Appendix D
Results from Technical Risk Reduction Program Activity 2a, Phase II, for GB and Activity 11 for VX

TRRP 2a, PHASE II, FOR GB ANALYSIS

The performance of the new analytical method was adequate to ensure that measured GB concentrations in the hydrolysate were low enough for secondary treatment using supercritical water oxidation (SCWO). Method detection limit (MDL) values in hydrolysate were 2.2 µg/L (2.2 ppb) with 68 percent recovery and were calculated in accordance with standard U.S. Environmental Protection Agency (EPA) methods (40 CFR Part 136, Appendix B). This value is well below the release criteria of 75 ppb for GB in the hydrolysate. A more significant performance parameter is the target action limit (TAL), which is the concentration for which 95 percent of the measurements will be below the release criteria (Malloy et al., 2007). In an analysis of GB performed on hydrolysate generated from two batch reactor studies conducted at Battelle, the TAL values were calculated at 57 ppb and 52 ppb.

The study also showed that the destruction method was effective for destruction of GB in a number of other matrices, including the diisopropylurea crystals that form from the diisopropyl carbodiimide during storage.

A series of batch reactor studies were conducted to validate the Blue Grass Chemical Agent Destruction Pilot Plant (BGCAPP) GB neutralization process (Malloy et al., 2007). Three different GB batches were used that had concentrations ranging from 75 percent to 90 percent, and diisopropylmethyl phosphonate and the stabilizer compounds made up the remainder of the material. The batch tests used 6 percent sodium hydroxide; the pH at the end of the batch runs was ~12.

At the conclusion of the hydrolysis experiments, an organic layer was present. The composition of this layer (present in some hydrolysates) was analyzed not by Battelle but by the Army’s Edgewood Chemical and Biological Center, which reported that the layer was largely tributylamine and some additional compounds that are manufacturing impurities in the tributylamine that was used by the Army to stabilize the GB. In all cases, the aqueous phase constituted >98 percent of the total hydrolysate volume, and the percentage constituted by the organic phase was very small. Methylene chloride extraction of the hydrolysates followed by gas chromatography and mass spectrometry (GC/MS) showed tributylamine, diisopropylmethyl phosphonate, dibutyl acetamide, and—in the case of the diisopropyl carbodiimide stabilized material—diisopropylurea and diisopropylnitrosamine. Residual GB was not mentioned.

Method application tests of hydrolysate produced on the bench showed that in 9 of 10 batches, GB destruction exceeded 99.9999 percent with greater than 95 percent confidence. In one batch, residual GB was detected at concentrations ranging from 61 to 74 ppb. This showed that the method was effective for analyzing the hydrolysate.

An issue of significant concern was whether GB could be analyzed in the solids that are found in the munitions. Crystals that tend to form in the munitions have been shown to be diisopropylurea, which is derived from diisopropyl carbodiimide (Rosso et al., 2005). The TRRP study showed that the analytical method worked well for detecting GB in the diisopropylurea crystals, and that GB associated with the diisopropylurea crystals was hydrolyzed (Malloy et al., 2007). For diisopropyl urea crystals that had been washed with caustic, residual GB was detected at high concentrations, on the order of 70 to 450 ppm. When the diisopropylurea crystals were mixed with GB/diisopropyl carbodiimide and then added to the reactor, no GB was detected.

The analytical method also worked well for measuring GB in the energetics neutralization hydrolysate. BGCAPP-104B had an MDL of 13 ppb, based on an analysis of spiked enegetics hydrolysates from the neutralization reactor.

The TRRP study also showed that GB could be reformed in the SCWO feed, but only when pH was lowered to acidic values. At longer reaction times, however, the GB concentration begins decreasing again. This is explained in terms of GB re-formation upon acidification, followed by acidic hydrolysis. GB re-formation without pH adjustment



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appendix d results from Technical risk reduction Program activity 2a, Phase ii, for GB and activity 11 for VX TrrP 2a, Phase ii, For GB aNalYsis lize the GB. In all cases, the aqueous phase constituted >98 percent of the total hydrolysate volume, and the percentage constituted by the organic phase was very small. Methylene The performance of the new analytical method was chloride extraction of the hydrolysates followed by gas adequate to ensure that measured GB concentrations in the chromatography and mass spectrometry (GC/MS) showed hydrolysate were low enough for secondary treatment using tributylamine, diisopropylmethyl phosphonate, dibutyl supercritical water oxidation (SCWO). Method detection limit (MDL) values in hydrolysate were 2.2 µg/L (2.2 ppb) acetamide, andin the case of the diisopropyl carbodiimide stabilized materialdiisopropylurea and diisopropylnitros- with 68 percent recovery and were calculated in accordance amine. Residual GB was not mentioned. with standard U.S. Environmental Protection Agency (EPA) Method application tests of hydrolysate produced on methods (40 CFR Part 136, Appendix B). This value is well the bench showed that in 9 of 10 batches, GB destruction below the release criteria of 75 ppb for GB in the hydroly- exceeded 99.9999 percent with greater than 95 percent sate. A more significant performance parameter is the target confidence. In one batch, residual GB was detected at con- action limit (TAL), which is the concentration for which 95 centrations ranging from 61 to 74 ppb. This showed that the percent of the measurements will be below the release cri- method was effective for analyzing the hydrolysate. teria (Malloy et al., 2007). In an analysis of GB performed An issue of significant concern was whether GB could on hydrolysate generated from two batch reactor studies be analyzed in the solids that are found in the munitions. conducted at Battelle, the TAL values were calculated at 57 Crystals that tend to form in the munitions have been shown ppb and 52 ppb. to be diisopropylurea, which is derived from diisopropyl car- The study also showed that the destruction method was bodiimide (Rosso et al., 2005). The TRRP study showed that effective for destruction of GB in a number of other matrices, the analytical method worked well for detecting GB in the including the diisopropylurea crystals that form from the diisopropylurea crystals, and that GB associated with the di- diisopropyl carbodiimide during storage. isopropylurea crystals was hydrolyzed (Malloy et al., 2007). A series of batch reactor studies were conducted to For diisopropyl urea crystals that had been washed with validate the Blue Grass Chemical Agent Destruction Pilot caustic, residual GB was detected at high concentrations, Plant (BGCAPP) GB neutralization process (Malloy et al., on the order of 70 to 450 ppm. When the diisopropylurea 2007). Three different GB batches were used that had con- crystals were mixed with GB/diisopropyl carbodiimide and centrations ranging from 75 percent to 90 percent, and di- then added to the reactor, no GB was detected. isopropylmethyl phosphonate and the stabilizer compounds The analytical method also worked well for measuring made up the remainder of the material. The batch tests used GB in the energetics neutralization hydrolysate. BGCAPP- 6 percent sodium hydroxide; the pH at the end of the batch 104B had an MDL of 13 ppb, based on an analysis of spiked runs was ~12. enegetics hydrolysates from the neutralization reactor. At the conclusion of the hydrolysis experiments, an or- The TRRP study also showed that GB could be re- ganic layer was present. The composition of this layer (pres- formed in the SCWO feed, but only when pH was lowered ent in some hydrolysates) was analyzed not by Battelle but to acidic values. At longer reaction times, however, the GB by the Army’s Edgewood Chemical and Biological Center, concentration begins decreasing again. This is explained in which reported that the layer was largely tributylamine and terms of GB re-formation upon acidification, followed by some additional compounds that are manufacturing impuri- acidic hydrolysis. GB re-formation without pH adjustment ties in the tributylamine that was used by the Army to stabi- 

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 reView Of SeCONdAry wASTe diSPOSAL PLANNiNg was evaluated by analysis of hydrolysate from one of the 1 g/L (1,000 ppm), which must be demonstrated for transfer method application tests 1 month after the hydrolysis was of the hydrolysate from the ANR to the SCWO. However, performed. One of the reanalyses measured GB at 5.7 ppb, the method is temperamental in that the baseline detector which suggested that slow re-formation might be taking response is substantial and varying, retention times vary, place. peak shapes are variable, and the detector is nonspecific. The TRRP also evaluated the performance of the GB Nevertheless, analysis of simulated ANR hydrolysate spiked analytical method for measuring agent in SCWO and reverse with 400 ppb EA2192 resulted in detection with good P&A osmosis (RO) effluents. Analysis of GB in simulated SCWO in analysis of hydrolysate derived from two VX batches. effluent using method BGCAPP-104b reproducibly mea- Re-formation of VX in the hydrolysate was a concern sured GB at concentrations below 5 ppb, with a calculated based on reactions of hydrolysis products catalyzed by sta- MDL of 0.63 ppb. Similar results were achieved for the RO bilizers (Brickhouse et al., 1998). This is considered more rejectate. These values are well below the target value of 20 likely to occur as the pH decreases from the high values (>12) ppb. When blended hydrolysate was evaluated, an MDL of found in the unmodified hydrolysate. As in previous cases, 1.7 ppb was measured. analysis was complicated by analytical difficulties stemming from the tendency of VX to protonate at pH < 12, which re- sults in inefficient extraction. Therefore, BGCAPP-204 was resUlTs From TrrP 11 For VX aNalYsis modified by raising the pH of the extract above 7 to drive the A TRRP was conducted to evaluate the analytical VX into the organic phase. Using this analytical approach, methods for measuring VX in the matrices anticipated at no VX was detected in the hydrolysate for up to 60 days. BGCAPP and the effectiveness of agent destruction. A However, because the recoveries were low, the possibility of precision and accuracy (P&A) study of the refined method re-formation in an acidified hydrolysate could not be com- (referred to as BGCAPP-204) was performed by conducting pletely discounted. Reanalysis using a liquid chromatography triplicate analyses on a hydrolysate spiked at four different method also failed to detect VX in the hydrolysate. However, levels. The P&A study produced a detection limit of 4 µg/L the TRRP report (Dejarme and Lecakes, 2008) stated that (ppb) and a limit of quantification (LOQ) of 10 ppb for VX. the study did not adequately represent process conditions The TAL, which accounts for the method imprecision, was planned for BGCAPP, and the authors recommended that a measured at 107 ppb, a value that is well below the 160 ppb more detailed re-formation study be performed. acceptance criteria of the SCWO. When the method was ap- Residual VX and EA2192 were also evaluated in the plied to hydrolysates from the three different VX batches, de- SCWO effluent and in the RO rejectate. To make the mea- tection limits were similarly low, ranging from 9 to 28 µg/L. surements, the analytical method for VX needed to be modi- A modified 12-sample P&A study of hydrolysates from four fied, because the effluents were slightly acidic, which im- different sources of VX showed an average detection limit of pedes extraction of VX. These modifications were effective, 4 ppb, an LOQ of 8 ppb, and a TAL of 125 ppb. When the resulting in VX MDL values of 14 and 12 ppb for the SCWO P&A study was extended to 48 samples over 4 days, the mean and RO effluents, respectively. For EA2192, MDL values of MDL was 16 ppb, the LOQ was 35 ppb, and the TAL was 290 and 470 ppb were achieved for the SCWO and RO ef- 107 ppb. A final test of analytical efficacy involved analysis fluents. The SCWO VX method is called BGCAPP-604, and of simulated agent neutralization reactor (ANR) hydrolysate the method modified for EA2192 is BGCAPP-704B. spiked with 80 ppb VX. In this study, VX was detected with Members of the public expressed concern about the good P&A in hydrolysate samples derived from two separate different chemistries of the two layers that emerge in VX VX batches. These studies indicated that the instrumental hydrolysate. Specifically, there is uncertainty over whether method used for clearing the VX hydrolysate for further VX could be present in the organic layer. In examining the SCWO treatment is adequate. hydrolysates from the four batches of VX, one of the four For instrumental analysis of EA2192, a liquid chro- had a layer that appeared to account for several percent matography method was developed that utilized either a of the total volume, while each of the other three had an diode array detector or an ultraviolet detector. Initial studies organic layer that accounted for a much lower fraction. In were conducted using liquid chromatography/electrospray TRRP activity 11, GC/MS analysis of the upper organic ionization/MS/MS, with the objective of confirming peak layer showed that it consists mainly of the disulfide, bis[2- identification, which cannot be done with confidence using (diisopropylamino)ethyl] disulfide, with lesser amounts of an ultraviolet detector alone. Once the peaks were identi- the thiolamine and related thiols, sulfides, and conjugates of fied in the liquid chromatogram, studies were conducted to those molecules with the stabilizer diisopropyl carbodiimide. evaluate the performance of the diode array detector method VX was not detected in this analysis; however, the MDL for (BGCAPP-304B), which produced detection limits averag- this approach is not known. ing 61 ppm. When the ultraviolet light detector was used, The TRRP activity 11 report (Dejarme and Lecakes, detection limits were calculated that ranged from 18 to 106 2008) concluded with remarks that while the BGCAPP VX ppm. These levels are much lower than the clearance level of clearing method was working, it should be tested to evaluate

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 APPeNdiX d its robustness in an actual plant neutralization environment. Dejarme, L., and G.D. Lecakes. 2008. Bench-Scale Evaluation of VX Hydrolysis, TRRP #11, Test Report, Rev. 0. Aberdeen Proving Ground, Furthermore, extensive testing to characterize the potential for Md.: Program Manager for Assembled Chemical Weapons Alterna- VX re-formation was beyond the scope of TRRP activity 11. tives. Malloy IV, T.A., L. Dejarme, C. Fricker, J. Guinan, G.D. Lecakes, and A. Shaffer. 2007. Bench-Scale Evaluation of GB Hydrolysis, TRRP #02a reFereNces Phase II, Test Report, Rev. 0. Aberdeen Proving Ground, Md.: Program Manager for Assembled Chemical Weapons Alternatives. Brickhouse, M.D., B. Williams, D. McGarvey, H.D. Durst, and R.J. Rosso, T.E., P.L. Abercrombie, A.B. Butrow, G. Hondrogiannis, J.M. O’Connor. 1998. Coupling reactions between dialkylcarbodiimides, Lochner, J.J. Loss, R.J. Malecki, J.M. Meuser, D.K. Rohrbaugh, and phosphonates, and thiols. Pp. 617-623 in Proceedings of the ERDEC Y.-C. Yang. 2005. Characterization of Solid and Liquid GB Samples Scientific Conference on Chemical and Biological Defense Research. Collected from M55 Rockets Processed at Anniston Chemical Agent Report number ECBC-SP-004. Aberdeen Proving Ground, Md.: Edge- Disposal Facility (ANCDF). Aberdeen Proving Ground, Md.: Edgewood wood Chemical and Biological Center, U.S. Army Soldier and Biologi- Chemical and Biological Center. cal Chemical Command.