Movement of TNT and RDX from composition B detonation residues in solution and sediment during runoff.

Energetics used in military exercises can potentially contaminate ground and surface waters. This study was conducted to evaluate the movement of Composition B, a formulation that includes TNT (2,4,6-trinitrotoluene), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), in runoff. Mechanisms of transport we examined include movement of energetics dissolved in runoff, as particles and adsorbed to suspended sediment, and in infiltration. Rainfall simulations were conducted under controlled conditions with two rainfall rates (approximately 30 and 50 mm h-1), two soils with different infiltration capacities, and four energetic particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). Particles remaining on the soil surface after rainfall were measured as well as energetics dissolved in runoff, in suspended sediment, and in infiltration. Greater concentrations of TNT than RDX and HMX were found dissolved in runoff due to its higher solubility and dissolution rates. We also found that particle transport in runoff increased with decrease in particle size. Smaller particle sizes also led to greater transport dissolved in solution. Relationships were found relating runoff and sediment yield to the transport of RDX and TNT. The results of this study allow improved prediction of Composition B transport in runoff and therefore its contamination potential.

Transport of insensitive munitions constituents, NTO, DNAN, RDX, and HMX in runoff and sediment under simulated rainfall.

Insensitive munition constituents derived from residues of low order detonations and deposited on military training grounds present environmental risks. A series of rainfall simulation experiments on small soil plots examined the effect of precipitation, soil properties, and particle size on transport of IMX-104 munition components: NTO (3-nitro-1,2,4-triazol-5-one), DNAN (2,4-dinitroanisole), RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7- tertranitro-1,3,5,7-tetrazocine). The primary pathways for rainfall driven transport were subsurface infiltration, off-site transport in solution, and transport in solid form including re-adsorption onto soil particles. The transport was solubility dependent with NTO moving mostly in solution, which was dominated by either runoff or infiltration depending on soil. DNAN, RDX, and HMX, were transported primarily in particulate form. The fine energetic fraction (<2 mm) showed the highest mobility, while the coarsest fraction (>4.75 mm) remained in-situ after rainfall. A simple linear model relating energetics transport with sediment yield and energetics particle size and was proposed. These findings provide the first comprehensive mass balance of munition constituents as affected by overland flow under rainfall. They improve our understanding of environmental fate of munitions, can further be used for predictive modelling, developing mitigation strategies, and regulatory compliance.

A laboratory rill study of IMX-104 transport in overland flow.

The deposition of explosive contaminants in particulate form onto the soil surface during low-order detonations can lead to ground and surface water contamination. The vertical fate and transport of insensitive munitions formulation IMX-104 through soil has been thoroughly studied, however the lateral transport of explosive particles on the surface is less known. The objective of this research was to understand the impact of overland flow on the transport of IMX-104 constituent compounds 3-nitro-1,2,4-triazol-5-one (NTO), 2,4-dinitroanisole (DNAN), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The effect of overland flow was examined in a rill flume using several flow rates (165-, 265-, and 300-mL min-1) and IMX-104 particle sizes (4.75-9.51 mm, 2.83-4.75 mm, 2-2.83 mm, and <2 mm). We found that the smaller particles were transported more in solution and with the sediment compared to the larger particles, which had a higher percent mass remaining on the surface. As flow rate increased, there was an increase in the percent mass found in solution and sediment and a decrease in the percent mass remaining on the surface. NTO fate was dominated by transport in solution, while DNAN, RDX and HMX were predominantly transported with the sediment. This research provides evidence of the role of overland flow in the fate of energetic compounds.

Detection Limits of Trinitrotoluene and Ammonium Nitrate in Soil by Raman Spectroscopy.

The detection limit of 2,4,6-trinitrotoluene (TNT) and ammonium nitrate (AN) in mixtures of Ottawa sand (OS) was studied using a Raman microscope applying conventional calibration curves, Pearson correlation coefficients, and two-sample t-tests. By constructing calibration curves, the conventionally defined detection limits were estimated to be 1.9 ± 0.4% by mass in OS and 1.9 ± 0.3% by mass in OS for TNT and AN. Both TNT and AN were detectable in concentrations as low as 1% by mass when Pearson correlation coefficients were used to compare averaged spectra to a library containing spectra from a range of soil types. AN was detectable in concentrations as low as 1% by mass when a test sample of spectra was compared to the same library using two-sample t-tests. TNT was not detectable at a concentration of 1% by mass when using two-sample t-tests.

Methods for simultaneous determination of legacy and insensitive munition (IM) constituents in aqueous, soil/sediment, and tissue matrices.

Currently, no standard method exists for analyzing insensitive munition (IM) compounds in environmental matrices, with or without concurrent legacy munition compounds, resulting in potentially inaccurate determinations. The primary objective of this work was to develop new methods of extraction, pre-concentration, and analytical separation/quantitation of 17 legacy munition compounds along with several additional IM compounds, IM breakdown products, and other munition compounds that are not currently included in U. S. Environmental Protection Agency (EPA) Method 8330B. The eight additional compounds included were nitroguanidine, 3-nitro-1,2,4-triazol-5-one, picric acid, 2,4-dinitroanisole, 2,4-dinitrophenol, 2-nitrophenol, 4-nitrophenol, and new surrogate ortho-nitrobenzoic acid (o-NBA). Analytical methods were developed to enable sensitive, simultaneous detection and quantitation of the 24 IM and legacy compounds, including two orthogonal high-performance liquid chromatography (HPLC) column separations with either ultraviolet (UV) or mass spectrometric (MS) detection. Procedures were developed for simultaneous extraction of all 24 analytes and two surrogates (1,2-dinitrobenzene, 1,2-DNB; o-NBA) from high- and low-level aqueous matrices and solid matrices, using acidification, solid phase extraction (SPE), or solvent extraction (SE), respectively. For low-level aqueous samples extracted by SPE, all compounds were recovered within current Department of Defense Quality Systems Manual (DoD QSM) Ver5.3 accepted limits for aqueous samples analyzed by EPA Method 8330B (57-135%), except NQ, which was consistently recovered at approximately 50%. Likewise, all compounds were recovered from six geographically/geochemically unique soil types within current QSM accepted limits for solid samples analyzed by EPA Method 8330B (64-135%). Further, the majority of compounds were recovered from four tissue types within current limits for solids, with generally low recovery only for Tetryl (from 4 to 62%). A preparatory chromatographic interference removal procedure was adapted for tissue extracts, as various analytical interferences were observed for all studied tissue types.

Photo-transformation of aqueous nitroguanidine and 3-nitro-1,2,4-triazol-5-one: Emerging munitions compounds.

Two major components of insensitive munition formulations, nitroguanidine (NQ) and 3-nitro-1,2,4-triazol-5-one (NTO), are highly water soluble and therefore likely to photo-transform while in solution in the environment. The ecotoxicities of NQ and NTO solutions are known to increase with UV exposure, but a detailed accounting of aqueous degradation rates, products, and pathways under different exposure wavelengths is currently lacking. Here, we irradiated aqueous solutions of NQ and NTO over a 32-h period at three ultraviolet wavelengths (254 nm, 300 nm, and 350 nm) and analyzed their degradation rates and transformation products. NQ was completely degraded by 30 min at 254 nm and by 4 h at 300 nm, but it was only 10% degraded after 32 h at 350 nm. Mass recoveries of NQ and its transformation products were ≥80% for all three wavelengths, and consisted of large amounts of guanidine, nitrate, and nitrite, and smaller amounts of cyanamide, cyanoguanidine, urea, and ammonium. NTO degradation was greatest at 300 nm with 3% remaining after 32 h, followed by 254 nm (7% remaining) and 350 nm (20% remaining). Mass recoveries of NTO and its transformation products were high for the first 8 h but decreased to 22-48% by 32 h, with the major aqueous products identified as ammonium, nitrate, nitrite, and a urazole intermediate. Environmental half-lives of NQ and NTO in pure water were estimated as 4 and 6 days, respectively. We propose photo-degradation pathways for NQ and NTO supported by observed and quantified degradation products and changes in solution pH.

Ice Core Perspective on Mercury Pollution during the Past 600 Years.

Past emissions of the toxic metal mercury (Hg) persist in the global environment, yet these emissions remain poorly constrained by existing data. Ice cores are high-resolution archives of atmospheric deposition that may provide crucial insight into past atmospheric Hg levels during recent and historical time. Here we present a record of total Hg (HgT) in an ice core from the pristine summit plateau (5340 m asl) of Mount Logan, Yukon, Canada, representing atmospheric deposition from AD 1410 to 1998. The Colonial Period (∼1603-1850) and North American "Gold Rush" (1850-1900) represent minor fractions (8% and 14%, respectively) of total anthropogenic Hg deposition in the record, with the majority (78%) occurring during the 20th Century. A period of maximum HgT fluxes from 1940 to 1975 coincides with estimates of enhanced anthropogenic Hg emissions from commercial sources, as well as with industrial emissions of other toxic metals. Rapid declines in HgT fluxes following peaks during the Gold Rush and the mid-20th Century indicate that atmospheric Hg deposition responds quickly to reductions in emissions. Increasing HgT fluxes from 1993 until the youngest samples in 1998 may reflect the resurgence of Hg emissions from unregulated coal burning and small-scale gold mining.

Natural and anthropogenic variations in atmospheric mercury deposition during the Holocene near Quelccaya Ice Cap, Peru.

Mercury (Hg) is a toxic metal that is transported globally through the atmosphere. The emission of Hg from mineral reservoirs and subsequent recycling in surface reservoirs (i.e., soil/biomass, ocean, and atmosphere) are fundamental to the modern global Hg cycle, yet past emissions from anthropogenic and natural sources are not fully constrained. We use a sediment core from Yanacocha, a headwater lake in southeastern Peru, to study the anthropogenic and natural controls on atmospheric Hg deposition during the Holocene. From 12.3 to 3.5 ka, Hg fluxes in the record are relatively constant (mean ± 1σ: 1.4 ± 0.6 µg m-2 a-1, n = 189). Past Hg deposition does not correlate with changes in regional temperature and precipitation, inferred from nearby paleoclimate records, or with most large volcanic events that occurred regionally, in the Andean Central Volcanic Zone (~300-400 km from Yanacocha), and globally. In B.C. 1450 (3.4 ka), Hg fluxes abruptly increased and reached the Holocene-maximum flux (6.7 µg m-2 a-1) in B.C. 1200, concurrent with a ~100-year peak in Fe and chalcophile metals (As, Ag, Tl) and the presence of framboidal pyrite. Continuously elevated Hg fluxes from B.C. 1200-500 suggest a protracted mining-dust source near Yanacocha that is identical in timing to documented pre-Incan cinnabar mining in central Peru. During Incan and Colonial time (A.D. 1450-1650), Hg deposition remains elevated relative to background levels but lower relative to other Hg records from sediment cores in central Peru, indicating a limited spatial extent of preindustrial Hg emissions. Hg fluxes from A.D. 1980 to 2011 (4.0 ± 1.0 µg m-2 a-1, n = 5) are 3.0 ± 1.5 times greater than pre-anthropogenic fluxes and are similar to modern fluxes documented in remote lakes around the world.

Effects of historical and modern mining on mercury deposition in southeastern Peru.

Both modern anthropogenic emissions of mercury (Hg), primarily from artisanal and small-scale gold mining (ASGM), and preindustrial anthropogenic emissions from mining are thought to have a large impact on present-day atmospheric Hg deposition. We study the spatial distribution of Hg and its depositional history over the past ∼400 years in sediment cores from lakes located regionally proximal (∼90-150 km) to the largest ASGM in Peru and distal (>400 km) to major preindustrial mining centers. Total Hg concentrations in surface sediments from fourteen lakes are typical of remote regions (10-115 ng g(-1)). Hg fluxes in cores from four lakes demonstrate preindustrial Hg deposition in southeastern Peru was spatially variable and at least an order of magnitude lower than previously reported fluxes in lakes located closer to mining centers. Average modern (A.D. 2000-2011) Hg fluxes in these cores are 3.4-6.9 µg m(-2) a(-1), compared to average preindustrial (A.D. 1800-1850) fluxes of 0.8-2.5 µg m(-2) a(-1). Modern Hg fluxes determined from the four lakes are on average 3.3 (±1.5) times greater than their preindustrial fluxes, similar to those determined in other remote lakes around the world. This agreement suggests that Hg emissions from ASGM are likely not significantly deposited in nearby down-wind regions.

Effect of bioirrigation on sediment-water exchange of methylmercury in Boston Harbor, Massachusetts.

Coastal marine sediments are important sites of methylmercury (MMHg) production, and dissolved efflux provides an important source of MMHg to near-shore, and possibly offshore, water columns and food webs. We measured the flux of MMHg across the sediment-water interface at four stations in Boston Harbor that span a range of infaunal population densities and bioirrigation intensities. At each station we carried out total MMHg flux measurements using core incubations and collected near-surface pore waters to establish MMHg gradients for diffusive flux calculations. The flux cores were also imaged by CT scanning to determine the distribution of infaunal burrows, and pore-water sulfide and 222Rn profiles were measured. Total MMHg fluxes, measured using core incubations, ranged from -4 to 191 pmol m(-2) d(-1), and total MMHg fluxes were strongly correlated with burrow densities at the stations. Estimated diffusive fluxes, calculated based on MMHg concentration gradients below the sediment-water interface, were much lower than total fluxes at three of the stations, ranging from 2-19 pmol m(-2) d(-1). These results indicate that MMHg exchange may be significantly enhanced over molecular diffusion in bioturbated sediments. Furthermore, burrow density provides a strong predictor of total MMHg flux. Pore-water exchange of both dissolved MMHg and 222Rn, a naturally occurring pore-watertracer, increased across the range of observed burrow densities, suggesting that the presence of burrows enhances both MMHg production and flux.