662.27 R845u / ( Water Survey Library o 4HiOO SLa$ 1 J TECHWCAL SEPWT AHtCO-TH 78057 ( '.f. w * > ' •••-' I itt.Tj AVlOUI-OZu^i AND UU rtA/iOulT^X.uANi fREATMFJMT OF P!NK W#*ER Sr -: ^ v^' Lji''ri-Vnni s fyrrr'f *«$• Vi 1 1 •’, *•• »J2 P*7: r.--'"-j '* Jp> JLM , '.gr. 3* 4^ Mg-jp'ft K! ^WrJ L. si tM mamth iV sad tesmi m «a afikial £*psirt» _ ... — /jT— .- _ .^. ,j| _. htmI(i gilt p ®©»hrJR» jpCHICy Or 99C&39R, :^$jpf£; > ciwjfcit UNCLASSIFIED xcurnTr a/i ,»’c*T o« or this mag* r »w i— o*- wwq REPORT DOCUMENTATION PAGE ARLCD-TR- 78f *D a. SOVT ACCIMKW 9 cov #«•> & LKraviolet-Ozor.e and Ultraviolet-Oxidant Treatment of Pink. Water. r AuTHonrv AMO AOONStf gate Reseatch Corp. West Loa Angeles. CA Naval Weapons Support Center Crane, IN • I COMTMOLLIMO OFFICE name AM** AMMWM ARRADCOM, TSD Scientific t Tech. Info. Div. Dover, NJ 07801 Rf AD WSTRUCTIOH* Pivrmr. COMI'I.KTWG KOftM iT t rm or nrrorr a ► emoo Coviaio 6 Jun 76— 3ff Dec 77 • . CONTRACT ON am AM T MUM* Interagency Argreement No. DA-0059. 10 >* HOG NAM tt (V(NT. PAOJfC T task AH* A A (OHM UNIT MUMRCMS m . 'r Wwmnrrr" (DRDAR Movmsimr If -fg fof ' W- UUUB 1 N OP »lg w 14 MOMlVoftlMO a 6 Em£y HAMt A AOOMCA<<<7 « ARRADCOM, I.CWSL Manufacturing Technology Division (DRDAR-LCM-SA) Dover, NJ 07801 >fUnf OMm) Ta" oistm)*utiom it at cm cm t Ultraviolet Pollution abatement 0*one Trinitrotoluene OxMant Amunition Pink Water Army Ammunition Plants mnM MK )|i at Wm) i FEB 2 1979 SEQOTty j B AMTRACT i**r ^^Pink water, a solution of trinitrotoluene (TNT and other nitro- bodiea* is a major pollutant at AAP's which manufacture TNT ard load assemble and pack bombs and other ammunition. Two of the new tech¬ nologies being investigated as alternatives to carbon adsorption, which is currently used to purify pink water, are covered in this report. One method involves the use of ultraviolet (uv) ozone; the other, uv*oxidant. oo ,sru U7j UNCLASSIFIED sccumrr cl 7ICATKM OF t* NAME (9hmt D«. Chi y / / w i , ^ 78 12 9.9. fl l A UNCLASSIFIED. UNCLASSIFIED WCU^TY CUMinCATlON Of THI* Data FOREWORD Experimental work for the* uv-ozone portion cf this study was conducted by Westgato Research Corporation. West Los Angeles, California. The uv-oxidant study was conducted by the Naval Weapons Support Center at Crane, Indiana. This project was conducted in conjunction with the US Environmental Protection Agency, under Interagency Agree¬ ment D6-0059. Dr. Herbert S. Skovronok of the Industrial Waste Treatment Research Laboratory, Edison, NJ, served as the EPA's Project Officer. mmm fer *ra u * ; in V DOC '• □ l HWO'tf" « □ wsrt- , -- 8* WSbi~ . - Dr 'viAL L * A 1 ) TABLE OF CONTENTS Page No. Introduction 1 UV-Ozone Treatment of Pink Water 2 Description of Ultrox Pilot Plant 2 Pilot Plant Operation 2 Test Procedures 3 Preliminary Testing 3 Pink Water Tests 5 Specific Analysis 5 Discussion of Test Results 9 Design of UV-Ozone Pilot Plant 9 UV-Oxidant Treatment of Pink Water 16 Description of UV-Oxidant Pilot Plant 16 Parameter Variations for Optimization of the System 17 Chemical Reactions 25 Additional Analyses 25 Design Parameters of Full-Scale Treatment System 26 Conclusions 28 UV-Ozone Treatment 28 UV-Oxidant Treatment 28 Recommendations 29 UV-O/one Treatment 29 UV-Oxidant Treatment 70 References 30 Distribution List 31 1 2 3 4 5 6 7 8 1 2 3 4 5 LIST OF TABLES Page Mo. UV- Ozone treatment of TNT In water 4 UV-Ozone treatment of ARRAOCOm pink water 6 Comparison of synthetic sample and 7 ARRADCOM pink water tests Analysis of synthetic sample and ARRADCOM 8 pink water Oxidation in the UV-2000 and UV-500 systt*ms 18 with Oxone or H^O^ Analyses of various concentrations of Oxone 20 and Oxone and H 2 0 2 Evaluation of UV-2000 system operating 22 in series mode Alternatives for treatment of pink water 23 LIST OF FICURES UV-ozone reactor assembly 11 Pattern of water flow through pilot plant reactor 12 The 920 m 3 pd (5000 gpd) pilot plant assembly 14 Effect of pink water dilution on TOC reduction 24 Basic design of the UV-oxidant system 27 * INTRODUCTION Pink water is: generated by il) trinitrotoluene (TNT) manufacturing plants, (2) load, assemble, and pack (T.A p ) operations, and (3) unloading or demilitarizing TNT-load- ed munitions. Pink wr.ter from manufacturing operations nay contain^ TNT, TNT isomers, and dini trotoluenes (DMT) , while pink water generated by LAP and demilitarization operationn may contain <* ''’NT, cyclotrineth^lenetrini tra- mine (Rux', cyclotetramethylenetetranitramine (H*X), and wax. The volume and concentration cf pink water streams vary widely, but, at full mobilization, volumes of 378.5 m^pd f100,000 gpd) per line at concentrations of 100 to 150 ppm are typical (ref 1). Currently, activated carbon i3 the most widely used process for pink water abatement. The carbon is used once, then burned, which results in a high cost operation and an air pollution problem. Systems for thermal regeneration and carbon reuse tried in the past involved a high risk of explosion and a hioh loss of carbon. A new thermal regeneration process using rotary kilns has been piloted and appears to be safe and cost effective, but has yet to be implemented. Consequently, new technologies for abatement of pink water, such as the uv-ozone and uv-oxidant processes described in this report continue to be investigated. The uv-ozone studies helped establish approximate oper ating levels for the number of uv lamps per stage and ozone mass flow required to treat actual pink wator. The uv-oxidant studies established the film depth and oxidant concentration required. 1 UV-07.0NE TREATMENT OF PINK WATER The objective or the uv-ozone testing was tg establish design criteria and cost figures for a 378.5 r* 3 pd (100,COO gpo) pink water treatment plant. Test runs were made in a 1000 gpd uv-ozone reactor. Operating and design vari¬ ables for the minimum power demand and retention time re¬ quired to obtain an effluent containing less than 1 mg/L c* TNT and less than 1 mg/L of RDX were defined. Description Of Ultrox Pilot Plant The Ultrox^ pilot plant, recently developed by the Wesigate Research Corporation, is designed to demonstrate the practicality and cost effectiveness of uv-ozone oxi¬ dation for destroying organics in wastewater. The pilot plant can vary (1) UV light input and intensity, (2) ozone introduction rate, (3) mixing, and (4) water flow. The reactor is made of 304 stainless steel, passivated and electropolished to reduce chemical attack and increase reflectivity. A separate NEMA cabinet houses the ballasts from the UV lamps. The reactor can accommodate ud to 30 low-pressure, 65- watt uv lamps and has six operating stages. From 0 to 30 lamps can be turned on in a test run. Ozone 3s uniformly diffused from the base of the reactor through spherical, porous spargers, a procedure that generates gas bubbles of less than 2.5 mm diameter to obtain maximum mass transfer. The number of spargers can be varied from stage to stage, and the overall pattern of ozone introduction and diffusion can be changed as desired. The reactor is designed for low-pressure operation (2 psig maximum) to reduce the cost for pumping water and compressing air for ozone generation. Low-oressure oper¬ ation rot only provides greater safety but also reduces the thickness, weight, and cpst of construction materials. Pilot Plant Operation The flow rate of the incoming pink water is measured by a rotameter located between the pump and the reactor inlet. The water is fed to the reactor by the use of a sealless, magnetic, gear-type drive pump with integral. 1. Registered trademark 2 solid-state speed control. The drive pump vt*ies the flow of pink water through the reactor from 7.6 x lO - '* m^/min to 7.6 x 10"^ mVmin (0.2 to 2.0 gpm) , and the retention time will vary from 37 to 375 minutes. In each stage the water is contacted by the ozone and, in certain stages, by UV light. The purified water, as it leaves the reactcr, over¬ flows into a gas-water separator to eliminate any entrain¬ ment of water in the exhaust gas and then drains by gravity to a receiving sump. No internal level controls are re¬ quired within the reactor. Test Procedures Previous experience with pink water and waters of similar composition proved that the following variables have the greatest influence on total power demand and re¬ actor size: 1. Ozone concentration in sparginq gas. 2. UV light intensity. 3. Placement of uv lamps within reactor. 4. Temperature, composition, and concentration of incoming water. 5. Flow rate. Preliminary Testing The TOC of the ARRADCOM pink water sample was 68 mg/L, which was derived from 140 mg/L TNT, 22 mg/L RDX, ard 10 mg/L wax. The synthetic solution for the shakedown tests was mixed to contain this concentration cf TNT; however, large amounts of undiosolved TNT were present which reacted as the oxidation progressed so that it was difficult to control operating conditions and effluent quality. This problem was corrected by dissolving small quantities of TNT in boiling water, diluting it, and inserting an in-line filter at the inlet of the pilot ^7ant to remove residual suspended solias. Several experiments were carried out under these conditions (Table 1). These experiments helped to establish approximate operating levv„ 7 j» for the number of UV lamps per stage and ozone mass flow required to treat 3 Table 1. tJV-ozone treatment of TNT in water — u — VC CP -p w m in in 3 H Ip C M O o o in so vo vo in vo vc in + 1 o o CM <0 u VO CM VO co CO £ P PO co co CM co CO 5 4> 0) —' 0 P a a H a E 0. > 3 £• « > 3 Z c o * o CM •o CM + 1 • Q) + 1 O SO z id o CM co «# m VO CQ r* *r V CM CM /ith the synthetic solution and the TOC was only reduced to 17 mg/L during a 240-min. residence time. The residence time and number of uv lamps had to be increased in subsequent tests (1028 and 1029) to obtain a creater degree of oxidation. It appears that the reduce', reactivity in the pink water sample was caused by the presence of wax and RDX which were not present in the synthetic sample. A comparison of pink water and the- synthetic sample based on the result': of tests No. 1024 and 1029 is shown ir. table 3. The ozone-to-organic carbon ratios are about the same for the first three stages and the last three stages; however, the uv input power-to-carbon ratio had to be increased in both the first three stages and second three stages to achieve 3 mg/L TOC and 5 mg/L TOC in the pink water after six stages. Specific Analysis Less than 1 mg/L TNT and 1 mg/L RDX remained in the effluent, but there was also some unidentified solid res¬ idue in both the pink water and the synthetic sample (table 4). Test No. 1029 indicated that the TNT and RDX levels were below 1 mg/L after the pink water had passed through the first three stages of the reactor. This re¬ sult was most encouraging, since at these operating con¬ ditions the residence time, the number of UV lamps, and the ozone mas3 flow input can be reduced by half of the tot-al values used in test No. 1029. 2. Registered trademark 5 Table 2. UV-Ozone treatment of ARRADCOM pink water T3 VO i •j \ tr h c £ u « u o c <0 Cr u c o O o O O 0 • • • V in CO rv H '•V 4-> u W g £ O' £ 'J O' ro £ p l 0 r—i P a O in o 0 0) • • • a > o CN VO m n O' fM > «0 3 •P % 3c o CN CN ♦ 1 + 1 P O C r- 0 u 00 r* o r—< VO VO r* c C *W -H •H r. • • £ £ w C c •H •H P P e £ 0 0 a a 00 r- 0 H r- 0 0 M H H c c 3 o o 4-* ^ 1 1 N N •o u C“. o o o o PO CN CO CO V 0 a> —■ £ £ O' O' a •r4 £ £ e P P a> o o H 0 0 O o o O H H c c 0 0 ♦ 1 41 *o •o • •H -H O O O 0 • O o z 4 XI i3 0 0 CN CN ao ov 05 05 H r-C P CN CN CN m O o o a> tH H rH • • • • H 0 A O T3 f /. t Table 3. Comparison of synthetic sample and ARRADCOM pink water tests CM ?! e o i « 'tO I R 0 O' 0 4J in to to o to L. ? ? U I o to 0 O 1 K 4J 0 to I 0 0 Ol 0 O 0 00 at 0 0 tr 0 4J m 3* m rv o m o r'- o Ol XJ M O 4J 5 C >» CO w 0 M a x i v Table 4 . Analysis of synthetic sample and ARRADCOM pink u 9) p © « 3 *0 © \ ps cr e •O o (A 00 VO x: x: XX x: x: u P P P p P p M © X © C c £ c c c C P C P >i >• >1 >i >i p P P P P Vi to 03 V) V) cu (U © 0* « • o s H ri C* ri n P n 1 1 1 1 1 1 l i p O o vn 00 Ov av • fN 04 r« N n n n N • O O o O o o o O P H H H p p P P • Discussion of Test Results The mass ratio of ozone to TOC in test No. 1029 for the first three stages was 13, which is 1.6 times the stoichiometric ratio for carbon oxidation to C0 2 . Bench and pilot plant tests on a variety of wastewaters indi¬ cated that the minimum stoichiometric ritio of ozone to TOC usually is bet wen 1.3 and 2.0, depending on the or¬ iginal TOC concentration and the chemical structure of the organic contaminants. (However, this calculation does not include hydrogen and nitrogen oxidation in either case.) On that basis, the pink water appears to be reacting nor¬ mally. It is more accurate to represent the total oxidation of TNT and RDX as follows: TNT C 6 H 2 CH 3 ( n 0 2 J 3 ♦ 18 °3 —* 7 co 2 ♦ 3 HN0 3 + 18 ° 2 + H 2 ° RDX C 3 H 6 N 3 (N0 2 ) 3 ^ 18 0 3 —► 3 C0 2 ♦ 6 HN0 3 ♦ 18 (> 2 The pink water contained 140 mg/L TNT and 72 mg/L RDX. According to the above equations, the theoretical amount of ozone required per liter to carry out complete oxida¬ tion is 813 mg. Since the testing found that 910 mg/L was required to obtain an acceptable effluent, the ratio of actual to stoichiometric ozone is 1.12:1 (or an ozone efficiency of 89.3%). Of course, part of the ozone may be lost by autodecomposition or volatilization. Although a greater number of UV lamps was required to oxidize the pink water than the synthetic TNT in water so¬ lution, the number of lamps required per square meter and reaction stage has not been defined. Further tests are re¬ quired to establish these exact numbers. Design of UV-Ozone Pilot Plant With data obtained from the 3.79 m 3 pd (1000 gpd) the following design criteria were established for the 18.9 a^pd (5000 gpd) pilot plant: 9 / / Dimensions Reactor wet volume...2.8 m 3 (675 qal) Reactor dimensions (W x L x H).0.9 x 1.8 x 1.5 m (0.3 x 6 x 5 ft) Water flow rate .18.9 m 3 pd (5,000 gpd) No. of UV lamps $ 65 W/lamp....144 Ozone required.17 kq/day (37.5 lb/day) Assembly The major components of the pilot plant are the reactor assembly, the NEMA ballast enclosure, and the ozone generator. The reactor assembly and the NEMA bal¬ last enclosure are assembled on the same skid and the ozone generator is mounted on a separate skid. The reactor assembly (fig 1) consists of a stain¬ less steel tank with baffles and a cover assembly made up of the reactor cover, ozone diffuser, UV lamps, and sup¬ porting structure. Construction % The reactor tank, 0.91m x 1.83m x 1.52m (3 ft x 6 ft x 5 ft) deep, is fabricated from 0.48cm (3/16 in.) 316 stainless steel sheet. The bottom of the tank is formed from stainless steel. All parts are certified heliarc welded. A 10.2cm (4 in.) wide lip is welded to the top of the tank to form a gaoker flange. A groove is cut into the flange to accommodate a rectangular Hypalon 3 seal to enclose the reactor. The tank is moulted by bolting onto the metal skid. Five baffles are located longitudinally to create six reaction stages. Water flows in an undulation path from stage to stage (fig 2). The baffles are designed for easy removal so that the number of reaction stages can be altered, as desired. The ozone inlet manifolds, lamp venting tubes, and lamp 3. Registered trademark 10 1.14 mm (45.00 in) GAS x SEPARATOR WATER LEVEL INLET EQUALIZER OUTLET EQUALIZER Fig 1 UV-ozone reactor aas« 2 mbly 11 u/ lamps D D « l-i fc« « M W E-» O g 0 « conduits are welded across the reactor and provide ade¬ quate crosswise stiffening. Longitudinal stiffeninq is achieved by three strips of stainless steel welded to the cover plate, the manifolds, the ozone air vent, and the wiring conduits. A diagram of the proposed pilot system is shown in figure 3, Cover Assembly The following openings are punched into the cover plate: 1. One hundred and forty four holes, 2.86 cm (1 1/8 in.) in diameter (in a geometric pat¬ tern) for the quartz tubes that enclose the UV lamps. Nipples are welded at the top surfaces of these openings so that the quartz tubes are sealed to the cover by compression nuts with O-rings. 2. Six hole*:, 2.54 cm (1 in.) diameter, for the spent ozone gas outlets. 3. Six holes, 3.81 cm (1 in.) square, for matinq with the lamp support structure. 4. Six holes, 1.59 cm (5/8 in.) diameter, for the outboard lamp support and cooling air vent lines. 5. Two nipples, 3.81 cm (l*j in.) NPT, for water inlets. The lower lamp support structure consists of 3.31 cm (1% in.) square tubes with a 0.159 cm (0.0625 in.) wall thickness. Holes of 2.54 cm (1 in.) diameter are drilled on the upper side of the tubes at appropriate positions to install the quartz tube support and sealing assemblies which *re welded to the upper side of the tube. A 1.27 cm (h in.) diameter hole is drilled through the outboard end of the conduit to attacn the vent tube which also acts as a support for the end of the square tube. The center of the square tube is supported by welding the ozone line to the diffusers running parallel to the conduits. NEMA Ballast Enclosure A standard 1.52 cm x 0.91 m x 0.31 m (5ft x 3ft x 13 CO t I Pig 3. The 920 m 3 pd (5000 gpd) pilot plant assembly I I lft) deep, 16-gauge NEMA cabinet is used to contain and cool 72 lamp ballasts. The ballasts are mounted on racks in six rows within the cabinet. A rotary air blower, mounted at the base of the cabinet, directs the air up¬ ward for cooling the ballasts. The air exits at the top of the cabinet. The cabinet door contains a mounted LED display behind a glass window. The display shows visually the number UV lamps "on" in the reactor. Elastomer gasketing and springloaded screw clamps seal the ^oor. Ozone Generators A number of manufacturers can supply generators which meet the 18.9 m 3 /d (5,000 gpd) pilot plant criteria of 17 kg (37.5 lb) of ozone per day. From some manufacturers, such as OREC or PCI, two 9.1 kg (20 lb) per day ozone gen¬ erators would be required since neither one has an off- the-shelf 18.2 kg (40 lb) generator. The Welsbach generator is oversized, but it can produce 18.2 kg (40 lb) efficiently by lowering the input voltage by means of a variable voltage transformer. U UV-OXIDANT TREATMENT OF PINK WATER Bench-scale studies researching the effects of short wavelength UV-light and H 2 02 in the treatment of explosive- contaminated effluents have shown this treatment to be very successful (ref 2). This photo-oxidative treatment appears to be effective not only in decolorizing pink water, but also in destroying TNT, RDX, FMX, and other nitrobod- ies with a concurrent reduction in TOC concentration. These effects have been determined by gas, liquid, arid thin-layer chromatography (GO, LC, TLC), total organic carbon (TOC), and 14C-labelec' TNT assays. The economic feasibility of usinq commercially avail¬ able UV water purification units in conjunction with an oxidizing agent was investigated during the bench-scale studies. Variables, such as oxidants, film depth, serial passaging, and wavelength of IT/ light, were also examined for optimization of treatment parameters. Description of UV-Oxidant Pilot Plant A small-scale pilot system was designed incorporating four UV-light,water purification units connected in series. These were Model 2000 units manufactured by the Ultrady- namics Corporation of Santa Monica, California, w5th four 40-W mercury vapor lamps (254 nm) protected by quartz jack¬ ets that are continuously cleared by a hydraulically oper¬ ated wiper assembly. The liquid capacity of each chamber is approximately 22.3 L (6 gal). The maximum film depth of approximately 5.72 cm (2% in). Pink water obtained from a bomb loading and steam-out operation at the Naval Weapon Support Center, Crane, IN, was used in the study. Bcifore being pumped into the sys¬ tem, the water was filtered to remove suspended solids which could interfere with the treatment. Because its in¬ tense color would negatively affect the efficiency of the system, the pink water was diluted 1:1 or 1:3 with tap water to yield the following average explosive and TOC concentrations (mg/L): 1:1 dilution 1:3 dilution TNT 70.9 RDX 72.4 34.1 27.0 16 (cont) 1:1 dilution 1:3 dilution HMX 9.4 4.1 TOC 52.6 27.0 Previous studies (ref 2) determined that 0.1% (H20 2 ) is the optimum concentration to use in treating pink water. A 35% solution of (Fisher Chemical Co.) was added to the pink water to yield a final concentration of 0.1% H 2 O 2 . The water was recycled from a reservoir through the Uv units at a flow rate of 2.73 m 3 /hr ^720 gph) in a con¬ tinuous flow mode. Only 7.58 to 11.4 L (2 to 3 gal) of the 128.9 L (34 gal) solution were retained by the fast reservoir. Tubing volume is considered negligible because of the fast flow rate. The actual residence time of the liquid in any one unit is about 0.008 hr. A smaller com¬ mercial unit has been used to study the efficiency of the photo-oxidative treatment of pink water with respect to film depth. A Model 500 unit (also manufactured by Ultra¬ dynamics Corn.) with a 2.54 cm (1 in) film depth was used. The static capacity of its chamber is approximately 2.84 I (3/4 gal). It resembles the UV 2000 unit in structure and appearance. One gallon of pink water (undiluted or diluted) containing 0.1% H 2 0 2 was recirculated through the unit and back into a reservoir at a flow rate of approximating 0.4 mVh (105 gph) . Parameter Variations for Optimization of the System Oxidizing Agents and Film Depth Studies To test the effectiveness of incorporating a different oxidizing agent, a monopersulfate compound, Oxone* was sub¬ stituted for the H 2 O 2 in a number of studies using the UV- 20C0 and UV-500 system. In both systems, overall effici¬ ency was significantly increased by using 0.3% Oxone in place cf 0.1% H 2 O 2 . Table 5 illustrates the results of treatment of a 1:3 diluted pink water solution in the UV- 2000 (4-unit system) at a flow rate of 2.73 m J /d (720 gpd). 4 . Oxone is a mixture of potassium monopersulfate, potas¬ sium hydrogen sulfate, and potassium sulfate, manufactured by E.I. duPont de Nemours, Inc. 17 o o in l 'd c Id CM O O CM o as o CM U I o § 0) c 0 ) o X X X o c •H 5 -H :* c o H i/> x e id <3 »o 4 ; •H (0 x o in x in 5 I Vi o X a— x W 0) M > 53 b w <*> X C id •u •»H X o \ § X 0) H cn cm co co + + + E- CC £ z z z E E- E- 00 VO VO xt in >h cm o c + E-i Z CM *H CM XT + CQ CM z E- + ^ E-' 03 Z Z 5 E-* E-< E-* O xT O CM + CQ cm 2 o Eh Eh z z £ E- O VO 00 CM CO in oo • • O CM CM CM CM O O o • • . O o cn xr O O CM O O O CM 00 O O CO I" 00 CM «—I CTn 00 • • C O CM CM CM O © CO fx H CM VO in o • • ©•HO CM CM O O 00 O O CM © © XT O O CO O © vo o o CO © o VO © © VO o © CM r* © © CM © o o CM © o © CM CM o O O CM © SC CM I rH go jz •H Vi *. O 4-1 a a> o X >1 w X H Eh *o a» x o a) X a; *0 *o a> •H • V*_| as a> (0 id o X c i*H G H C >* a> >i rH Vl rH o o a x a a id e a rH fH rH rH in rH 0 id © © o O O O © CD o O CO O CO C X -H o © o XT O O av o o ffi o o C C 'd CO CO CM CM P CO -H a> O rH Id X a a> 6 0 E v- 3 o c •H © co in © co in © O rH © O rH •HHt . J X x 4 . ft. id id rs N Vi o rH o o 0) •o M 3 0 e u 18 I and in the UV-500 system at a flow rate of 0.4 m 3 /h (105 gph) using either 0.1% ^2^2 or 0.3% Oxone. The solutions were analyzed by liquid, gas, and thin-layer chromatography for explosive residues and TOC concentrations. From the results in table 5 it is evident that Oxone is far superior to H 0 O 2 with respect to deoolorization time, TNT elimination, and “'degradation of polynitroaromatic by¬ products with corresponding reductions in TOC concentra¬ tion:: These results also show that the 2., • cm (1 in) film depth of the (JV-50Q system Compared to the 5.72 cm (2*5 inj film c’epth of the UV-2000 system) enhances the efficiency of the treatment with either oxidizer. Various concentrations of oxone were also studied, and the potential of a combination H^O^/ Oxone treatment was examined. Because of the limited time available, only the effects of 0.3% and 0.2% Oxone on diluted pink water in the UV-2000 unit:*, and 0.3% and 0.7% Oxone on undiluted pink water in the UV-500 system were examined. A combi¬ nation of 0.1% H ? 0 2 and 0.1% Oxone was also examined in the UV-2000 system. Table 6 illustrates the parameters and results of the treatment. Treatment of 1:3 diluted pink water in the UV-2000 system with 0.3%, 0.2* and 0.1% Oxone and .0.1% H-O- dre comparable. The TOC levels were appreciably reduced .-rf’ no detectable amounts of explosives or polynitroaromauics were found after 3 hours of exposure. Treatment of an un¬ diluted pink water solution with 0.7% Oxone in the UV-500 system is not as efficient as treatment of a 1:3 diluted pink water solution with 0.3% Oxone, but it is feasible if environmental trade-offs are allowed. The same is true of a 1:1 dilution of pink water treated in the UV-2000 system with 0.3% Oxone. Flow Rates and Operations of Units In Series Two flow rates were examined in the UV-2000 system. There appeared to be no major difference in results be¬ tween flow rates of 2.04 and 2.73 m 3 ph (540 and **20 gph) while operating in a continuous flow mode. If the ulti¬ mate treatment were direct passage and not recirculation of the pink water through the UV system, the flow rate would not be critical, but the total UV exooture time or contact time of the solution in the units would be. Op¬ eration in a continuous flow mode through one to four UV- 19 Table 6. Analyses rious concentrations of CM C CN re n c * c o X o © (O l © O \ \ \ \ E-* < fr rt. E E- < Z CL Z c. 2 0 Z Q. E~ CN £h CN E-< CN E- CN + + + + CO ■N 1 Oh • • • • © co © © \ \ \ \ 00 H 00 o • • • • CN VO H in CN T CN CN \ \ \ \ 0) 4) 0) 0) u O o o tO ^ K *3 •—i u u • U H • 4-> © V © ■P O 4-> O CN CN CN CN © o O © • • • • © o © © \ \ \ \ r- in in CN • • • 00 CN CN H H •H c H © © • • • • © o © O \ \ "n. \ VO in © CN •n H CN H H H O © O © • • • • © © © O \ \ \ \ 00 CO CO CN l o CN CN CD O. Z *“• E- ♦ \\ E- < + in CO o o o in I g o o in \ CN O • O CM O • o \ m CN © • o \ 00 co o \ f- < + 00 \ o • co CN co o \ o CN o • o \ CO o • o \ VO © CN H O • o \ o 4J O — <0 u v x: C CN o U 0) CO CO co CO vo CO e gs 09 U 0> tr — «* 4-> G JC G CN o O VO rH E \ \ \ \ • \ y 00 rH 00 o pH ■rr C • • • • \ • (0 E- CN VO pH m m in 4J CN * CN CN CN rH 3 O O CD \ \ \ \ 00 0) 4) 4) 4) 4) o o\ in U CD O O O O \ • \ • • u r- X . 40 40 40 pH O CN O O CN O 4J 4-> O CN in 40 O CN CN ^- “T4- o o o O o O • • 4J • • • • o o X >- X o o o O \ \ C r-4 5' \ \ \ \ o av ■H 40 X IT) in • • 0 . c CN • • • m VO < ao CN CN »—t in r-4 Ha rl o o 0 o o O o • • • • • • o o +J X o a o o \ \ c c a \ \ \ \ 00 o o • • I Eu CN »n pH CN VO 00 5 \ CN Tj- 40 tr H rH pH pH pH rH 4) -H c o o o o O I; >• • • • • • • x» o E o o o o o o r- \ \ \ \ \ \ u c E- 00 •*r m m o o 0 CN VO CN CN m VO U-4 -H <#> +J 1 + at 40 -rH 4-1 4) 4) 4) O 4) •rH C (1) • 0 • O • O . o • c • C • C •h a X -H Cr O X o x O X OXO CN O CN O CN •u o O N 40 o o 0 O X X X 40 C 4J C 4) u o O C H-> 0) r-4 O 4 >1 *J -H 4-> Eh 40 rH CL. 40 *0 TJ o O o o O o < Eh 4) * \ CN rH CN CN CN pH TJ « TJ »Q XS rH 4> 4) a — n r-'O <«-*, — •0 40 H g 4J tr o a, o a o a o o o a E« X •4) 3 40 - om am am o o om o 4-» rH 4) o g o g o g o o o g 4h lOOMO * * % h > h a o r- O -rH •• •• •• •• — •• 5 a rH pH pH pH pH rH JC TJ 4> N >1 »—4 <0 C «0 » * CQ g a >i ja •o 0) N N r—4 <0 c 4} 0) Eh 0) y X s •o c (0 % I < CM <0 XI 23 Trace&r-of polynitroaromatic compounds. (3 hr in W-2000 system) l \ o o o o o U3LLYJ4 mid HI 3fY3HDaa XNSIDgSd l i Figure 4 . Effect of pink water dilution on TOC cannot oxidize it. The significant reduction of TOC and rapid decolorization observed with the sample irradiated at 254 nm is a good indication that this shorter wave¬ length has a pronounced effect on the overall efficiency and effectiveness of the photo-oxidation system. Chemical Reactions The proposed mechanism of action of the and Oxone (monopersulfate compound) in the treatment is the produc¬ tion of OH radicals which are ultimately responsible for the destruction of the explosives in the water upon expo¬ sure to UV light. The mechanism of each is outlined below with RH representing the explosive. H 2°2 2** OH RH + 'OH + R' + H 2 0 R* —* cleavage of ring H00S0 3 *0H + *0S0 3 RH + *0H -*R* + H 2 0 R' —cleavage of ring Additional Analyses In addition to explosive analyses, the treated samples with the higher TOC levels (2 mg/L) were analyzed for nitro- soamines (ref 3,4) and sulfonates (ref 5,6). No detectable levels of these products could be found by TLC procedures (sensitivity 50 npb) in samples irradiated in the UV-2000 or UV-500 system with either H 2 0 2 or Oxone. In each case using H 2 0 2 , the peroxide level was moi- itored in the treated samples. The levels of residual peroxide range between 30 and 100 ppm after 3 or 5 hours of exposure in the UV-2000 system and 1.5 hr in the IV- 500 system. With direct passage (instead of recirculation) of the pink water through units in series, the H 2 0 2 will probably be completely destroyed, since UV efficiency is enhanced with decolorization. The pH of the pink water solutions containing 25 or Oxone was monitored before and after treatment. Before treatment, the pH values averaged 7.3 and 3.2, respectively. After treatment, the values fell to 6.4 and 2.4. If the extremely low pH of the treated water with oxone poses a problem, it can be economically and simply neutralized by the addition of lime after treatment and before discharge. Design Parameters of Full-Scale Treatment System If pink water is to be treated effectively in the sys¬ tem, it must be filtered to remove suspended solids before irradiation. This can be accomplished by use of a filter between the source of the effluent and the sump where it is discharged. The trapped explosive crystals could be reclaimed, if desired. After eliminating the suspended solids, the liquid is diluted, if necessary, and pumped into a mixing tank where metered additions of hydrogen peroxide or Oxone are made. To be certain that a homogeneous solution is prepared, the pink water and oxidant are further mixed by an in-line triblender after which the mixture is pumped into the UV- sy3tem for treatment. Figure 5 illustrates the basic design of the system. After treatment, the water can be discharged directly into a sewer line or, if H 2 C >2 were used as the oxidizer, it cculd be recycled through the system for di¬ luting untreated pink water. The treated water originally containing Oxone cannot be recycled without further treat¬ ment, since residual amounts of potassium and sulfate ions in the treated water would increase with each fresh addi¬ tion of oxone. f ' 27 Figure 5. Basic design of the UV-oxidant system m CONCLUSIONS UV-Ozone Treatment 1. Data obtained from a 3.79 m 3 pd (1000 gpd) pilot plant demonstrated the feasibility of using uv-ozone to oxidize TNT and RDX in aqueous solution and to produce an effluent containing less than 1 mg/L of TNT and RDX. 2. A design was generated for a 18.9 m J pd (5,000 gpd) modular uv-ozone pilot plant for treating pink water. The proposed design would allow a single unit to be used for low-flow applications or multiples to be used in-series for full mobilization requirements. UV-Oxidant Treatment 1. From the optimization studies using commercially avail¬ able UV water purification units, the treatment procedures incorporating Oxone are more efficient than H 2 0 2 in re¬ ducing the total organic carbon levels. 2. A design for a 378.5 m^pd (100,000 gpd) uv-oxidant treatment plant was proposed. 28 RECOMMENDATIONS UV-Ozone Treatment 1. A 5000 gpd (18.9 m'pd) pilot plant should be evaluated at an ammunition plant in order to determine the operating conditions required for achieving the minimum fixed and operating costs for a 378.5 ra 3 pd (100,000 gpd) plant. 2. An economic analysis should be performed on the 18.9 m^pd (5000 gpd) unit after process parameters nave been optimized. UV-Oxidant Treatment 1. A study should be made to develop a new design for the UV-oxidant process that would be suitable for purification of larger volumes of pink water to enhance the economics of the process. 2. Further studies of the process should be made only if more cost-effective equipment is developed to process the volume and concentration of pink water to be expected in a full-scale plant. 29 REFERENCES 1. J. Patterson, N. I. Shapira, J. Brown, W. Duckert, and J. Poison, "State-of"the-Art: Military Explosives and Propellants Production," Environmental Protection Agency (E.P.A.) Report 600/2-76-2/3 a, b, c, October 1976. 2. C. C. Andrews and J. L. Osmon, "The Effects of Ultra¬ violet Light on TNT and Other Explosives in Aqueous Solution," WQEC/C 77-32, Naval Weapon Support Center, Crane, Indiana, 1977. 3. E. Zuesh, G. and J. Sherma, "CRC Handbook of Chroma¬ tography, Solvent 3," CRC Press, Cleveland, 1972, p. 445. 4. E. Merck, "E. M. Reagents: Dying Reagents for Thin- Layer and Paper Chromatography," Darmstadt, W. Germany, 1975, p. 37, p. 83. 5. Ed Hais, I. M. and K. Macek, "Paper Chromatography," Academic Press, New York, 1963, p. 637. 6. Standard Methods for the Examination of Water and W astewater , 14th edition, American Public Health Association, Washington, DC, 1976, 493-495. 30 DISTRIBUTION LIST Commander U. S. Army Armament Research and Development Command ATTN: DRDAR-CC DRDAR-LC (2) DRDAR-LCM DRDAR-LCM-SA) (6) DRDAR-SC DRDAR-TSS 15) DRDAR-LCU-P Dover, NJ 07801 Commander U S. Army Materiel Development and Readiness Command ATTN: DRCDE-E DRCIS-E DRCPA-E DRCRP-I C'RCDL DRCSC-S 5001 Elsenhower Avenue Alexandria, VA 22333 Commander U.S. Army Armament Materiel Readiness Command ATTN: DRSAR-iR DRSAR-iRC DRSAR-IRC-P DRSAR-IRC-E DRSAR-PDM DRSAR-ASF DRSAR-LC DRSAR-LEP-L Rock Island, IL 61299 31 Commander USDRC Installations and Services Agency ATTN: DRCIS-RI-IU DRCIS-RI-IC Rock Island, IL 61299 Project Manager for Munitions Product.on Base Modernization and Expansion DARCOM ATTN: DRCPM-PBM-EC DRCPM-PBM-T-EV Dover, NJ 07801 Department of the Army Chief of Research, Development and Acquisition Washington, DC 20310 Director U.S Army Industrial Base Engineering Activity ATTN: DRXIB-MT Rock Island, IL 61299 Department of the Army Chief of Engineers ATTN: DAEN-2CE Washington, DC 20310 Com: :ander ARRADCOM Chemical System Laboratory ATTN: DRDAR-CLT Aberdeen Proving Ground, MD 21010 Defense Documentation Center (12) Cameron Station Alexandria, VA 22314 Commander Mobility Equipment RSD Command ATTN: DRDME-GS Fort Bel voir, VA 22060 32 Commander U.S. Army Construction Erjyineei ing Research Laboratory ATTN: CERL-ER Champaign, IL 61820 U.S. Army Engineer District, New York ATTN: Construction District 28 c ederal Plaza New York, NY 10007 Commander Mila.^ Army Ammunition Plant ATTN: SARMI EN Milan, TN 38358 Commander Newport Army Ammunition Plant ATTN: SARNE-S Newport, IN 47966 Commander Pine Bluff Arsenal ATTN: SARPB-ETA Pine Bluff, AR 71601 Commander Radford Army Ammunition Plant ATTN: SARRA-IE Rad f ord, VA 24141 Commander Ravenna Army Ammunition Plant Ravenna, OH 44266 O .r.mander Sunflowar Army Ammunition Plant ATTN: SARSU-0 Lawrence, KS 66044 33 Commander Volunteer Army Ammunition Plant ATTN: SARVO-T Chattanooga, TN 34701 Army Logistics Management Center Environmental Management ATTN: Mr. Otto Nauman (2) Fort Lee, VA 23801 Project Manager for Chemical Demilitarization and Installation Restoration ATTN: DRCPM-DRR, Mr. Harry Sholk Aberdeen Proving Ground, MD 21010 Commander Cornhusker Army Ammunition Plant ATTN: SARCO-E Grand Island, NB 68601 Commander Holston Army Ammunition Plant ATTN: SARHO-E Kingsport, TN 37662 Commander Indiana Army Ammunition Plant ATTN: SAR.N-OR Charlestown, IN 47111 Commander Naval Weapons Support Center ATTN: Code 5042, Mr. C.W. 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Broadway White Plains, NY 10603 U.S. Army Materiel Systems Analysis Activity ATTN: DRXSY-MP Aberdeen Proving Ground, MD 21005 Weapon S ► .tern Concept Team/CSL ATTN: DRDAR-ACW Aberdeen Proving Ground, MD 21010 Technical Library ATTN: DRDAR-CU-L Aberdeen Froving Ground, MD 21005 Technical Library ATTN: CRDAR TSB-S Aberdeen Proving Ground, MD 21010 37 I / / Technical library ATTN: DRDAR-LCB-TL Benet Weapon # Laboratory Watervliet, NY 12189 Commander U.S. Army Medical Bioengineering R&D Laboratory SGRD-UBG-L Fort Detnck, Frederick, MD 21701 7 \ i I * i j i '• I 4 38 I UNIVERSITY OF ILLINOIS-URBAN A I DATE DUE CALI HUMBER 662.27 R845#4^^ DATE DUE: Qh^S'^U I m 16 ws 7 / 9/91 VOLUME: COPY: HISSING: IN USE fiaoUUilJlT moxth ^ fT“" OKU CTkk AUTMOll Roth Tint Ultraviolet - ozone and LT l-tTTTVTTrl^T —~TryrvfrHTTi—rrew n 3 0112 099059369 DEMCO