AD-A280 125IEIIIIIIIIU

Evaluation of Pre-extractionAnalytical Holding Times forTetryl in SoilThomas F. Jenkins April 1994

a ELECTE

94-17284

94 6 7" 0407

A sAudy was conducted to experimentally evaluate ft maximum acceplablepre-oxhcion analytical holding times (MHTs) for MW In soil. Three soilsforted wiNh teriy at the low micrgram-per-grom level were used In Ihe study.Sorwamples of each soil wm extracted with acelonlle in an ultrasonic balhalier being held for 0, 1, 3 and 7 days at eithw room lemperalure (220C), underredigeaton (2C0) or frozen (-150C). Exlraot were analyzed by RP-HPLC.Te* concendwallons In soils stored at room temperature and under refrigerationdeclined rapidly over the 7-day study period and several transformationproducts a=ccnumfad. Aier 7 days ofMorage at 200, er concenkations werereduced by 46, 97 and 99% In the three soils sludied. When the soils werefe tee were no slalstcallysignfloantanal loosses overft 7-day studyperiod (95% confidence level). On to basis of too results of two expedments,he recommended MHT for soils containing le"yt Is 7 days I kepfroznm. Longerholding timesmay be possible, bueywr n invesigated hem. RefrigerationIs Inadequalo pw t slgnlflcantransform•lon of ten/l In soil samples beingheld for analysis. A question regarding the ability to use analyforlifled soil tomImic field-conlaminaled soils In holding time studies Is raised.

Forconvemslo ofaS1 mek unlist o U.SJBfltsh customary unlis of measrmentconsul ASTM Skandard E380-. , iAtdo Pracilb forA . of* Me#*Vaf, n of L#^b pubdleed by I* Americani Sociely for Testing and Merials,1916 Rac St., Phlaodelphi, Pa. 19103.

ThW r•ot Is printed on paper ta conlains a minimum of 50% recycedmatri0l.

7- ,

Special Report 94-5

US Army Corpsof EngineersCold Regions Research &Engineering Laboratory

Evaluafion of Pre-extractionAnalytical Holding limes forTetryl in SoilThom F. Jenkins Mccesion For April 1994

NTIS CRA&M

DTIC TABUllannounced 0Justification ................-

By--- --- ---- -

Distribution I

Availability Codes

• Avail and I or

Dist Special

A fsdorUS& ARMY ENVIRONMENTAL CENTERSR-ApfEC- mS ; R-nbuApproved for l:b IIfrleome dleftmlon ig unrdled.

PRUWACE

This report was prepaed by Dr. Thomas F. Jkins, Research Chemist, GeologicalSciences Branch Reearch Division, U.S Army Cold Regions Research and EnghieeringLaboratory. Funding was provided by the U.S. Army Env tal Center (ABC) (for-merly the U.S. Army Toxic and Hazardous Materials Agency), Aberdeen Proving Ground,Maryland, Martin H. Stutz, Project Monitor.

The author gratefully acknowledges Dr. C.L Grant, Professor Em'eritus, University ofNew Hampshi, Martin H. Stutz, AEC, and Marianne EL Walsh, CRREL, for their technicalreview of this manuscript Susan M. Golden, Science and Technology Corporation, isacknowledged for conducting many of the experiments described. Patricia Schumacher isacknowliedged for careful preparation of the analytical stock standard for tetryL MarianneWalsh is cited for GC-MS analysis of extracts from field-contaminated soil from theNebraska Ordnance Plint in Mead, Nebraska. Lawrence Perry and Chad Pidgeon are alsoacknolmdge for supplying background chrmiatograms, of the soils used in this study.

This publication reflects the personal view of the author and does not suggest or reflectthe po&c, practices, program, or doctrine of the US. Army or Government of the UnitedState. The contents ofthis reportare not tobe used for advertising orpromnotional purpssCitation of brand names does not constitute an official endorsement or approval of the useof such commerciml products.

ii

Evaluation of Pre-exv aton AnalyticalHolding lmes for Tetayl in Soil

THOMMEF.JENKINS

IW1ODUMMON ourimowledge. band on best judgment and coimins-ftec with other methods for sernivolatile organics.

A serious environmental problem facing the U-S. According to, the ASIM (1986), MMT is defined asmilitary as the presence of soil contaminated with the "maximumn period of time during which a prop-residues of munitions compounds at alargenumber erly preserved sample can be stored before suchof its installations. One of the most commonn prob- degradation of the constituenit of interestP P occurs orleans comes from the manufacture, use, storage and change in sample matrix occurs that the systematic

demiitaizaionof high explosives. These residues error exceeds the 99% confidence interval (not to ex-are oftm composed of nitroaromatics and nitra- ceed 15%) of the test about the mean concentrationmines, along with their mnfc urngipurities found at zeo time." Holding time studies are oftenand environmental transformation products (Walsh configured to experimentally assess stability, usu-et a.1.1993). Sh-nce many of these compounids are rela- ally using analyte-fortifled. samples.tively stable in the environment and quite mobile in Recently, Maskarinec et aL (1991) estimatedthe soil, they have become sources of groundwater maximum pre-extraction holding times for severalpollutio at military facilities (Pugh 1962, Spaulding nItroaromatics and nitramines in soil and waterand Fulton 1968). samples. Similar studies were reported by Grant et

Tetryl (2A,4,trintrophenylnitramine) can be clas- al. (1993a~b) using a slightly different experimentalsified as either a nitroromatic or a nitramine. It was protoicol. Neither of these studie included tetryl,used by the U.S. Army as early as 1904 as a booster even though it is a target analyte of SW846 Methodin anumber of munitions formulations (Kayser etal. 8330, probably because it has been less frequently1984). While the use of ktetyl was discontinued in found in samples from military sites compared. with1979, residues of tetryl have been identified at a other high explosives such as TNT (,,-rntonumber of military faciltie in the United States toluene) and RDX (hexahydro,-1,3A,5-tront-1,3,5(Keirn et al. 1961, Batzer et al. 19e2, Walsh et Al ftiazine) (Walsh et al. 1993). In addition prelimiary"1993)- experiments indicated that -nvironmenital transor

aboamtory methods have been developed to matir products of fttryl eluted at similar retentioncharacterize sites potentially contaminated with times and, thun initerfered, with determination Of..-tI IrI atic and nitramine explosives. Becase ex- other nitroerorniaticsand their- t ~ransration prod-

plosves residues in contamninated .oik wene known ucts. Thus, unike sotne of the other analytes of in-to be composed of a variety of dwemicais often cc- tIerPet in Method 6330, which could be studied to-currkig togethe and many of theme chemiucals are gether, tetryl had to be evaluated. separately.known to be tiurmafly laile, most methods me While the fafteofftetrl uanderenvironmrentalmcn-based on Hl-Nrfoiannce Lpiqud Qarmawagra- ditios is not cornpliety understood, It is knownplay (HFLC (AQAC 1990, ASMl 1991, IIPA 1992) Oiteryaa4.toyroyipht Astion

Whlealos al ~s peifcaiosin thememeth and blo, F fmtLma Kayme et AL (19M4) Axmdvw bind on experlmatal umub (Jkinak et AL " Uttylpholk m umwdaambluat fthtlngoa=%&imp9, fmaet a 1990) Oe Maximau pMre*extrat tiornat hutMa oder of manitude feder tiwthy-1o9*,1g 7hwP*N o(l@7 daysfor silMad water drolyrn 11e mvor pIMl-otorkfanaftlan productaylu ka SWS6 Muthod, W30 (EPA 1992) wn4 to deetdw Nnuylcm de(-th-A

trinif•oaniline). The products detected from hy- contents were stirred at room temperature for adrolysis in the dark were pH dependent. Under week. The solution was then filtered through 0.45-acidic conditions, the major organic hydrolysis pm nylon membranes into a clean brown glass jug.products detected were picric acid (2,4,6-trinitro- No solvents, other than water, were used in thephenol) and N-methypicramide. Under basic condi- preparation of this solution.tions, the rate of reaction was faster and the major The concentration of tetryl in the fortification so-transformation products were methylnitramine and lution was determined against standards preparedpicrate ion. in acetoitrile (Jenkins et aL 1986, SW846 Method

Recently, Harvey et aL (1992) studied the bio- 8330) and diluted 1:1 with reagent grade water priortransformation of tetryl in soil They concluded that to analysis. The concentration of tetryl in this spik-the truformation in soil was extrenely rapid and ing solution was determined to be 30.6 mg/Lthat the primary trar mation product was N-methylpcramide. Unfortunately, they chose to ex- Soilstract tetryl and its transformation products from soil Blank test soils were obtained locally from Ver-using Soxhlet oeraction prior to RP-HPLC analysis. mont (Windsor), New Hampshire (Charlton) andSubsequent research has indicated that tetryl is not New York (Fort Edwards). These soils were airstable to this procedure Genkins and Walsh 1994) dried, ground with a mortar and pestle and passedand their condcumis, relative to the instability of through a 30-mesh sieve (590 pm). Some physicaltetryl in the soil and the transformation products and chemical properties of these soils are presentedproduced, are suspect. in Table 1. Replicate 5.0 + 0.1-g subsamples of each

blank soil were placed in individual 20-mL glassscintillation vialks

OBJIBCTIVE

The major ocie of th~is study is to estimate Table 1. Physical and chemical properties of test soils.

the MHT for tetryl in soil This will be done by forti- soafying several different soils using an aqueous spik- Fort Edi. Wdasor sady Curton s4

ing soution and measuring the concentration of p.ut day 1m kumtetryl and any observable transkmation products pH U 62as a functim of time. TCHC 0.5 1.1 1.8

Cay () 70 30 20CEC O(•mq/I00 g >1o 3.5 73

-oWA Lral oqp ic aubom

_ _esicl "Candma meapadty

All stmndds and test solutions of teyl wereprepared • m StandardAnalytical ReferenceMate- A field-contaminated soil containing tetryl andrials (SARM) obtained from the U-. Army Envi- some of its transformation products was obtainedronnental Cene (USAEC), Aberdeen Proving from the Nebraska Ordnance Plant, Mead, Ne-Groud, Maryland. The aqueous solution used for braska. The soil was air dried, ground with a mortarsoil fortification was prepared in reagent grade wa- and pestle and mixed thoroughly.ter obtained fom a Milfi-Q Tlype I Reagent GradeWater System (Miflipore Corp.). Methanol used in Soil wetting and analyte spikingthe preparation of HPLC eluent and acetonitrile Prior to the onset of the experiment, previouslyused for soil extraction were HPLC grade from air dried test soils were rewetted. Because the tex-Ailtech and Baker respectively Eluent was prepared ture and water holding capacity of the various soilsby combining equal volumes of methanol and water differed, the volume of water added to each soil wasand vacuum filtering through a nylon membrane varied such that, after spike additions were also(0.45 pm) to degas and remove particulate matter. made, there was no evidence of bee-standing water.

For the three initially blank soils, 020 mL of reagentTetryl fortification solution grade water was added to the Windsor sandy loam

The soil fortification solution was prepared using and 1.00 mL was added to the Fort Edwards Claywater. The SARM for tetryl was placed in a brown and Charlton silty loam. After water addition, allglass jug, reagent grade water was added, and the soils were allowed to stand at room temperature in

2

the dark for 3 days to allow microbiological activity Method 8330) with two differences. First, the soilsto reestablish (Maskarinec et aL 1991, Grant et aL were not air dried prior to extraction, because it was1993a). judged that the time required to dry the soil in the

The three initially blank soils were fortified by vials at room temperature could result in analytecarefully adding 1.00 mL of aqueous tetryl spiking loss and confound the effect of the holding timesolution to each test vial. Except for the soils desig- temperatures. Second, a 5-g portion of soil was usednated for 30-minute exposure and those to be stored for the fortified samples, instead of the usual samplefrozen, the spiked soils were immediately placed in size of 2 g, to conform to the test protocol used ear-the dark at the appropriate storage temperature. The her for TNT, TNB, 2,4-DNT, RDX and HMX (Grant30-minute samples and the samples to be frozen et al. 1993a).were permitted to stand for 30 minutes at room tem-perature in the dark after fortification to allow time RP-HPLC analysisfor tetryl to interact with the soils prior to either ex- All soil extracts were analyzed by Reversed-traction or freezing. Phase High Performance Liquid Chromatogra-

phy (RP-HPLC) on a modular system composedSoil holding time test parameters of a Spectra-Physics Model SP8800 ternary HPLC

A summary of the test parameters used for the pump, a Spectra-Physics Spectra 100 UV variablesoil holding time study is presented in Table 2. For wavelength detector set at 254 nm (cell path 1 cm),the fortified soils, three storage conditions were ex- a Dynatech Model LC 241 auto sampler equippedamined, room temperature (22 ± 2°C), refrigerator with a Rheodyne Model 7125 Sample Loop Injec-storage (2 ± 2-C) and freezer storage (-15 ± 2-C), all tor, Hewlett Packard 3393A digital integrator andin the dark. Portions stored under these conditions a Linear strip chart recorder.were extracted after 1, 3 and 7 days of storage and All extracts were analyzed on a 25-cm x 4.6-mmthe tetryl concentration determined. Because of ex- (5 gm) LC-18 column (Supelco) eluted with 1:1pected variability among subsamples, triplicate por- methanol-water (v/v) at 1.5 mL/min (Jenkins et aLtions were analyzed for each storage temperature 1989). Samples were introduced by overfilling a 100-for each storage time. pL sampling loop.

Table 2. Experimental factors for soil holding time study. Soil extraction for GC-MS analysisA 2.0-g portion of the field-contaminated soil

Fow • from the Nebraska Ordnance Works was extractedFactmor No. of kv els with 10.0 mL of acetonitrile as specified above

Analytes 1 Tetryl (Jenkins et aL 1989). A 2.0-mL aliquot of the extractSoils 3 Fort Edwars, Charlton, Whidsor was fitered through a Millex-SR filter into a glassStorage temp. (C) 3 -15, 2. 22 scintillation vial and the acetonitrile was allowed toStorage time 4 30 rin, 1 day, 3 days, 7 days evaporate to about 0.5 mL in a fume hood. A 2.0-ILReplicates 3 aAbc aliquot was analyzed by GC-MS as described be-

low.

Soil extraction for RP-HPLC analysis GC-MS analysisFor extraction, the vials containing the soil were GC-MS analysis was conducted on an HP5992

allowed to warm to room temperature and 9.00 mL MSD (mass selective detector). The sample was in-of acetonitrile was added. The vials were vortex troduced into the MSD through a Hewlett-Packardmixed for I minute and placed in a sonic bath for 18 5890 Series 2 gas chromatograph operated in thehours. The temperature of the bath was maintained splitless mode. An HP-5 (cross-linked 5% phenylat less than 250C with cooling water The vials were methyl silicone, 25-m x 0.20-mm x 0.33-pm filmthen removed from the bath and allowed to stand thickness) column was maintained at 75°C for 2undisturbed for 30 minutes. A 10.00-mL aliquot of minutes and then the oven was temperature pro-aqueous CaCI2 (5 g/L) was then added and the soil grammed at 200C/min to 240-C and held for 10particles were allowed to flocculate for 30 minutes minutes.before a 5-mL aliquot of the supernatant was fiteredthrough a 05-pim Millex SR filter Data analysis

This extraction procedure was based on the The mean and standard deviation for each set ofmethod developed by Jenkins et al. (1989) (SW846 triplicate measurements were calculated. Using the

3

8wd LOW

ompo Ony 3 Cay Day?7bum~~~~~ Ru ýgmip un7T=60 r r~)f-~V

c

Aý

CAno~k~h ReII Ck (wn embTm(mn' N WTM(mFim . -PL dottgm frM"cbcýkllrffd inw d kmaU

Chow" I * I I

O 4812Y41

0.10D~y DayS 3O I Day?7

AA

UA

i i 12 4 2 4 12 0 4 I* * ' I' 12-Riwonmim Rom go ~ma This OW RP"' This (.M) PAN ON This OMk)

Figure 2. RP-HPLAC dmmatogmmsu aforet cts of yL-f"~IIW COwlton silty loam soi.

3a DayS3 Day?7

fus~s ~r) D j CPr')E-~I

L* 3

Aaoomoon Thng po~) PaguAon Thu (min) Reunio Thus (umi) Roudsi Thia(ffm)

Figur 3. RP-HPLC chrom"atfoginr ext ict of tetrl forilfid For Ekw*r dlay.

4

3O00dmat yak.. W initial conotaiu we 1

deftsmirtd pacnt recoveries for each period.

RESULTS AND DISCUSSION 1 otEwf

Conmitraton of tetzyl Vs&reffigerator holding time

Qhromatograms fromn several of the soil ex-

conceritratinof teryl can beseen after only 3 Fi4.Tbl(a)days at room temperature, and three apparent rtransfohmaionpout lbldA n 0 2 4 6 a

tion, te tetny o tce smetratir s rdue b igr 4 efy concentnition asafitnction of holding ieo

much fiaser than that for the W~indlsor soil, both at over 99% loss of tetryl after 7 days of refrigerationroom temperature and under refrigeration. The The relative amounts of the various transformationsamne three transaformation products observed in the products observed for thi-s soil appear to be differentextracts of the Windsor soil are again evident After from those, observed for the Windsor and Charlton7 days under refrigeration, the initial concentration soils. One of the reasons for the different behavior ofof teIy is reduced by 97%. this soil is its pHK which is 8.4 compared to 6.2 for

FIrgure3 pesenits cho-at- rm of the extracts Windsor and 6.0 for Charlton (Table 1). As discussedof Fort Edwards clay. Peaks labeled as D, E and F are above, Kayser et al. (1984) observed that hydrolysisimpurities present in unfortifled Fort Edwards clay, products were different at acidic and basic pH andThe rate of degradation of tetryl in this soil is even that hydrolysis proceeds much faster under basic

conditions. Perhaps the very rapid loss of teIy forthe Fort Edwards day is partially attributable to hyf-

Table 3. Causcurtration (WSl) of "eIy as a function of drolysis rather than biodegradation The lower vi-holding time for three tes soils. tial concentratoio of tetryl for this soil, relative to

Windlsor and Charlton, may be a reflection of rapidSlokmget ý tewnquiowhaw( hydrolysis during the 30-mintute period where tetryl

I*Min 22222 11 was allowed to interact with the soil before initial(dip) 22±22±2 15±2 extraction.

W8iw Sm4iI Lmn Plots of the concentration of tetryl hor the thre0 5.48*0.74 5&48*k0.74 5.48 *0.74 soils vs. refrigerator holding time mre shown in Fig-1 3.16*0.13 &92 *0.70 5.00* 0.13 ure 4LClearly,te"I is not stabilized adequately us-7 0.66*0.42 4.9415:.09 4.10 *0.78 ing refrigerator storage for the current 7-day hold-

Owfito sitty Lm0 5.58*0.0 52% *0.04 5.58*0.04 Effect of freezing1 0.30*0.12 2.82 *0.10 4.07*10.05 Storage by freezing improves the stability of3 &0.0*0.00 0.917*0M.02 5.47*0.16 tetayl substantiall Figure 5 shows the concentra-

7 0.4:kow 0.7*002 500i .16 tion of tetryl as a function of freezer holding time forFort Edwmrds Mly the three soids studied. Linear regression analysis of

0 4.43*0.29 4A63* 0.29 4.43:k 029 the mean teIy concentration vs. holding time for1 0.03 * 0.02 0.17*0.04 3.75 *0.11 the three soils results in a slope of -0.021 and an in-3 0.00 0.06t* .01 3.43±*0.05 tercept of 4.624. The slope, however, was not statisti-7 0.M 0.04±*0.01 4.05±*0.06 cafly different from zero at the 95% confidence level,

5

6 experiments indicate that their results probablywere an artifact of the Soxhlet extraction proce-

dure they used (Jenkins and Walsh 1994). Identi-fication of transformation products of tetryl by

* GC-MS is complicated by the instability of the4 . nitramine nitro group to GC-MS analysis

o (Tamiri and Zitrin 1986). For tetryl itself, a loss ofNOý, apparently caused by thermolysis in theinjector, results in the formation of N-methy-lpicramide (Fig. 6). Walsh and Jenkins (1992)

12- identified three compounds when acetonitrileo Windsor extracts of tetryl-contamninated soils were ana-* Chariton lyzed by GC-MS: N-methylpicramide, 4-o Fort Edwards Samino-2,6-dinitro-N-methylaniline and 2,4,6-

trinitroaniline (Fig. 7). A major portion of the N-

SI I methylpicramide found was probably createdU2 4 6

Hokding Trm at - is- c (days) by degradation of tetryl in the injection port ofthe GC-MS. Likewise, 4-amino-2,6-N-methyl-

Figure 5. Tetryl concentration as a function ofholding time for aniline could have resulted from loss of NO2samples stored frozen at -150C. from the nitramine NO2 portion of 4-amino-N-

methyl-N,2,6-trinitroaniline in the injector (Fig.indicating that there was no statistically significant 8). Microbiological reduction of tetryl to 4-amino-N-loss of tetryl for freezer storage at -15°C over the 7- methyl-N,2,6-trinitroaniline is consistent with theday study period. In addition, no accumulations of production of 2-amino-2,6-dinitrotoluene and 4-transformation products A, B or C were observed af- amino-2,6-dinitrotoluene from 2,4,6-trinitrotolueneter 7 days of frozen storage. Longer storage periods (McCormick et al. 1976) and 3,5-dinitroaniline fromwere not tested, but future work should assess the 1,3,5-trinitrobenzene (Walsh et al. 1993). A standardpossibility of longer-term storage. of 4-amino-N-methyl-N,2,6-trinitroaniline was not

availkble, but either unknown A or B in the chro-Transformation product of tetryl matograms shown in Figures 1-3 may be ascribable

Harvey et al. (1992) investigated the environmen- to this compound. On the basis of the retentiontal transformation of tetryl in soils and concluded times of the transformation products of TNB andthat the major microbiological pathway resulted in TNT relative to the unaltered compounds (Walsh etthe production of N-methylpicramide. Our recent al. 1993), peak B is most likely due to this compo-

nent.Peak C in Figures 1-3 appears to be caused by N-

H 3Cý,MNN0 2 HS3QNH methylpicramide. This peak, along with peak A,

02N N0 2 O 02 I'l NO, Ho was also observed by RP-HPLC in the extract of a0+ HN03 tet-yl-contaminated soil from Mead Nebraska (Fig.

9). Thus, it appears that N-methylpicramide is anNO2 NO2 environmental transformation product of tetryl as

To"• mehpkunmle reported by Harvey et al. (1992); however, it doesnot appear to be the major one, and it could be at-

Figure 6. Hydrolysis of tetnyl to N-methylpicramide during tributable to hydrolysis rather than microbiologicalGC-MS analysis (aftr Tamiri and Zitrin 1986). degradation (Kayser et al. 1984).

H3Q , N H H3C , NH NH2

0 2 N NO2 02N NO2 02N ,, N0 2

I ~ I IFigure 7. Chemical structures for com-pounds identifed by GC-MS analysis

NO2 NHi NO of extract of field-contaminated soiln-Opt/cramide 4-amlno-2,6-dntro-N-methylanilne 2, 4, 6-trlntroanillne containing tetryl.

6

H A , M e N 0 2 H3 C\ N H

N ON + Figure 8. Possible decomposition reaction

occurring during GC-MS analysis of ex-NH2 NH, tract ofield-contaminated soil containing

4-amino-N,,.6-tunitroanilin. 4- mio-2.-nhtro-N-methaniikne et nl.

I i I I I i Ii I

0 4 S 12 16R*e.tko Tm (mi)

Figure 9. RP-HPLC cmat m of etractfmm fld-conminated con-- tehyL

CONCLUDING REMARKS tified soils. This assumes that tetryl that is fortifiedinto a soil behaves in a similar manner to tetryl that

Results from this study indicate that refrigeration has been in contact with soils for years under fieldis inadequate as a means of stabilizing tetryl in conditions. Elsewhere, Grant et aL (1993a) observedtetryl-fortifled soils. After only 7 days of storage at a large difference in nitroaromatics' (TNT, TNB and2"C, losses of tetryl ranged from 46-99%. Losses 2,4-DNT) stability between fortified and field con-were reduced or eliminated when the fortified soils taminated soils. Analysis of tetryl-contaminatedwere frozen at -15°C. Since longer holding times soils conducted years after contamination revealswere not tested, a MHT of 7 days is recommended large concentrations of intact tetryL Whether this in-when the soil is maintained frozen. creased stability, relative to fortified soils, is from the

Several transformation products were observed difference in concentration of tetryl present, the dif-as tetryl concentrations declined. Two of these are ference in microorganisms present or their activity,thought to be 4-amino-N-methyl-N,2,6-trinitroani- or some other factor is uncertain. Additional re-line and N-methylpicramide. Because tetryl is sub- search is urgently needed to determine if holdingject to hydrolysis as well as biotransformation, the time studies, like the one discussed above, ad-mechanisms of transformation are very uncertain. equately mimic field-contaminated soil. If not, the

The above study was conducted using tetryl-for- results may be meaningless.

7

LITERATURE CITED chromatographic method for the determination ofextractable nitroaromatic and nitramine residues in

AOAC (1990) Munition residues in soil, liquid chro- soil. Journal of the AOAC, 72: 890.899.matographic method. Official First Action, Septem- Jenkins, Ta. and M.E Walsh (1994) Instability ofbet, 1990. Method 991.09, Second Supplement to the tetryl during soxhlet extraction. Jourmal of Chroma-15th Edition of Qificia Methods of Analysi. Associa- togniphy, 662. 178-184.tion of Official Analytical Chemists, pp. 78-80. Kayser E.G., N.E. Burlinson and D.H. RosenblattASTM (1986) Standard practice for estimation of (1984) Kinetics of hydrolysis and products of hy-holding time for water samples containing organic drolysis and photolysis of tetryL Silver Spring,and inorganic constituents. Method D4841-88. Phil- Maryland: Naval Surface Weapons Center, Reportadelphia: American Society for Testing and Materi- NSWC TR 84-68.al& Keirn, M.N., C.L Stratton, J.J. Mousa, J.D.ASTM (1991) Method for analysis of nitroaromatic Bonds, D.L Winegardner, H.S. Prentice, W.D.and nitramine explosives in soil by high perfor- Adams and V.J. Powell (1981) Environmental sur-mance liquid chromatography. Method D5143-%0. vey of Alabama Army Ammunition Plant. Aber-Philadelphia: American Society for Testing and Ma- deen Proving Ground, Maryland: U.S. Army Toxicterials. and Hazardous Materials Agency, USATHAMA Re-Batzer, J., S. Haverl, S. Frostman and J. Retzlaff port DRXTH-AS-CR-81104.(1982) Installation restoration survey: Joliet Army Maskarinec, M.P., C. Bayne, LH. Johnson, S.K.Ammunition Plant. Aberdeen Proving Ground, Holladay, RA. Jenkins and B.A Tomkins (1991)Maryland: U.S. Army Toxic and Hazardous Materi- Stability of explosives in environmental water andals Agency, USATHAMA Report DRXTH-AS-CR- soil samples. Oak Ridge, Tennessee: Oak Ridge Na-82143A. tional Laboratory, Report ORNL/TM-11770.Bauer, C.F, S.M. Koza and T.E Jenkins (1990) Col- McCormick, N.G., EE. Feeherry and H.S. Levinsonlaborative test results for a liquid chromatographic (1976) Microbial transformation of 2,4,6-trinitrotolu-method for the determination of explosive residues ene and other nitroaromatic compounds. Appliedin soil. Journal of the AOAC, 73:541-552. and Environmental Microbiology, 31: 949-958.EPA (1992) Nitroaromatics and nitramines by Pugh, D.L (1982) Milan Army Ammunition PlantHPLC. Second update to the 3rd Edition, SW846 contamination survey. Aberdeen Proving Ground:Method 8330. Washington, DC: U.S. Environmental U.S. Army Toxic and Hazardous Materials Agency,Protection Agency. USATHAMA Report DRXTH-FR-8213.Grant, C.L, T.E Jenkins and S.M. Golden (1993a) Spaulding, R.F. and J.W. Fulton (1988) Groundwa-Experimental assessment of analytical holding ter munition residues and nitrate near Grand Island,times for nitroaromatic and nitramine explosives in Nebraska, U.S.A. Journal of Contaminant Hydrology, 2:soil. USA Cold Regions Research and Engineering 139-153.Laboratory, Special Report 93-11. Tamiri T. and S. Zitrin (1986) Capillary column gasGrant, C.L, TZ. Jenkins and S.M. Golden (1993b) chromatography/mass spectrometry of explosives.Evaluation of pre-extraction analytical holding Journal of Energetic Materials, 4: 215-237.times for nitroaromatic and nitramine explosives in Walsh, M.E. and T.F. Jenkins (1992) Identification ofwater. USACold Regions Research and Engineering TNT transformation products in soil. USA Cold Re-Laboratory, Special Report 93-24. gions Research and Engineering Laboratory, SpecialHarvey, S.D., R.J. Fellows, JA. Campbell and D.A. Report 92-16.Cataldo (1992) Determination of the explosive 2,4,6- Walsh, M.E., TY. Jenkins, P.S. Schnitker, J.W.trnitrophenylnitrmine (tetryl) and its transforma- Elwell and M.EL Stutz (1993) Evaluation of RP-tion products in soil. Journal of Chromatography, 605: HPLC Method 8330 for characterization of sites con-227-240. taminated with residues of high explosives. USAJenkins, T.E, N.F Walsh, P.W. Schumacher, RH. Cold Regions Research and Engineering Laboratory,Miyares, CF Bauer and CL Grant (1989) Liquid CRREL Report 93-5.

8

REPORT DOCUMENTATION PAGE FeMB No. 704018

ftuvi 6WINO Ofm bmPWsNm Ow ft bwd,VAI1215bfoa1 JdssmO" A* ,ii, Sum 20. om

1. NCY USE OyM.Y(as.bb) j REPORTC 1 9 9 4 REPORT TYPE ANM DAEMS COVERED

4. TITLE AND SUBTITfLE 5, FUNDING NUMBERS

Evaluation of Pie-extraction Analytical Holding Times for Tetryl in Soil

AU NTHORS

Thomas F. Jenkins

7. PERFORMdING ORGANIZATION NAME(S) AND ADDRESS(ES) S. PERFORMING ORGANIZATIONREPORT NUMBER

U-.S Army Cold Regions Research and Engineering Laboratory72 Lyme Road Special Report 94-5Hanover, 114ew Hampshire 03755-1290

9. SPONSORINGdMONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORINGAONITORING

U.S. Army Environmental Center AEC EOTNME

Aberdeen Proving Ground, Maryland 21010-5401 SFIM-AEC-TS-CR-94028

11. SUPPLEMENTARY NOTES

12. DISTRIBUTUPAVALABLITY STATEMENT i1b. DISTRIBUTION CODE

Approved for public release; distribution is unlimited.

Available from NMI, Springfield, Virginia 22161

I&. ABSTRACT (Abtwsm, =569

A study was conducted to experimentally evaluate the maximum acceptable pie-extraction analytical holdingtimes (MHTs) for teIy in soil. Three soils fortified with tetryl at the low microgram-per-gram level were usedin the study. Subsamples of each soil were extracted with acetonitrile in an ultrasonic bath after being held for0, 1,3 and 7 days at either room temperature (2rQC, under refrigeration (2*C) or frozen (-15*C). Extracts wereanalyzed by RP-HPLC. Tetryl cocetrations In soils stored at room temperature and under refrigerationdeclined rapidly over the 7-day study period and several trans orat products accumulated. After 7 days ofstorage at 2C, tetryl concentrations were reduced by46, 97 and 99% in the three soils studied. When the soils werefrozenI, there were no statistically Significant analyte losses over the 7-day study period (95% confidence level).On the basis of the results of these experiments, the recommended MHT for soils containing tetryl is 7 days if keptfrozen. Longer holding tinme may be possible, but they were not investigated, here. Refrigeration is inadequateto prevent significant transformation of tetryl in soil samples being held for analysis. A question regarding theability to use analyte-fortified soil to mimic field-contaminated soils in holding time studies is raised.

14. SUBJECT TERMS 1I& NUMBE~ff PAGES

Exposves Munitions Tetryl W6 PRICE CODELaboator andses Pollution

17. SECURITY CLASSIFICATION I&. SECURITY CLASSIFICATION I19. SECURITY CLASSFICATION 20. LIMITATION OF ABSTRACTOP REPORT IOF THIS PAGE OFABSTRACT

UNCLASSFEMD j UNCLASSIFIED I UNCLASSFEUD ULNSN 7540.O-SM-280 Stmiwd Form M9 (Rwv 2.9)

PMeUMNbydAND VA Z30-162WI02