- - u 0 u. C
C 0 CC C2U 6 .
t- Lu' CA - 31V Ct u~ - 3E CC L LC
f - C. r > 4 9c MCIn
I- m a, cc
V. 0 1' !. :0 14 4 -r
V L, - U' V O -
W C to 0. CL ICCI -
C 0- C rJ
-Lin1 ::E C. i ;- r. 0 C 1 4 .1 -166
M~C C0 CL w -v ;
44 4I E
N C.C L.U V1 aC IN is u-
4 to4 -. -. 0 cC V C0V 020 3 ).
cc -- N - in & Ci- to 3) U
c4 LI o 9
11 L3 I4 ItUir4 W L4 a 3 *C4 -
I.. C3 &. M -z 1 : rWo.0 . 40 4 1 . *I UU 0 -2
C.04 -r -
I~C - .0C CC
IIn
0 C .Lc.
t .a I U 2
n)o., 9" 6C U .. - I I -
Cc-' 44LI0 :"C O -z -
I- C .Ofl aN- 0 IN 4 0 z a,
L C4 CC. fi, w4M. 0 0 .L I Zt 'a 't u a
0~ 'a U a C*C V L.040 f
F4 i ,0 ) 4 L a IL'0 ll I - C a '
ri4o -c ~&V 2 8 in
60 112U i- .U
141 ~4LL *UCL - '~ -~ain L' ULC 4C-6 t s.~- ,-- * ~ ~ui-I8 a
U'~~ iU c. UP.,4
42 g'~: 54
9~ W a0 -O g.w I~ c t .. Zi CCL
V.C C
-C .Q C>L Cor Zrn-u. ;I Z
L Inh~
z - C' a a i C~. av~3.
~~: ~ uFC f a I 0 u at- i.C -t' :2ti- 5 ar0r
Vt U if 0L u) ofi C ; - . 81 .w
Cr~ft LOU- a--
0 S. aL~t Q
sC~3 m 214£r o6. -)0 6. C 0 F. !
U~I C C~~fV L ! F
4- -t-
v. -c .
vati 0- 1 0
EL Gk I- -a --
316 - ~ 0-m 6 -0-r-
31- 0 j CL
*~~~L rca~i±-j
Iu 4 ; Z' RS ft: . -;3 -0 ;- -:- - ;U ;fU ;; I
4 Us a~ .- c - 0~ ui -! I - - 3 'Vtfl U0 u ~ EllI gItr~f~ Etf Q U U m
1-6 UC - 6.
:!C - -
4 55
c ~ ~ ~ ~ 6 c-c t wr L401 R 6 0 r-
-E r : L r-
6 1 31 - 0 - , C 4 I -9 1W c .- R- 6,-
> - Gc-t t3~~ ~ ~ 4 ,-r ,
1 L .! i C ,
Ct u1 - a fo f
10 'p 41
cc 0.- 001 * Lsc 0-.~4J-
6
0L 6
in~ =I 0 1 00 3z
;i 00 )wILo-Q~~d' .. 0.. L, - w Ag 6
cc- - 6- C - u : cC
0 >C 3 . : L t -2
IIV
* z 0 L 6 CC 6 I00
wt0 a ru a 40r0~ 0 0 I
CL 10 06 aL
0 0
go ..2 40 L
!o- z
-~~~ . - -
~~I-. L
IL,
56
-V) L L
Li " - >. .. €-- IL 0 A
o- o- S. LCCLIL1 29L tv-)U
F. 4. L a
rU-C C
Ilk -I
6 L -V++ C -r_ -L R L 9 8 1 B --zQ C- . i. -
- - U .' 1 -
ON IL '. L V.. : V cf| , ;:: '" _ . it .
-. - *'S :au -o .;. :L L..
-
-. t+ - .I: ! -.i. .*~ 0A
LL
3. IVL v. 3CL L -
lDO+ U + CL. :+ :+ ; ...- ! .. .R-
0~ ~ 1- 6mr---
',-- s---.:C ,t § ';.J.
.4 ZC L -10!~~ 1; -1-op
ta L.:N55 -- o o. em I, r C
0 -a I- I~ L
57
c c
a C -
Z C
IL-
3 T IL
~c
-c 44 9 C L
0 . ~ 0
rae -, If 4
6 EU
404 ?.2. IL04
3C a r
06 6 04 , *1.- 0L 'UC 44 VV a
'9 C owC. s
C40 U
C..146 i CA - '
in I=
I . .4 w 4No~~ 10*s4*
C )..Ea4-43 C Ia6 58
* c
a . 6 :2
i~h q
EL 3
L tIf.OL
-r ~~~ C c6- L0--I~~ > n-
II
-1 It :1 ItS. II.
. L
;; In ~t - -VUtft !46II
' t 2 t-i' 40 a '0 Lb) * -
C ~~~ oat~ -2I -, N v-ts ct
in 6e± A 1 0
AD U C I tt :
in fo I's 2 v- LL0
N ~ - r-4 ~ rc. ctc r-
-~1 L -r~9v-
I. -C 0A. La Lo Z ~4 lic )k r- r rt s
- ± ~ :~~n.; fi%± ~ 2T
2 6 Ll
.4 - * i~ *~~v-j t ~jc-59
L 14 L L C
z 00 I 0 b , W
0 o
L. 3 c~S .L ) &eC - LU E C- trU 3i E~ V UE~
U LE C.0W
LM L.. S.
0- W - -1 - --
-I V
ci-S
c- I. C at W
0- 0 U
0 MML6 .-,6 64
S. a 63 21aig-c..-i8u 0,S.- 4,
SO- --ihI *
;U 1.111h~
60
11C 0- -c -
6. W c0 c~
IE v
0 -S
6 . cg 4,0
4 0 1 c 'c 0U
mc:~
54, CL -1 L 4 f c3
C - IC C. LN v. L dCL 4
lz C I I IC CCO
I1 141 0
~~ClIe U~~ U it si in ( .4, 3,C.E CI
A. r.
-~~ .4 >U. t
- ~--
* uL 16 ±L~
*!--r c 5 . cCcC'
c -c
*~ ts !-- - 4
~~06-0 30, 30 L ~ ~ - e
3 4, .00 - P L~61
Cit .1
3 0
t4
262
L . L
0 ct
it 3 v0
3 C - a
--- ISL 1
IL - - -N" i :.;). 9 i -C,20C
VI
-~ A I.- C.. lowf3
U
-g v
C.I' 61 C.t
40 -p g I .
6 a ft C.ft v
ft
.- '.2
5 A63
a. ~C. - C
C3 E
0 z 7
5 0 L -
r u a C- (z C,
-6 r 0 a,0 0
- ; 0 0 C
-0 , Z mo c , ~3~1 0 -2 - .4-
CP0 -. E : 3 -0 3a - 31 3
0~ ~ Cc 3
00 0
z 1c 00 3
-. Igo C -- on0- -' .
a 4. ON .0 a 03
0 -C 0 0 0
20- -; a 3- 2
C3 0I~ . -. - *R I -COO. - -I. .c
r a K N aI
6 0 C c
3c3
l0 - 4C 6 a
u 9
bI w -4 S-
In 0 r3C 3
CD - 5' ~ 1.*I64
a A
12
3 3
-o~ ~ C 4
r r
r t -. ; IC Zt
c c -m CroCC. 0. A-- - 04
; N. - 9r. 0 -
Cr r - 0 0 IF C
L. It I r
z 6.t - - g 1 1 -
z > 3 a.0:t--C4- . v~ C Ic c
CcC
c t z Z - 4. I C 0.- t
rO C
kl c0 0- C R. :Zl
V . Q v C , L; C 4.
ap S 10 rt 1414C IL
1414C.~ -4' . 4. - f
C- L~ .3-U 3 0 g1
-Lft C c t104
CR614 CC ~ lC
al gC 31 C-
-o 1 - ~ VI .zVol 0- 0 f
I" 34 6.4 '' ~" ~m OS v ..5
IC
11. c
0 -
u 0 I. C0 0
c Co L. 3 c
In I
C - c a,
L C ,0 4
00 v. IC -z I - Ic
41 0L .L 0.. ' - C C .C
u, c IC- o ,
4n C c-. > .t- cc- 0
~o r o~ 0 LO
C C~C 0 oC I -CIL,
NOI 40 0-0IZO
0-IC ~L.0C0U.C IC o
3 0 L 4 0.~- U 0 0
£C
in 0
wo 0i - I L0 1 .0
v~a £ 01 fCLUE 1. 1 C 0 09I. C
0~ ~~~~~ Co I. E .C ..4w w El s In -4 40 U0
2- 3
66l ~ 1
- vL
IC v. 4 ~ 4.4
ep 2-1
c cD 4'- ix 6 6I
L 0 L t
IL V .'Go.I ; ~ o t: d6~ L1
IA~~~~ 0uv *I3A ,
Vk24 la ' R vL
4' ~ ~~ ~ -4.~' IsC4 Ol~-' vA~'C C
*1m z
m" o4-. 2
I ii67
Z Z L
0L c
C. In , .-. K..0
CU A. a . a.u-
Z 0- E o.
a. - V -2j lk ,a
M -1 a ~ .go u. -z 0 V
lcu;S a 8 . l Mnrc U8 'aUO OC C 0
'a It 0 31 -
- L.z La -- in 41 i - 0a a
w 31 '4 - 9; L% A- 0 ILI a -0 0
ONO - u C &A -ua.--~~ c-c*a.. . C Is - a C
ina~ ni) 61. W 9L
-oa 0 uc C.iV
68
7E
0 Cc
NL 6
I
(,Co.
1 3. - N.C.
z I
+Or
, .: : !c 1
g*o -, ;i 1: - - -:
- .-- I- .,
42 , C ,, 4 C
; . . M .-- --
[-i " + - " +. +.- 3,, I, , .-VI r IEl0; iII" il
3ll- i t - 1 l 1' 13t .-,, t ,,,
A z
low a' a I.m
69
0 - C- - 3 W -
,.- 0- -6 1,0- '0-
C C
r>. 0 4, 08 4 -. 0 -
1- L -r C~'4 0C, CC v C 0 .x4
4,4 c L
4C4 x u 00 r~ 0or . L4, a4, c 0 4:4 ! '
0 > FC U L.t... LO u -MV m 4,> C- C 433
!. C10E 1 0. L, W4 I , M0 *E 0tC44 0
C tc0. c ~ C Z EE r U cc C 0-~~~d 31 0 9~~C04 . -0 4 0
10 z 08t - ,4
-0 ACm
41 W). rCC o U 0 , ; )Lwgi eo f- .M.>- U- c 8 -1-, I..C L Ur. a f143 ! . - - E' 1
to Z002S ,11
'A - 2- . -Z00
Ou 2 2o. 4. CU
-3C VFz
.31 0, 430 4 a4 uI
u ~ . 2~
K ~ ~ n -C 04
L.4
I: 0
a-" 44 U 0IlA 3 .1 &3.It
- U~ I m- o.K' -3 *0 -a- 3": ;~ '
ca A~ S 3 I:~4 4 46 - .
toS- C0 ~ U -
70
. C .III Ls CcS
a 4 c c o- b I L
0 _z L t- C
Q - k k oC
f 0 ; 1£o -% so - :
CO - S. ~ . ~ S *V'
~ ~ ~ 3 3 ~to- 6 ~ . E:~ 0
q IN '3 -S i S 0 )
c I I., u I - V.
!:, 16, a" - C V7 .1o a Z a 00 >~u ~
Sm2
3-0 u* 2a~e-- ~ fl.. In
71C
ai
0 c
4.
_ C: - _1 l
- u = , - c "
601
04
IL "6 ',-m - _. .z
r., .':~~~ ! : .. -41041 1 1. " "
* I . .~ it N - a. o- N "' L . -- . -. a'" "
-I - l4 41 . -.t4 ft
:mg
| 72
.- - - -
2zn).-.j *Wo 2 0 It C ) l-z X*I- *.wZw -- C - t 0 wa v. -CW -W.cz 0cCU w 2 0' g = tou~--
--j AD W. 2- u- C CW Z.-1 0wUXW.L ) x Oh0N U) Z ~0 1$- a z0 C U)I- W 2 L -x- I w I-& 0.aIu w - - 0
-X Li e-' 2 0 0: OAC 62
~~LL L -
,A U) ZCJ a2 W0W-). 0 --C- WM W OC Un ; .- W.c ±- -CAL - s ft - C ~ 2 N O
-..U 2 z~ A 0 Zw &6A. W0.. Z NCw 20 _*C- u C- 0z O U 0w--- LIx XI ;X- - )1-- - -
U) z. Z O IL ~ of=I&C
; '0C: cP. w r o w~ 0 = 0-
ZJ~ 2Lr u.Uw. 02 0 i-OKm=- w. x p x X Z CC WZU I- 0~ ZCO L.L0 U I)~ _ .O C ) o- CCW$ - - W..
*l C - >.2 - -' -C 0 a M4- ;tL--Z20-X 3. z 0 .W OWZ, ZW- .- 2
* - Z.~Cu - C IIJ r2z-2C . Z ft uX0 C- Li z. U) w) -- zO -- FzI C0 - x i ccWi C- 0Kt 6-W 0 CZ
J -0'*- -- > 2)O 0 W-.. M-C. WW~k%- W- .W O W W- L C- P- ~IMENC .- Li W-jA En
CAU W-Z- IL X) 1 ~ 0WCZ)= WU Li.j XO 0* ..* -u, a=U CZ w -0020 -I&- aCZ i
- 0) 0- ±2 Za w-C-2 C W ,& A -* ij 0 - - L U) - c o -00LiL w b- -a. 0 ~
C .- OK Z.W 0 m - _;.' 0h 3- 0W c0 N* ~ ~~ 0.L. 0-C Wd. -: U W 6-- =- 2& U) Z -OU
W M J- Z C C)- U) =I CI WC*0XU IC - - '- w a01 -U, -- t ~ w -w CZ ± - 0z0.jwz m M- 4 0 )-C-IS= O,-c- LAI 20- 0 c: o ZI:*-z-z v 2.--*X-1 u c.Z...Z-xcC Li-u 0- w.f - ftC 02±W I.CA 0) U
- Z-- w WL - '- acC IC U)i oW.I-W'-XWW Z-- X W CWo CW W I-- AL)u or z c C K CL Lk 0 U) tX JZj.XW &Lc j ±*A. *L0 - 0ft xI C 2 * - 00 '
0.21U Z'2-Wwr'J * a. n o:o .j -v z zw >O±w 0- c ~ C:.. c '0f~± w 00iX-nwa u C 'CW. O0c- i-U IL M wv t
- t~ 0j : . 2 = 'C. Z. U NS Z - ~; *C w- Zw '2W Q fC la (DwwZ w Lit W0 fZ~j -
ff J >,k L L) w~ i TJ k& I X -2J0- T I) w0 C 6''W L
=-ZZ W ~u a-ai0C w a: 2 - 0: L-J) .0)22:O~j Za i" oO Zj -a . aftft WI fW -WO) Qt La'x w 0-~u w cxOWOOWZA.20I22 Q L)
MW Ziw ft 2. MC- Z -- LW LIA.--W 0 0. V, C.
-)Z CZZ ZW Z~c fz C XI a73v
- ~ IaA7- W4N~
U, . I X )xZ N* -
12 x aou o4z:
a: -s -i_
I- ~ ~ cr U . ,..Zt.~j~ CaI uIL
4V) Z U.
xa 0 0z
r J z 0 -, I- 4Ia~U se -o--z(.
0~~u m. W .l~o
ts N w w.UJ=J C . Qa IL x D - X .
N4 .4 C- 4- x. 0
40* c XW
ta Ia-..u
£z w
x 0 - 0 A
z W~gwt'
- -ON~ I N--~ N wc~ *~zxO ~ *W 10 *i-w- CaZ-J
0j LU7 C 10X 0 Z M-
V4! o. zW Ca
S C -7aii - U _ .. A *-i 1-L
74xto-00X
KW
51~
cAKa~7
0 c0Wz
o zo -n z
.Cx
LI. L it
0 0
LIW
z
- o o£o a o
z -
C 75
£0 9
-~ -J
a . w
-Ir 0 ) **
4a IL.OP n
-- !e.,
r0 0
02
46 c *>. c-L zt. z C0UD tiL
Lou - &. . i - 0 C-Z
* G :
albi&- C
L' ca CDo m = ZOA'0 ZD 01 -- 0
Sso- 0 . ~ N2 C
m -V * ... ;: z ~ a
w I, V g I
'a, -. L76
.. a- V 40AAI . -
t~~~~.c 0 =. Si.C4 aS0 . -
0 I V0 u 6C 4 0 0 1.
itV cf c v B.t -C"-'" U ri4 r- O 0)i
g :go .. IC 0. b 0 -3 0 4Ix !* a 0 0 O , e 0 U
-j r C -lb Mo 0 b 0 I" " -Si C a to :0 t) U oU
O 40 O0 i' U 0 S 0 0 is Si* CCS allt 10S. 2 1-00
" " ,I 6- . . . . C.OO- Si i Si0 +' -
•O' "* " - to *O 0'0 UO 0 5 &. . -C . L0 & 0 10 Go 0
-, 0 . - 0 i - L 0 c & U z.," ,,,,i 6 U 0 Si O iU. S .-0
-.2 0 k+
l -*- '0 IV 6 + O- SI.6.3U-5 - -. J U
Z .1. - Si U J: o[ 0 c U,. c. . C
£ Lio IIIn+ I ,. O o ' i I ..6.6 s.2 0 0.
IL v a U a. 0~ III a Co -.
. * - 0 U U - - ~ C, -)
-5 *N CD -e V .C 0)' 0 X-z. .0 lb iLU 6n ' -0 - S~ so L c
*1"0~ LU asIS C c- 0, C SV, c.S -2i V U C-C i It~
I'CIb C I )*+ '0 i-4.'0 ULO- "€ 1.1.i 0 - '..1-
j c2 I- C, x i '.N UV 0. .IL. SC 1. L IL S.
Oi Si z0C ~ S IO ~ -U) 0 - K
* 6.'a 0 6so Si l -0 - L U .C, U K
5- 6 SS.J CL c z i U 0 C.
0 ~ 60 &i 'or M . C.' *-
U~ cCD c Ls 0 ~ 06 U U 6.. iSc' Si a 2 r 0 C -ZS* Si& U5 W X C--
-w -W 0 0C Si ,6 r. &. - .~4W SiC.- I~ '0 - I. - U0. -Si. In X p~
o Cc 0. r It V '0j Z 5 - '0 i
00 C- (D I~ *C 0.0 c v 6 '-0t
00~ UU CW :' 0ai0i. 0 6. - o
~~v L vi ~ zu St.SU o S
0- mU u- 6 U 160U a4 Cr
0Li a , aX Q. ;.~~~~ -1. C- Si 81 C- u)k'), 0 C 6&.. 00 S 6 .1 0 i -
V U-t.3 U 00 --. i *- L r
-. 6 ~ o C 6-0 61 C) 6.6ft 0 - V~ Ur0N 62 C D i x OU O U-0 I. L. C T UZ
V " W C'I6 Q0r CL M jUCM a 0 c SigU' I'L Si M U =rL '0C r9)o ul s a ~ ~ '0C WUOc C tz.'U SSUS. Z Li --.
77
3 op -0 -I "
35. v .m' z5 06 IA. a D c.0 to g'm mcc .v b Q .2 C& '. . 'a' 2a~-a C.r 1. - c V 5.t
of 2~ Ce a r. 4 ~ -C fta' aL0 C. . 0- . 9c~ 0.E '. *6 0 .U..1- 5.~~~ fAC U'. 3,bl ff C
5 c2.C Z .6 .. 5 a' C. lbb c
r5 om .-aS 5 3 1c 3* -a. =at! -V ' 0 ; z amI .e . 1*' 3'
0 - J C~ N V. 5. L '0 11 .. 'S
.. .3 5.-* h; acl at. s 5. g. *
a'.', ~ ~ ~ ~ ~ V 07.u a.. c z4 U *15-
5.0 L - 2.CofN5.-.' . LN .0 0 3CC ' - 0. m *- e.. - a m A * -. a !!.&7
wk a6a a..55N2~' . cJ .. 3 - a:- I0_2
3z-o'C aa-.-a CN 8 L Z C to L9
-C*-D.~'. Ci~£. 0 L, a' :1 L - LI 0 b
3O x cvsat .'a16 ..IE~a &I 1. 0 1 1
15 ca, .n c VL i: Lct4 o 3 0 ..It m 15..Z a0 ~ oa Ec C- fC- 1 0 a a cam
a' N ' .b.. ! . i .I*g
L is U c IT-sa'S a maIO - z vIl5 ' Go a' to v &- .
N.j C 0.9 'o~lb.. tsml. 1 0 a' 10 0 £i-g - .. *0. - . .. z s V L52.lb 1.2. x~ -a~ r- ILL to *X o v: R F .U-l oac cs.s ! '. *On c ~ . CC 0o MI~. 11~7 a) . ucL 01. L UWap- 6 GLo 1.-- C..C CL (n .c C ci.52 5 9
C. c i C ' V-- - . to z.- i- J t 'r - aiC
U.ILMNCC. o cc, -Aa~' f5l L .l -' L. M In -= I--we a
J; a 2. p3 c sc In F& Go a Ie61 1.6 =I- c LW a.5N.OCL S W& . 05u -a a. 9n 0.: uCZlZ
W - r 6& 6,c 78
fo f~£7 *V 05 w '.
M.~ T i Z* e 0 IL
036 M0 L- U of -to
F15, .4.£. I015 UI
C. P. 0 I. k.
*.- , I, r, r af4 .-) .0 1x L x. v
v' C ;LC w.~1 .' CI IL I.V0 V - C o L )r- CLX U 'L
* '- o 0 L 6- L wiwV 15-S U L J
Li 'r -0 C.C61w - n M t
0c6.C v CV 0 C. 0o w 6--(
m ri 6.~ it-- 6. I. C' C' 0. .LMi
L M ~ . ): i
CDLf CD Cr t~ t
*~~s 11. 0 U
o 1. to uc 9oC ai t*0. n-oxN N l I w -u
C) 6 -a -W .! II In V) Ne 0* L -Iv- L~6i a- m5 V. GoC i- 6-I uIZ
UC 0 .f - C6 .7 0 -1 W I
Qi - asct; U.6110- cu Cnw -;v-o- W6'. e*:%fUS P .. V ,0 u I W,1 65 fo CD L
I6 6-w S a- 0 2- 2 mf IL t NXC. f% .I .
C~ItJIC2 .'-C- C Z N OL 0--15jLU796
LL)40
LA. 3
Usa. EnwL
w CD -
a, a
-1 - 3
UI aJU
00 U.to N u
r) - 1- c
U. Z 01 3K
Z~~ mW
a: .' 93 0 .0 0
C DC 0 cV 00 0x c.. a
g~u L. C al ml .rU ell~
M ZL --IZ a r. . m l -'
tr Cj U r-a a~3 * l- ULIZ ~ ~ ~ ~ ~ ~ G C"C'GZOC P ~ W EU . n-
r~r0 Z 0 . . CIL L. a~ .'-3D to OD zN 9 ll LI-Z 'NLOON-a r 0f w U' .' 'L 1 .1 I
o- CL z. U.vI C
L z go 6aU) m v' a'l ;; .
- '" 0 0.2 w u0. W LDC w N L
'- m QN CA OD qC' cc vi 010 0
Jr,I 3 C L i W t2 - h n n
80
CD
uj C.*1
flt a.tp0
jo-
Ac X
c C.
t- V do
2A Z L)~~
0 w soC. U. EU
0. 1
F4 -j 7-6
~~l.* L VI7. .WC CD tr4
it v IM r ,,,z
to L) . L6
U Za.~ C IZ .1
-c -' rW W0 61-
81
to .1f-- Wj %)
.0 w U. C
a 'a a L0.
n Eu CA
- Eu E Ct.)
'A E
t-~ Lo m A = 0 . L
CC
02 Im 2r a cA C.IQ I Z, 0o xh )
01 ff vI O - CEuC I.0 w A f N 1C -01
fa- VC. mo $)M C V . Cie- 0- E - "v U. S. uu 2 w a in~ r_. : 1 r fr, E.
ib 2 c ~ Cs a of. u m w 0 64 4. (n Eu 2a to
Eu 'A ).1 £! L)~ 'L. al~. Eu so a I-- Ib* too . G
2 0: GoC to (2 m c u a-: oG o . :a
&n W- *- P4 .4uE 0-w to $. c. I.~ .' . V3 ki IL1 CA v fm I L - C -- N CL C
so . -of. M 0 X -.- .. I.- C..
5.j w W0aO. 0 .-L WA Co-. 0w O C 0 C fn ~ 'A -uznu-w 0MI CC? . C. C N Lir ;U N 1u -1 Q CC #w w L a c at l Z ~ k uw w-" ,P,
mm 0m 2 b, ud Q -20 -j = i 0 ' -0 a L- 02 In o Z (M 0 i - a N
r. 0 WOO . 2 c Eu . C0 U c is CC C CA
ta 0. * -C zA W-u2. 1 9L L) C> xA W~ f ut In co
C 'VC *2 * C ... 2 'A' 'u *0 ' 1 'AC*82-
in v
z. a, L,
6. 00J
l C a
to 0i a, Nf 0
so 0 - in r0 faa 61 M
IL f S c N 0 6-cw o 0 *p r . S In C
;l IN0 L a g. .r . a, .
CO A v. C 0x
- C. Ia. to £6 50IS Aft 0 so. a LI aL1. a
-M C1p 11 ; a,$ C.u ~ 0aa:'., v a,52Cu u U M 4 0 V
v.* C 6. aZ-0 0 *- U iz.J a, -n a,~ Z In
to6 %, og 05, C.
0 00nI c D5jc 0 1 . C )Io- st Ii~ CD ft to i sV N i Z M 6 0 .L SOU .a M C M a .0 3 070 s
11'L C, W W£.c 0 0" 5 an soU-0- .Qok M ~ w u a, a, so a 0 go 0- I5- 01O 0 .0 M£ p5 1. le U) M a
UC .2 6 .. 1 so to m ~ I f, c10in o . n r L. 6. 5 00 V C o *a, CL
Rlb. 0- -j 40. V.u-. 2L a, a a, Af a, ., a . C .0a z u C -C W* a, N52 1 0. Cl
4u* U. 97* 22 0 L W t- u c .- C~ z. r a0 u 6. w #(0 , 7&oZU a, Cal 0W- N - =cQ:MwwwQ / aw a. .C a am
0*a, C, M0 WI C J Z W CC CD 6. M~ oI -00 r
-20~~~~~~~.. ...... , 0 Z UOU ~ a...*
-J
__ L
IILI
-7tit
0u 2
U N -t
IL 0.
U 0U
0n v wammt o( .C . 0 ?1 M
4) Z - n 4i 0. U *
UC.
o07
84 -
* 5- C 4 I * I 5.5. VS. .1 .. ~ 1 C ~ IA.5
L, 0 'A. 1. so
LO ;6. 1.
CC
r 1.
-0 c0 5
a I -.
Go 2 J- Za
c F.
x N c rALI L
L ~ C - r- C 0 .
g, Z
12L CA' .5.cSZ 91 J- a Xt0a .
5. & . L)m( . -a . nm.V ) 6 .* I - 0 'W.-iI. ;c
It S. La 0 M Lg m 'a 13 M cm. z.' oil- &~-
on 3 aIL 0r. -,Pc In..-.' IL Cl -. C.a~ m-~,-. a. V0 . 6 v 0 u.- Cc r C- oM 4
.13 *13SrL 2r o: a. *- .. 4w 0.
C4 0U mC Z -0 0 .' v ' 6C a 0 L to L
;:-- ;o -50C NC !J ; :S WC *~ fl T: -1;-
a'~~~~~t c~ cSU IL .. C.W t x0~ .~t~J '.X.r r C U 0 .1-La P-C ) 0 w. x C v 6. * LI W 5.13 C-u2m )g
-: s-. w w w I=C uc 4) Z0 at mcU &2V .C OCSSI Z) C" (P 0 1 U 2Q-. a.. L13 Cn'XC- M .
in &1 CL'L- CC '5 3 3 Iwo~ g In in n ~ .I
£ 7C5461L5la... -D )-.WO 6-460O- 4' b85W
*.a ED 01- -0 r w - c V- -u -
c 0 W. . s .- M n-r mc s- 0 c- Ifa N~ M~~u cm to M~ mw ap m C& c0' . z" I o "eus I Ir l £ .C 0 le - N
"V .,- ") Lfl0 O Cf.OL .0 a 30
Z~~~~JC m t O - n0 ~ ~ .. .- .. 0 ...Z.tC . . .C. ..,- u* c 8 U , ousm * a ' - .I *u cl mc.I .,'m ,.,Cn r6., nr-cS I- m.-l- r, ,o L.
r0 0 0 NO Ia US~ -a, c ID x 0 8. . - " .
3 - .- a .' c ma rNm .m c-a , ,-n Go -
.'-C c -CU *- 1& 0 I IC-ssra
ap0 0 - c .'Inl -tr. V CL g- 3ci U a s t o .cL*-0, *- .'-*-E la c- in" 1 - I I c ,- 1- -' . ,. 0 ' a C-, D O ;. . Go' c
30. "* l I ~ " "Ii' O ' .n -is - [- - lac c -,.a - -O Ow:3- -
U1 Z O a, 2- c co c- I 0 * -0 -CA A -v a-~ .0i 0s Zxt* c' 0 ISc
"- .o.,. i.- ,. .' mp . aac3{" .' e1 m u= m ' c. i- c' . ".Z
r ~ ri Wm cs LC) 5 .~--L. 0 Cin 1 .'g ~~C C c OE.e*a0 '.
6. do a is-a *- -N c D T, 3O, -.'L "0ic 0.' o
.... • X O ' *W m e- ..Ok O. I f I 0"J a- " - =5l.r ., ' c "J, a ' -
3• Lfl CZO ,a .'i- N * i- - C"C' inS i- ia 5*,1.* -"t, Sr' .1*'
-.c i. . - -~us..' t- a N V1 c-, .- € ''u I- ' -
i*"P .- z is - z r us aIs . m 3 NV r-e -O =I ,r, os mc... ," Nm"a= -
C., - a *I .' ia -u3Z '0 ' Ii 1. 3-cI-i - U' £ "! .
•.N m 0 a ( e oWa C t C E .. Jm ' - K- . i- "s M. L .- C. . 3.. .. . .-- . c .- go
", £ Ji c , " n. - C- 0A10Wa.'Co iim*-la N- 3[l Nc es ~ v'IGI ~ c mus in. iso a (. Aftn~ IA. aci
*~~~~ &- CA U-c i ' 00 c i a * 6 a 1O .
* c i w . -sZ- u * ,..,an.~* -m m-i
C. r.) is cn. a- .m i o~ a m ~ ~ .-x~ C -- N0 * L.'E-I m ci x a -m -
u c86Mi, x3L3 - V u
wa - I- ac II &~-i 0 so-u - S. a - N 'I0 -~Nm- ~ ~ S CC 00 C1- .30n~.i~- CA U- c -
fn- 9t* Im 3ei ;; 3Nt-mrn'a. c 3cu -
C ~ c ra w cs in..i-na '-s wom i. Wa C ctoEuc.r - MM c~-fla -a Lc~ .' I u-. IA.c~c. C.. ucI.a
ADm5 0ii5 61vv~c cU 15 isJ .amu al caC 4w Z
. M go c is a-- V 0 - a -0'
-I-0 3.~ Z~3.~. I tnVZIi PA. 1
- W~iw'' - 10 us *1 1 lt a ro~tACo. C co~n,5 -i .t v V I u N w0a~C..
s- wW a V asis usn n r' o oL- .- .s t- a . . ' -; rc
En W9 V a u . a- V c& E "f 0- N 0 1 i in
86
Uv
4-& 'C c CD. S
9..-I U 6 . 4 0 9. 9 . 4Lmu.' c. W C mU C
r -2 .3
SiS US SS LII
21-: ; - 2-4Ur SiC Ca 10 4CCl
.0L a cc N- t,
*~ .1S V t.3 £LjSC~~~~ 10 Lp V0 L WWC -. DI
0, -- aa-z.0 $. U. . 3 W~9' L c ?
no l 0 i 11 a & LL
P-i fa 0i 3 . L) c 9 o . 0 C j 19 in Si *
9. 2 1J $ALI C C ;a S 1. 'C IA I~--
Si v 0 aI MC . II
S F,-~~ z-L *- 'in V) - C,4S
r .9 C 6 la ~ ' $.- .. J2 x tiC. r w 'C,-
&. . C.. is: so- G'- LaJ r- W, L 0
.. s 6-2 to I. CU~ C3 to 2 *I
A 919 v-u w M IL -& - - S C'Z Li. C %9 1.- ML WC' v I. wxf .' Z .W
(LIc w CC SLCV' Q9 - U * ~ U ±' * U* 5. vs JO-U S)'3 CsC 2 *I 0IWI2 US IOCW29.
LI .C.' UC i~~jn~i ~ D Z i CC S 2 .S I C
9.C I& -'3 C0 4-2 toI~ -j Cu' CLIO to 'sSc LC) 5 I~ OL-IO '3 * -i ~ .I ~
* ~ ~ C, 2- a c.* sI .~ O C 90 - C i C. 5 C I '
sv. to1- CUl ; C ±' :C .. L S- .~ .~ wo r ao~ 6- cIt 00 .s'' L,0L We ** C. c9 >~ tpv~I a,- -U C .
I ~ . 'C t .ij 4f9 t' * LoZ C)L U. Go ;W. MC 0I* mn
g i 0 0 SC.'' fo . *OC 1~ s - ' - -: U) co.. 2s c
6. CL . 3.1 C * .v: C- Z CD En 9. -0- S..C c - &W9. Z tIL 'C C. oU~. 9 10 flI.J~ C- ZC W -W~ AL- .a#P4 c L C
N r w voSi - in: a:C U- UC WI I - W
SW.1f~ A 2C .fi I * .6 W, 11 2 . -l u Z E91 uSn&. )I v M . . - Z Si U Ct
3..C i.6m U C. & Crr .L CC. 34*n .0-~n CS a U * - L =UWCS.WSts~ILC. (1i &. l~ cW S *±:'25 C. ~ ~ l~ U
0~i a)I'.h-IS 9 CL u ZN. -55.Ct IU U E
£ 15MG 0 -UI -INU ~ a..~ SO C) X 5.*87
CkCf
x 3j :2
o to
- ED- '3
C m CA3 (a .0Mq r
-. '3 -SI. -
' ~ d N
WU
SI -- -88
-C CD.Is.x
oil 10 tomcb..C~~~ CCc.O i
u ei'- " aV.c
- o a:.5
. f.. -1in -. a
- - -. v Tv a'a~ .' z L). 4F *n a
*--'.-r 31a
.1. 'LSZ 01 VI .J u.'4V:IL a. a -. c z ~j2 C4.. In a0..
-cc oC I,,- m o~o 0& -3C toc .'U- * fs' a - .
~LC 42C& 2v' Uw -0r,.Jfi.5-Je . 6
w0 Q S. 6, *
Zo -) V2 ~- C 34 Cr' u ~ l' 0 0 0P ~ ,. c ~ Vw 054 -.- 'fl %WU 0.' a fVtJcX. % g
-L L2~~W C C ''~ 420 40 rW O' f5 Aft o t. L N fC ~ ~ c ;S g, UIN -: , U ~ .
I, ift o - - 0>
2~4bw
00
aaa SI 40 zI
Go -m . L- -
Li .1. M CW A
r4 02 01 2- M.C. - C .
U.> 0C tJ x r . ) J .
*~~ 'J L C' U.V ,.J L
0 C.. . 0 ' .'- 0 '- u -1~ CZn9- W C) z--- - I1.1tr
M1 ii' 0 CDc .15 1)0 I- V.W
CI0 ~ r). L CD ca
tl# Cc 4 CCD . CD1.01.W ~ 11 0-'.~ 1 5 MC, 41~0 10 all, .
awl~~.. 1. .D A in tj*0V - .* . ..I O -C '. ins ). N0C -v NO .CU) 10a
X . - o a .I1I0 In to2..
ow-~ ' v1 c w oW - C> -
ZC - 0 0 1.5 L 0 L . a . I-
90
z U
0l eq4
NNC
00
(%
I-91
5.0 DISTRIBUTION LIST
1. Defense Technical Information System 12/1 (copies/repro-Cameron Station dlucible copies)Alexandria, VA 22314
2. HQDA 1/05001 Eisenhower AvenueATTN: DRCDRA-MP (Stolarick)Alexandria, Va
3. Commandant 1/0U.S. Army Engineer SchoolATTN: ATZA-CDD (Maj. Mundt)Fort Belvoir, VA 22060
4. Commandant 1/0U.S. Army Quartermaster SchoolATTN: ATSM-CDM (Maj. Mcllrath)Fort Lee, VA 23801
K5. Commander 1/0U.S. Army Mobility Equipment Research
& Development CommandATTN: DRDME-PEAFort Belvoir, VA 22060
6. Commander 1/0U.S. Army Mobility Equipment Research
& Development CommandATTN: DRDME-ZKFort Belvoir, VA 22060
7. Commander 2/0U.S. Army Mobility Equipment Research
&Development CommandATTN: DRDME-GFort Belvoir, VA 22060F8. Commander 4/0U.S. Army Mobility Equipment Research
&, Development CommandATTN: DRDME-GSFort Belvoir, VA 22060
92
FIL7E
