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TECHNICAL REPORTS

Organic Compounds in the Environment

Contribution of Hydrolysis in the Abiotic Attenuation of RDX and HMX in Coastal Waters

Biotechnology Research Inst., National Research Council of Canada, 6100 Royalmount Avenue, Montréal, Québec, Canada H4P 2R2

^* Corresponding author (jalal.hawari{at}cnrc-nrc.gc.ca).

Received for publication August 23, 2007.

	ABSTRACT

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Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E_a, ln A, k₂) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30–50°C, pH 10–12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60°C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO₂^–, O₂NNHCH₂NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10°C would respectively take 112 ± 10 and 2408 ± 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.

Abbreviations: DW, deionized water • E_a, activation energy • k₁, pseudo-first order rate constant • k₂, second order rate constant • ln A, Arrhenius factor • UXOs, unexploded ordnances

	INTRODUCTION

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THE sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds from these UXOs may occur through mechanical stress, corrosion, or low-order remedial detonations, thus constituting a major source of contamination of marine and estuarine sediments (Darrach et al., 1998). After migrating from the source into the overlying waters, the released chemicals can accumulate in aquatic organisms and cause adverse ecological effects (Yinon, 1990; Robidoux et al., 2000).

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are two widely-used cyclic nitramine explosives. They have been shown to be toxic to various terrestrial and aquatic organisms (Yinon, 1990; Talmage et al., 1999; Robidoux et al., 2000; Rosen and Lotufo, 2006). A more accurate assessment of the natural attenuation of the two nitramines in marine media would thus contribute to the understanding of the long-term fate of these chemicals in the sea as well as the environmental impact of their potential leaking from UXOs.

Various abiotic (hydrolysis, photolysis, oxidation, reduction) and biotic (aerobic or anaerobic) reactions can be responsible for the transformation of chemicals once they have been released in the environment. Based on previous studies on alkaline hydrolysis of RDX and HMX (Hoffsommer et al., 1977; Heilmann et al., 1996, Balakrishnan et al., 2003), at the pH generally encountered in marine environments (8.0), one can expect a slow but significant removal of those chemicals due to alkaline hydrolysis.

Several researchers have investigated the kinetics of the alkaline hydrolysis of RDX and HMX (Epstein and Winkler, 1951; Hoffsommer et al., 1977; Heilmann et al., 1996; Hwang et al., 2006). The reaction was shown to be a second-order reaction with respect to RDX (or HMX) and OH^– concentrations. Hoffsommer et al. (1977) and Heilmann et al. (1996) identified NO₂^–, NH₃, N₂O, HCOO^–, and HCHO as the main products of hydrolysis at pH 11 to 13, but more recently we demonstrated that the pH employed was a determining factor for the stoichiometry of the reaction with milder pHs (pH 10) favoring the formation and stability of 4-nitro-2,4-diazabutanal (NDAB), O₂NNHCH₂NHCHO, in addition to NO₂^–, N₂O, and HCHO (Balakrishnan et al., 2003).

The present study was initiated first to determine the contribution of alkaline hydrolysis in the transformation of RDX and HMX in coastal waters and second to provide rate constants that are needed to support predictive models of overall explosives degradation in coastal environments. Kinetic parameters of alkaline hydrolysis (k₂, Arrhenius factor (ln A), and activation energy (E_a)) were measured in deionized water at various pHs and temperatures, and used to predict the alkaline hydrolysis of RDX and HMX in coastal samples at 50 and 60°C, after verifying the effect of NaCl on the kinetics. Predictions were then compared with experimental measurements for abiotic degradation of RDX and HMX in natural coastal waters to evaluate the role of alkaline hydrolysis in the in situ natural attenuation of nitramines.

	Materials and Methods

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Chemicals
1,3,5-Trinitro-1,3,5-triazine (RDX, purity > 99%), and 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX, purity > 99%) were provided by Defense Research and Development Canada (Valcartier, QC). 4-Nitro-2,4-diazabutanal (NDAB) was purchased from SRI (Menlo Park, CA). Acetonitrile (CH₃CN, HPLC grade) was from Fisher (Nepean, ON) and deionized water (DW) was obtained with a Milli-Q^UV plus (Millipore, Mississauga, ON) system.

Coastal Waters Collection and Characterization
Three coastal water samples of different salinities (Marine (M); Estuarine (EST); and Freshwater (F)) were collected in June 2006 near the mouth of the Delaware Bay. After collection, samples were shipped on ice to BRI and stored at 4°C until use. The pH of each sample was measured at 21°C using an Accumet AB15 pH meter (Fisher, Nepean, ON) equipped with a glass electrode with a single junction and Ag/AgCl reference. The electrode was calibrated before measurements using buffer solutions (pH 4.00, 7.00, and 10.00) from VWR (Montreal, QC). Three replicates were measured for each sample on three different days. Anions were analyzed in samples M, EST, and F by ion chromatography as described previously (Balakrishnan et al., 2004). Metal analyses were performed by Bodycote Testing Group (Pointe-Claire, QC) using inductively coupled plasma mass spectrometry (ICP–MS). Relevant physicochemical properties of the three waters are summarized in Table 1 .

Abiotic Degradation in Natural Coastal Waters
Experiments were performed in duplicate under static conditions, away from light, in an Isotemp Standard Lab Incubator (Fisher Scientific, Nepean, ON) at 50 and 60°C. Solutions of RDX (10 mg L^–1) or HMX (3 mg L^–1) were prepared by stirring the desired amount of solid explosive in natural waters (M, EST, and F) at room temperature. After 96 h, the solutions were filtered under sterile conditions through a 0.22-µm GP Express PLUS membrane from Millipore (Mississauga, ON) and placed in the incubator, which corresponded to the start of the experiment (t₀). At specific times (t), samples were withdrawn and analyzed for RDX or HMX, and their transformation products as described below.

Chemical Analysis
RDX and HMX were analyzed by HPLC using a Supelcosil LC-CN column (Supelco, Oakville, ON) as described previously (Monteil-Rivera et al., 2005). Formaldehyde (HCHO) was analyzed after derivatization with 2,4-pentanedione as described by Fournier et al. (2002). Nitrite was first reduced to nitric oxide by KI (0.1 mol L^–1) in the presence of sulfuric acid (0.1 mol L^–1) before detection with an Apollo 4000 Free Radical Analyzer (World Precision Instruments, Sarasota, FL). Calibration was performed by adding different amounts of a standard potassium nitrite solution to the iodide solution and measuring the NO by monitoring the current change. 4-Nitro-2,4-diazabutanal (NDAB) was analyzed by HPLC using an ICSep ICE-ION-310 column (Transgenomic, San Jose, CA) as described previously (Fournier et al., 2004).

	Results and Discussion

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Alkaline Hydrolysis of RDX and HMX in Deionized Water
Kinetic measurements were performed for the alkaline hydrolysis of RDX and HMX in deionized water at temperatures ranging from 30 to 50°C and with NaOH concentrations of 10^–4, 5 x 10^–4, and 10^–3 mol L^–1 for RDX and 10^–3, 5 x 10^–3, and 10^–2 mol L^–1 for HMX. Figure 1 shows examples of first-order plots obtained for RDX (with 10^–3 mol L^–1 NaOH) and HMX (with 10^–2 mol L^–1 NaOH). Similar linear plots were obtained for all conditions investigated. However when using NaOH at 10^–4 mol L^–1, data collected after more than 24 h started to deviate from linearity, likely due to the consumption of hydroxide ions by both RDX and dissolved CO₂. For instance, a drop of 0.6 pH units was measured after 3 d at 45°C. For this reason, only data collected within the first 12 h were considered for all experiments performed with 10^–4 mol L^–1 NaOH. For each concentration of OH^– investigated, pseudo first-order rate constants, k₁, were obtained from linear regressions of the experimental first-order plots. The resulting k₁ constants varied linearly with hydroxide concentration (Fig. 2 ) thus allowing the determination of second-order rate constants, k₂ ( = k₁/[OH^–]), from linear regressions of k₁ vs. [OH^–] plots. All pseudo first-order and second-order rate constants are reported in Table 2 . As seen by comparing the second-order constants, k₂, for RDX and HMX, HMX hydrolyzed approximately 10 times slower than RDX (Table 2), in accordance with the higher reactivity of RDX toward hydroxide previously reported (Heilmann et al., 1996; Balakrishnan et al., 2003).

View larger version (12K): [in this window] [in a new window]   Fig. 1. First-order plots for (a) RDX (45 µmol L–1) and (b) HMX (10 µmol L–1) alkaline hydrolysis (symbols are mean value and error bars are standard errors of triplicate experiments (n = 3)).

View larger version (13K): [in this window] [in a new window]   Fig. 2. Pseudo-first-order constants for RDX and HMX alkaline hydrolysis as a function of hydroxide concentration.

[1]

where A is the Arrhenius factor (in L mol^–1 h^–1, if k₂ is expressed in L mol^–1 h^–1); E_a is the activation energy (J mol^–1); R is the gas constant (8.314 J K^–1 mol^–1); and T is the absolute temperature (K). Arrhenius plot determined in the present study for HMX (Table 2) was in excellent agreement with the plot previously reported by Heilmann et al. (1996) despite the different temperature ranges investigated in the two studies. For RDX, however, Heilmann et al. (1996) generally observed higher hydrolysis rates than us. The study conducted by Heilmann and coworkers covered a range of higher temperatures (50–80°C) while our study was focused on a temperature range (30–50°C) closer to the ambient conditions expected to prevail in natural environments. It is possible that the use of higher temperatures by Heilmann and coworkers resulted in the removal of the more reactive nitramine, RDX, by other degradative reactions such as thermal degradation. For example, we observed a 5% loss of RDX in a solution containing the nitramine in deionized water (pH 5.5) that was kept at 80°C for 1 h, when alkaline hydrolysis was calculated to be negligible under these conditions ([OH^–] = 3.16 x 10^–9 mol L^–1; k₁ (80°C) = 1.821 x 10^–5 h^–1; 5% loss in 117 d).

The applicability of data obtained in deionized water to predict transformation of nitramines in saline media was verified by conducting hydrolysis of RDX or HMX with NaOH (10^–3 mol L^–1 or 10^–2 mol L^–1, respectively) at 40°C in the presence of 3% (w/w) NaCl. The presence of sodium chloride did not affect significantly the kinetics of hydrolysis, thus suggesting the possible use of kinetic parameters established from experiments conducted in deionized water to predict hydrolysis kinetics in brackish or marine water.

Abiotic Degradation of RDX and HMX in Natural Coastal Waters
Kinetics Measurements
According to the kinetic parameters determined in the section "Alkaline Hydrolysis of RDX and HMX in Deionized Water," alkaline hydrolysis of RDX and HMX at 20°C would require concentrations of free OH^– at least equal to 10^–4 and 10^–3 mol L^–1, respectively, to be measurable in the laboratory at a reasonable time scale (days to months). Reaching these concentrations of free hydroxide in the collected coastal samples (pH8, Table 1) would imply adding large amounts of base, which would result in the precipitation of calcium, magnesium, and strontium hydroxide in the marine and estuarine samples (see Table 1 for cation content). To fasten the reaction without affecting the composition of the natural waters, it was decided to increase the temperature of the reaction medium.

The three sterilized natural waters (M, EST, and F) were therefore used to measure kinetics of abiotic degradation for RDX and HMX, away from light and under static conditions at 50 and 60°C. Disappearance of RDX and HMX followed first-order kinetics in the three sterile waters and the first-order constants, k₁, obtained through the linear regression analysis of the plots of ln(C_t/C₀) vs. time are given in Table 3 together with the r² values.

Prediction of Rates of Alkaline Hydrolysis in Coastal Waters
Prediction of alkaline hydrolysis of RDX and HMX in the three natural coastal samples required knowing the concentration of hydroxide in each of the samples. Activity coefficients of H⁺ (_H+) and OH^– (_OH-) were thus first determined in samples F, EST, and M using the Debye-Hückel limiting law (Eq. [2]) for freshwater (I < 0.005 mol kg^–1) and the Millero ion pairing model (Millero and Schreiber, 1982) for the two other media. The latter was applied using the program called "Acid-Base" (Buzko et al., 2004) developed by the IUPAC (2000) with temperature equal to 21°C and salinities of 15,740 and 31,685 mg L^–1 for samples EST and M, respectively.

[2]

where A is a constant unique to the solvent and temperature (A = 0.512 at 25°C for water), z_i is the charge on the species i, and I is the molal ionic strength of the solution.

Hydroxide concentrations were then determined in the three samples using the pH values measured at 21°C (see Table 1) and the general pHmetry Eq. [3], [4], and [5]. The resulting values of _H+, _OH-, and [OH^–] are reported in Table 4 for samples M, EST, and F. Concentration of hydroxide followed the order M > EST > F, in agreement with the order of rates measured for RDX abiotic degradation (see section "Kinetics Measurements").

[3]

[4]

[5]

where () represent activities and [] represent concentrations, _i is the activity coefficient of the species i, Kw is the water ionic product (10^–14 at ionic strength I = 0 and 25°C), and Kw* is the apparent ionic product at a given ionic strength.

[6]

[7]

[8]

with [OH^–] = , as deduced from the pH measured at 21°C in the natural samples, and ln A and Ea which are given in Table 2. We should note here that although low (and even lower than the concentrations of nitramines introduced in the present experiments), the concentrations of free OH^– were found unchanged at the end of the reactions. The constant pH values observed in samples M, EST, and F were likely due to the presence of numerous hydroxylated and carbonated soluble complexes, which acted as pH buffer in the media. In an open natural system, the pH would also remain constant.

The predictions of disappearance of the two nitramines in the three coastal water samples assuming alkaline hydrolysis as the only degradation process are presented in Fig. 3 and 4 together with the abiotic degradation measured experimentally. Overall, hydrolysis rates fell in the same range as the disappearance rates measured abiotically in the absence of light, thus suggesting that alkaline hydrolysis was a predominant degradation process. Experimental rates for RDX degradation, however, tended to be higher than the predicted rates of alkaline hydrolysis suggesting that additional processes may have contributed, in lesser extent, to the disappearance of RDX in natural samples. Whether these degradative processes were of metallic or organic origin remains unclear. The agreement between predictions and experiments was better for HMX than for RDX, and was better at 50°C than at 60°C. Data collected at 60°C with RDX clearly showed a deviation from the pseudo first-order kinetics (Fig. 3) indicating the occurrence of an additional process. Thermal decomposition has probably occurred at this temperature as supported by the loss of RDX at 60°C in the control (dionized water (DW), pH 5.5, 13% loss in 37 d) where conditions were not met to allow alkaline hydrolysis to take place ([OH^–] = 3.16 10^–9 mol L^–1; k₁ (60°C) = 2.512 10^–6 h^–1; 1% loss in 166 d).

View larger version (38K): [in this window] [in a new window]   Fig. 3. Comparison between abiotic degradation in natural samples (M = Marine, EST = Estuarine, F = Freshwater; mean value ± standard error (n = 2)) and predictions of disappearance based on a hydrolysis process for RDX.

View larger version (36K): [in this window] [in a new window]   Fig. 4. Comparison between abiotic degradation in natural samples (mean value ± standard error (n = 2)) and predictions of disappearance based on a hydrolysis process for HMX.

View larger version (37K): [in this window] [in a new window]   Fig. 5. Time courses for abiotic degradation of RDX (left column) and HMX (right column) in coastal samples at 50°C (symbols are mean value and error bars are standard error of duplicate experiments (n = 2)).

	Environmental Significance and Conclusion

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Using the present kinetics data in combination with kinetics data of other transformation processes, especially those of binding to sediments, biodegradation, photolysis, and reaction with metals, should allow prediction of the overall in situ natural attenuation of nitramines in coastal environments.

	ACKNOWLEDGMENTS

 
Dr. Michael T. Montgomery from Naval Research Lab., Washington, DC, is thanked for providing the coastal water samples. Drs. Sonia Thiboutot and Guy Ampleman from DRDC Valcartier, DND Canada, are thanked for providing chemicals. Stéphane Deschamps, Alain Corriveau, and Chantale Beaulieu are thanked for technical assistance. Funding was provided by U.S. DoD/DoE/EPA Strategic Environmental Research and Development Program (SERDP ER 1431).

	NOTES

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All rights reserved. No part of this periodical may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher.

	REFERENCES

TOP NOTES ABSTRACT INTRODUCTION Materials and Methods Results and Discussion Environmental Significance and... REFERENCES

 

• Balakrishnan, V.K., A. Halasz, and J. Hawari. 2003. Alkaline hydrolysis of the cyclic nitramine explosives RDX, HMX, and CL-20: New insights into degradation pathways obtained by the observation of novel intermediates. Environ. Sci. Technol. 37 :1838–1843.[Medline]
• Balakrishnan, V.K., F. Monteil-Rivera, A. Halasz, A. Corbeanu, and J. Hawari. 2004. Decomposition of the polycyclic nitramine explosive, CL-20, by Fe⁰. Environ. Sci. Technol. 38 :6861–6866.[Medline]
• Buzko, V., I. Sukhno, and A. Polushin. 2004. Calculation of thermodynamic properties of aqueous electrolyte solutions: Electrolyte activity coefficients, osmotic coefficients and water activity using Pitzer-Mayorga and Lin-Tseng-Lee models and the ionic activity coefficients in electrolyte solutions, ionic activity coefficients in seawater using the Millero-Pitzer model. Version 2.0. IUPAC, Research Triangle Park, NC.
• Darrach, M.R., A. Chutjian, and G.A. Plett. 1998. Trace explosives signatures from World War II unexploded undersea ordnance. Environ. Sci. Technol. 32 :1354–1358.
• Epstein, S., and C.A. Winkler. 1951. Studies on RDX and related compounds: VI. The homogeneous hydrolysis of cyclotrimethylenetrinitramine (RDX) and cyclotetramethylenetetranitramine (HMX) in aqueous acetone, and its application to analysis of HMX in RDX (B). Can. J. Chem. 29 :731–733.
• Fournier, D., A. Halasz, J. Spain, P. Fiurasek, and J. Hawari. 2002. Determination of key metabolites during biodegradation of hexahydro-1,3,5-trinitro-1,3,5-triazine with Rhodococcus sp. Strain DN22. Appl. Environ. Microbiol. 68 :166–172.[Abstract/Free Full Text]
• Fournier, D., A. Halasz, J. Spain, R.J. Spanggord, J.C. Bottaro, and J. Hawari. 2004. Biodegradation of the hexahydro-1,3,5-trinitro-1,3,5-triazine ring cleavage product 4-nitro-2,4-diazabutanal by Phanerochaete chrysosporium. Appl. Environ. Microbiol. 70 :1123–1128.[Abstract/Free Full Text]
• Halasz, A., J. Spain, L. Paquet, C. Beaulieu, and J. Hawari. 2002. Insights into the formation and degradation mechanisms of methylenedinitramine during the incubation of RDX with anaerobic sludge. Environ. Sci. Technol. 36 :633–638.[Medline]
• Heilmann, H.M., U. Wiesmann, and M.K. Stenstrom. 1996. Kinetics of the alkaline hydrolysis of high explosives RDX and HMX in aqueous solution and adsorbed to activated carbon. Environ. Sci. Technol. 30 :1468–1492.
• Hoffsommer, J.C., D.A. Kubose, and D.J. Glover. 1977. Kinetic isotope effects and intermediate formation for the aqueous alkaline homogeneous hydrolysis of 1,3,5-triaza-1,3,5-trinitrocyclohexane (RDX). J. Phys. Chem. 81 :380–385.[CrossRef][Web of Science]
• Hwang, S., D.R. Felt, E.J. Bouwer, M.C. Brooks, S.L. Larson, and J.L. Davis. 2006. Remediation of RDX-contaminated water using alkaline hydrolysis. J. Environ. Eng. 132 :256–262.[CrossRef]
• IUPAC. 2000. Ionic strength corrections for stability constants. IUPAC, Research Triangle Park, NC. Available at http://www.iupac.org/projects/2000/2000-003-1-500.html (verified 21 Feb. 2008).
• Millero, F.J., and D.R. Schreiber. 1982. Use of the ion pairing model to estimate activity coefficients of the ionic components of natural waters. Am. J. Sci. 282 :1508–1540.[Abstract/Free Full Text]
• Monteil-Rivera, F., L. Paquet, A. Halasz, M.T. Montgomery, and J. Hawari. 2005. Reduction of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine by zerovalent iron: Product distribution. Environ. Sci. Technol. 39 :9725–9731.[Medline]
• Robidoux, P.Y., C. Svendsen, J. Caumartin, J. Hawari, G. Ampleman, S. Thiboutot, J.M. Weeks, and G.I. Sunahara. 2000. Chronic toxicity of energetic compounds in soil determined using the earthworm (Eisenia Andrei) reproduction test. Environ. Toxicol. Chem. 19 :1764–1773.[CrossRef][Web of Science]
• Rosen, G., and G.R. Lotufo. 2006. Toxicity and fate of two munitions constituents in spiked sediment exposures with the marine amphipod Eohaustorius estuaries. Environ. Toxicol. Chem. 24 :2887–2897.[CrossRef][Web of Science]
• Talmage, S.S., D.M. Opresko, C.J. Maxwell, C.J.E. Welsh, F.M. Cretella, P.H. Reno, and F.B. Daniel. 1999. Nitroaromatic munition compounds: Environmental effects and screening values. Rev. Environ. Contam. Toxicol. 161 :1–156.[Medline]
• Yinon, J. 1990. Toxicity and metabolism of explosives. CRC Press, Boca Raton, FL.

This Article Abstract Figures Only Full Text (PDF) Free Alert me when this article is cited Alert me if a correction is posted Services Similar articles in this journal Alert me to new issues of the journal Download to citation manager Citing Articles Citing Articles via Google Scholar Google Scholar Articles by Monteil-Rivera, F. Articles by Hawari, J. Search for Related Content PubMed Articles by Monteil-Rivera, F. Articles by Hawari, J. Agricola Articles by Monteil-Rivera, F. Articles by Hawari, J. Related Collections Other Contaminants Organic Compounds