Insights into the dissolution and the three-dimensional structure of insensitive munitions formulations

Two compounds, 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) are the main ingredients in a suite of explosive formulations that are being, or soon will be, fielded at military training ranges. We aim to understand the dissolution characteristics of DNAN and NTO and three insensitive muntions (IM) formulations that contain them. This information is needed to accurately predict the environmental fate of IM constituents, some of which may be toxic to people and the environment. We used Raman spectroscopy to identify the different constituents in the IM formulations and micro computed tomography to image their three-dimensional structure. These are the first three-dimensional images of detonated explosive particles.     

Laboratory testing of a continuous emissions monitor for hydrochloric acid

Continuous monitoring of exhaust flue gas has become a common practice in power plants in response to Federal Mercury and Air Toxics Standards (MATS) standards. Under the current rules, hydrochloric acid (HCl) is not continuously measured at most plants; however, MATS standards have been proposed for HCl, and tunable diode laser (TDL) absorption spectroscopy is one method that can be used to measure HCl continuously. The focus of this work is on the evaluation and verification of the operation performance of an HCL TDL over a range of real-world operating environments. The testing was conducted at the University of California at Riverside (UCR) spectroscopy evaluation laboratory. Laboratory tests were conducted at three separate temperatures, 25ºC, 100ºC, and 200ºC, and two distinct moisture levels for the enhanced temperatures, 0%, (2 tests) and 4%, over a concentration range from 0 ppmv to 25 ppmv-m at each of the elevated temperatures. The results showed good instrument accuracy as a function of changing temperature and moisture. Data analysis showed that the average percentage difference between the ammonia concentration and the calibration source was 3.33% for varying moisture from 0% to 4% and 2.69% for varying temperature from 25 to 100/200ºC. An HCl absorption line of 1.742 μm was selected for by the manufacturer for this instrument. The Hi Tran database indicated that CO₂ is probably the only major interferent, although the CO₂ absorption is very weak at that wavelength. Interference tests for NO, CO, SO₂, NH₃, and CO₂ for a range of concentrations typical of flue gasses in coal-fired power plants did not show any interference with TDL HCl measurements at 1.742 μm. For these interference tests, CO₂ was tested at a concentration of 11.9% concentration in N₂ for these tests. Average precision over the entire range for all 10 tests is 3.12%.

Implications: The focus of this study was an evaluation of the operation performance of a tunable diode laser (TDL) for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of changing temperature from 25ºC to 200ºC and moisture from 0% to 4%. Such as an instrument could be used for continuous monitoring of exhaust flue gas in power plants once the Federal Mercury and Air Toxics Standards (MATS) standards have been fully implemented.     

Effect of NOx Control Processes on Mercury Speciation in Utility Flue Gas

Abstract

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NO_x control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NO_x control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH₃, has been evaluated. The influence of NH₃ on fly ash Hg reactions also is being investigated.     

Evaluation of NO(x) flue gas analyzers for accuracy and their applicability for low-concentration measurements

The requirements of the Texas State Implementation Plan of the U.S. Clean Air Act for the Houston-Galveston Ozone Nonattainment Area stipulate large reductions in oxides of nitrogen (NO(x)) emissions. A large number of sources at Dow Chemical Co. sites within the nonattainment area may require the addition of continuous emission monitoring systems (CEMS) for online analysis of NO(x), CO, and O2. At the outset of this work, it was not known whether the analyzers could accurately measure NO(x) as low as 2 ppm. Therefore, NO(x) CEMS analyzers from five different companies were evaluated for their ability to reliably measure NO(x) in the 2-20 ppm range. Testing was performed with a laboratory apparatus that accurately simulated different mixtures of flue gas and, on a limited basis, simulated a dual-train sampling system on a gas turbine. The results indicate that this method is a reasonable approach for analyzer testing and reveal important technical performance aspects for accurate NO(x) measurements. Several commercial analyzers, if installed in a CEMS application with sampling conditioning components similar to those used in this study, can meet the U.S. Environmental Protection Agency's measurement data quality requirements for accuracy.     

Effect of NOx control processes on mercury speciation in utility flue gas

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NOx control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NOx control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH3, has been evaluated. The influence of NH3 on fly ash Hg reactions also is being investigated.     

Phosphorus and nitrogen runoff from a forested watershed fertilized with biosolids

Municipal biosolids are typically not used on the steepest of forested slopes in the U.S. Pacific Northwest. The primary concern in using biosolids on steep slopes is movement of biosolids particles and soluble nutrients to surface waters during runoff events. We examined the pattern and extent of P and N runoff from a perennial stream draining a small, forested 21.4-ha watershed in western Washington before and after biosolids application. In this study, we applied biosolids at a rate of 13.5 Mg ha(-1) (700 kg N ha(-1) and 500 kg P ha(-1)) to 40% of the watershed following nearly 1.5 years of pre-application water sampling and 1.5 years thereafter. There was no evidence of direct runoff of P or N from biosolids into surface water. Elevated surface water discharge did not change the concentration of PO4-P, biologically available phosphorus (BAP), bioavailable particulate phosphorus (BPP), or total P nor did it affect the concentration-discharge relationship. Some instances of total P concentrations exceeding the USEPA surface water standard of 0.1 mg L(-1) were observed following biosolids application. However, total P in 27 Creek was predominately in particulate form and not labile, suggesting that detritus moving into the main creek channel and ephemeral drainage courses may be the principal P source. Ammonium N concentrations in runoff water were consistent before and after biosolids application, ranging from below detection limits (0.01 mg L(-1)) to 0.1 mg L(-1); no concentration-discharge relationship existed. Biosolids application changed the 27 Creek concentration-discharge relationship for NO3(-)-N. Before application, no relationship existed. Beginning nine months after biosolids application, increases in discharge were positively related to increases in NO3(-)-N concentrations. Nitrate concentrations in runoff following biosolids application were approximately 10 times less than the USEPA drinking water standard of 10 mg L(-1).     

Revegetation of high zinc and lead tailings with municipal biosolids and lime: greenhouse study

Acidic (pH 4.1) and high Cd, Pb, and Zn mine tailings (mean +/- SD: 17 +/- 0.4, 3800 +/- 100, and 3500 +/- 100 mg kg(-1), respectively) from an alluvial tailings deposit in Leadville, Colorado were amended with municipal biosolids (BS) (224 Mg ha(-1)) and different types of lime (calcium carbonate equivalent of 224 Mg ha(-1) CaCO3) in a greenhouse column study to test the ability of the amendments to neutralize surface and subsoil acidity and restore plant growth. The types of lime included coarse, agricultural, and fine-textured lime (CL, AL, and FL), sugar beet lime (SBL), and lime kiln dust (LK). The FL was also added alone. All treatments increased bulk pH in the amended horizon in comparison to the control, with the most significant increases observed in the FL, SBL+BS, and LK+BS treatments (7.33, 7.34, and 7.63, respectively). All treatments, excluding the FL, increased the pH in the horizon directly below the amended layer, with the most significant increases observed in the SBL+BS and LK+BS treatments (6.01 and 5.41, respectively). Significant decreases in 0.01 M Ca(NO3)2-extractable Zn and Cd were observed in the subsoil for all treatments that included BS, with the largest decrease in the SBL+BS treatment (344 and 3.9 versus 4 and 0.1 mg kg(-1) Zn and Cd, respectively). Plant growth of annual rye (Lolium multiflorum L.) was vigorous in all treatments that included BS with plant Zn, Cd, and Pb concentrations reduced over the control.     

TNT particle size distributions from detonated 155-mm howitzer rounds

To achieve sustainable range management and avoid or minimize environmental contamination, the Army needs to know the amount of explosives deposited on ranges from different munitions and how these are degraded and transported under different geological and climatic conditions. The physical form of the deposited explosives has a bearing on this problem, yet the shapes and size distributions of the explosive particles remaining after detonations are not known. We collected residues from 8 high-order and 6 low-order non-tactical detonations of TNT-filled 155-mm rounds. We found significant variation in the amount of TNT scattered from the high-order detonations, ranging from 0.00001 to 2% of the TNT in the original shell. All low-order detonations scattered percent-level amounts of TNT. We imaged thousands of TNT particles and determined the size, mass and surface-area distributions of particles collected from one high-order and one low-order detonation. For the high-order detonation, particles smaller than 1 mm contribute most of the mass and surface area of the TNT scattered. For the low-order detonation, most of the scattered TNT mass was in the form of un-heated, centimeter-sized pieces whereas most of the surface area was again from particles smaller than 1 mm. We also observed that the large pieces of TNT disintegrate readily, giving rise to many smaller particles that can quickly dissolve. We suggest picking up the large pieces of TNT before they disintegrate to become point sources of contamination.     

Effect of amendment C:N ratio on plant richness, cover and metal content for acidic Pb and Zn mine tailings in Leadville, Colorado

Biosolids and woody debris were applied with target C:N ratios of 8:1 to 50:1 to phytotoxic, acidic, high metal mine tailings to test the effect of amendment C:N ratio on native plant restoration. Total soil C decreased over time indicating an active microbial community. The 8:1 treatment initially had no growth, the highest plant cover for the final sampling (86.8+/-13.8%) and the lowest number of species (3.33+/-0.4). The greatest number of species was in the 30:1 treatment (5.44+/-0.45). Plant cover increased over time for all treatments from 44.7% in 2001 to 71% in 2005. This response was consistent across all except for the 30:1 treatment, which showed a slight decrease in the final year (65+/-11%). Volunteer species and evidence of animal grazing were observed in all amended plots. Results indicate that a C:N ratio>/=20:1 increased species diversity.