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.     

Dissolution kinetics of high explosives particles in a saturated sandy soil

Solid phase high explosive (HE) residues from munitions detonation may be a persistent source of soil and groundwater contamination at military training ranges. Saturated soil column tests were conducted to observe the dissolution behavior of individual components (RDX, HMX, and TNT) from two HE formulations (Comp B and C4). HE particles dissolved readily, with higher velocities yielding higher dissolution rates, higher mass transfer coefficients, and lower effluent concentrations. Effluent concentrations were below solubility limits for all components at superficial velocities of 10-50 cm day(-1). Under continuous flow at 50 cm day(-1), RDX dissolution rates from Comp B and C4 were 34.6 and 97.6 microg h(-1) cm(-2) (based on initial RDX surface area), respectively, significantly lower than previously reported dissolution rates. Cycling between flow and no-flow conditions had a small effect on the dissolution rates and effluent concentrations; however, TNT dissolution from Comp B was enhanced under intermittent-flow conditions. A model that includes advection, dispersion, and film transfer resistance was developed to estimate the steady-state effluent concentrations.     

RDX and TNT residues from live-fire and blow-in-place detonations

Snow was used as a collection medium to examine 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues post-detonation of 60-, 81-, and 120-mm mortar rounds, 105- and 155-mm howitzer rounds, M67 hand grenades, 40-mm rifle grenades, and blocks of C4. Residue-covered snow samples were collected, processed, and analyzed for explosives without cross-contamination from previous detonations and other potential matrix interferences. Detonation trials were performed following standard military live-fire and blow-in-place techniques. When possible, replicate munitions were detonated under similar conditions to provide a more reliable estimation of the mass of unconsumed high explosive residues. Overall the amount of energetic residues deposited from live-fire detonations were considerably less than the energetic residues deposited by blow-in-place detonations.     

Effective elution of RDX and TNT from particles of Comp B in surface soil

During live fire training exercises, large amounts of explosives are consumed. Low order detonations of high explosive payloads result in the patchy dispersal of particles of high explosive formulations over large areas of firing range soils. Dissolution of explosives from explosive formulation particles into soil pore water is a controlling factor for transport, fate, and effects of explosive compounds. We developed an empirical method to evaluate soils based on functionally defined effective dissolution rates. An automated Accelerated Solvent Extractor was used to determine the effective elution rates under controlled conditions of RDX and TNT from soil columns containing particles of Comp B. Contrived soils containing selected soil geosorbants and reactive surfaces were used to quantitatively determine the importance of these materials. Natural soils from training ranges of various soil types were also evaluated. The effects of geosorbants on effective elution rates were compound- and sorbent-specific. TNT elution was less than that of RDX and was greatly slowed by humic acid. Iron and iron-bearing clays reduced the effective elution rates of both RDX and TNT. This empirical method is a useful tool for directly generating data on the potential for explosives to leach from firing range soils, to identify general bulk soil characteristics that can be used to predict the potential, and to identify means to engineer soil treatments to mitigate potential transport.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

A morphological investigation of soot produced by the detonation of munitions

The morphology of three different detonation soot samples along with other common soot materials such as carbon black, diesel soot and chimney soot was studied by elemental and proximate analysis, X-ray diffraction and electron microscopy. The goal of this study was to better define the morphology of the detonation soot in order to better assess the interactions of this type of soot with explosive residues. The detonation soot samples were obtained by the detonation of artillery 155mm projectiles filled with either pure TNT (2,4,6-trinitrotoluene) or composition B, a military explosive based on a mixture of TNT and RDX (trimethylentrinitramine). The carbon content of the soot samples varied considerably depending on the feedstock composition. Detonation soot contains less carbon and more nitrogen than the other carbonaceous samples studied, due to the molecular structure of the energetic materials detonated such as TNT and RDX. The ash concentration was higher for detonation soot samples due to the high metal content coming from the projectiles shell and to the soil contamination which occurred during the detonation. By X-ray diffraction, diamond and graphite were found to be the major crystalline carbon forms in the detonation soot. Two electron microscopy techniques were used in this study to visualise the primary particles and to try to explain the formation mechanism of detonation soot samples.     

Use of noise attenuation modeling in managing missile motor detonation activities

The Sound Intensity Prediction System (SIPS) and Blast Operation Overpressure Model (BOOM) are semiempirical sound models that are employed by the Utah Test and Training Range (UTTR) to predict whether noise levels from the detonation of large missile motors will exceed regulatory thresholds. Field validation of SIPS confirmed that the model was effective in limiting the number of detonations of large missile motors that could potentially result in a regulatory noise exceedance. Although the SIPS accurately predicted the impact of weather on detonation noise propagation, regulators have required that the more conservative BOOM model be employed in conjunction with SIPS in evaluating peak noise levels in populated areas. By simultaneously considering the output of both models, in 2001, UTTR detonated 104 missile motors having net explosive weights (NEW) that ranged between 14,960 and 38,938 lb without a recorded public noise complaint. Based on the encouraging results, the U.S. Department of Defense is considering expanding the application of these noise models to support the detonation of missile motors having a NEW of 81,000 lb. Recent modeling results suggest that, under appropriate weather conditions, missile motors containing up to 96,000 lb NEW can be detonated at the UTTR without exceeding the regulatory noise limit of 134 decibels (dB).     

Use of Noise Attenuation Modeling in Managing Missile Motor Detonation Activities

Abstract

The Sound Intensity Prediction System (SIPS) and Blast Operation Overpressure Model (BOOM) are semiempirical sound models that are employed by the Utah Test and Training Range (UTTR) to predict whether noise levels from the detonation of large missile motors will exceed regulatory thresholds. Field validation of SIPS confirmed that the model was effective in limiting the number of detonations of large missile motors that could potentially result in a regulatory noise exceedance. Although the SIPS accurately predicted the impact of weather on detonation noise propagation, regulators have required that the more conservative BOOM model be employed in conjunction with SIPS in evaluating peak noise levels in populated areas. By simultaneously considering the output of both models, in 2001, UTTR detonated 104 missile motors having net explosive weights (NEW) that ranged between 14,960 and 38,938 lb without a recorded public noise complaint. Based on the encouraging results, the U.S. Department of Defense is considering expanding the application of these noise models to support the detonation of missile motors having a NEW of 81,000 lb. Recent modeling results suggest that, under appropriate weather conditions, missile motors containing up to 96,000 lb NEW can be detonated at the UTTR without exceeding the regulatory noise limit of 134 decibels (dB).     

Dissolution kinetics of sub-millimeter Composition B detonation residues: role of particle size and particle wetting

The dissolution of the 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from microscale particles (<250 μm) of the explosive formulation Composition B was examined and compared to dissolution from macroscopic particles (>0.5 mm). The dissolution of explosives from detonation soot was also examined. The measured mass transfer coefficients for the microscale particles were one to two orders of magnitude greater than the macroscopic particles. When normalized to particle surface area, mass transfer coefficients of microscale and macroscale particles were similar, indicating that the bulk dissolution processes were similar throughout the examined size range. However, an inverse relationship was observed between the particle diameter and the RDX:TNT mass transfer rate coefficient ratio for dry-attritted particles, which suggests that RDX may be more readily dissolved (relative to TNT) in microscale particles compared to macroscale particles. Aqueous weathering of larger Composition B residues generated particles that possessed mass transfer coefficients that were on the order of 5- to 20-fold higher than dry-attritted particles of all sizes, even when normalized to particle surface area. These aqueous weathered particles also possessed a fourfold lower absolute zeta-potential than dry-attritted particles, which is indicative that they were less hydrophobic (and hence, more wettable) than dry-attritted particles. The increased wettability of these particles provides a plausible explanation for the observed enhanced dissolution. The wetting history and the processes by which particles are produced (e.g., dry physical attrition vs. aqueous weathering) of Composition B residues should be considered when calculating mass transfer rates for fate and transport modeling.     

Dissolution rates of three high explosive compounds: TNT,RDX, and HMX

Incidental exposure to high explosive compounds can cause subtle health effects to which a population could be more susceptible than injury by detonation. Proper source characterization is a key requirement in the conduct of risk assessments. For nonvolatile solid explosives, dissolution is one of the primary mechanisms that controls fate and transport, resulting in exposure to these compounds remote from their source. To date, information describing dissolution rates of high explosives has been sparse. The objective of this study was to determine the dissolution rates of three high explosive compounds, 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), in dilute aqueous solutions as a function of temperature, surface area, and energy input. To determine each variable's impact on dissolution rate, experiments were performed where one variable was changed while the other two were held constant. TNT demonstrated the fastest dissolution rate followed by HMX and then RDX. Dissolution rate correlation equations were developed for each explosive compound incorporating the three aforementioned variables, independently, and collectively in one correlation equation.     

Concentration,size, and density of total suspended particulates at the air exhaust of concentrated animal feeding operations

Total suspended particulate (TSP) samples were seasonally collected at the air exhaust of 15 commercial concentrated animal feeding operations (CAFOs; including swine finishing, swine farrowing, swine gestation, laying hen, and tom turkey) in the U.S. Midwest. The measured TSP concentrations ranged from 0.38 ± 0.04 mg m^?3 (swine gestation in summer) to 10.9 ± 3.9 mg m^?3 (tom turkey in winter) and were significantly affected by animal species, housing facility type, feeder type (dry or wet), and season. The average particle size of collected TSP samples in terms of mass median equivalent spherical diameter ranged from 14.8 ± 0.5 µm (swine finishing in winter) to 30.5 ± 2.0 µm (tom turkey in summer) and showed a significant seasonal effect. This finding affirmed that particulate matter (PM) released from CAFOs contains a significant portion of large particles. The measured particle size distribution (PSD) and the density of deposited particles (on average 1.65 ± 0.13 g cm^?3) were used to estimate the mass fractions of PM₁₀ and PM_2.5 (PM ≤10 and ≤2.5 μm, respectively) in the collected TSP. The results showed that the PM₁₀ fractions ranged from 12.7 ± 5.1% (tom turkey) to 21.1 ± 3.2% (swine finishing), whereas the PM_2.5 fractions ranged from 3.4 ± 1.9% (tom turkey) to 5.7 ± 3.2% (swine finishing) and were smaller than 9.0% at all visited CAFOs. This study applied a filter-based method for PSD measurement and deposited particles as a surrogate to estimate the TSP’s particle density. The limitations, along with the assumptions adopted during the calculation of PM mass fractions, must be recognized when comparing the findings to other studies.

Implications: The concentration, size, and density of TSP samples varied greatly with animal species, housing facility type, feeder type, and season, suggesting that PM emission data derived from limited measurements may not be readily applied to estimate the overall emission from concentrated animal feeding operations (CAFOs). This study also affirmed that particles released from CAFOs is of relatively high density (~1.65 g cm^?3) and with diameter mostly larger than 10 µm, indicating that regular PM abatement devices, such as cyclones, fabric filters, or even a simple downward-facing exhaust duct, may be employed to mitigate the TSP emission with acceptable efficiency.     

High uptake of 2,4,6-trinitrotoluene by vetiver grass--potential for phytoremediation?

2,4,6-Trinitrotoluene (TNT) is a potent mutagen, and a Group C human carcinogen that has been widely used to produce munitions and explosives. Vast areas that have been previously used as ranges, munition burning, and open detonation sites are heavily contaminated with TNT. Conventional remediation activities in such sites are expensive and damaging to the ecosystem. Phytoremediation offers a cost-effective, environment-friendly solution, utilizing plants to extract TNT from contaminated soil. We investigated the potential use of vetiver grass (Vetiveria zizanioides) to effectively remove TNT from contaminated solutions. Vetiver grass plants were grown in hydroponic systems containing 40 mg TNTL(-1) for 8d. Aqueous concentrations of TNT reached the method detection limit ( approximately 1 microg L(-1)) within the 8-d period, demonstrating high affinity of vetiver for TNT, without any visible toxic effects. Results from this preliminary hydroponic study are encouraging, but in need of verification using TNT-contaminated soils.     

Accumulation of sulfur and heavy metals in soil and tree leaves sampled from the surroundings of Tuncbilek Thermal Power Plant

In this study, the quantities of sulfur and heavy metals, resulting from the Tuncbilek Thermal Power Plant (TPP) in Turkey, have been assessed in tree leaves and soil samples within a 10 km radius of the plant. Leaves of Salix alba L., Populus tremula L., Robinia pseudoacacia L., Quercus infectoria L., Pinus nigra Arn. ssp. pallasiana (Lamb) Holmboe. trees have been used with the aim of determining how far the gas and particles emitted from the TPP are carried, and for assessment of environmental impact. The results obtained from locations chosen at various distances to the TPP, indicate that the contaminating agents are very dense and effective; particularly in the prevailing wind direction and within 10 km of the plant. They gradually lose their density and effect beyond this distance. The sulfur and heavy metal analyses made in soils taken from these locations indicate a similarity with the data obtained from the leaves.     

Characterization of particle number concentrations and PM<Subscript>2.5</Subscript> in a school: influence of outdoor air pollution on indoor air

Background, Aim and Scope  

The impact of air pollution on school children’s health is currently one of the key foci of international and national agencies. Of particular concern are ultrafine particles which are emitted in large quantities, contain large concentrations of toxins and are deposited deeply in the respiratory tract.     

Field validation of sound mitigation models and air pollutant emission testing in support of missile motor disposal activities

The U.S. Department of Defense approved activities conducted at the Utah Test and Training Range (UTTR) include both operational readiness test firing of intercontinental ballistic missile motors as well as the destruction of obsolete or otherwise unusable intercontinental ballistic missile motors through open burn/open detonation (OB/ OD). Within the Utah Division of Air Quality, these activities have been identified as having the potential to generate unacceptable noise levels, as well as significant amounts of hazardous air pollutants. Hill Air Force Base, UT, has completed a series of field tests at the UTTR in which sound-monitoring surveillance of OB/OD activities was conducted to validate the Sound Intensity Prediction System (SIPS) model. Using results generated by the SIPS model to support the decision to detonate, the UTTR successfully disposed of missile motors having an aggregate net explosive weight (NEW) of 56,500 lbs without generating adverse noise levels within populated areas. These results suggest that, under appropriate conditions, missile motors of even larger NEW may be detonated without exceeding regulatory noise limits. In conjunction with collecting noise monitoring data, air quality data was collected to support the development of air emission factors for both static missile motor firings and OB/OD activities. Through the installation of 15 ground-based air samplers, the generation of combustion fixed gases, hazardous air pollutants, and chlorides were monitored during the 56,500-lb NEW detonation event. Comparison of field measurements to predictions generated from the U.S. Navy's energetic combustion pollutant formation model, POLU4WN, indicated that, as the detonation fireball expanded from ground zero, organic compounds as well as carbon monoxide continued to oxidize as the hot gases reacted with ambient air. Hazardous air pollutant analysis of air samplers confirmed the presence of chloromethane, benzene, toluene, 1,2-propadiene, and 2-methyl-l-propene, whereas the absence of hydrogen chloride gas suggested that free chlorine is not generated during the combustion process.     

Field Validation of Sound Mitigation Models and Air Pollutant Emission Testing in Support of Missile Motor Disposal Activities

Abstract

The U.S. Department of Defense approved activities conducted at the Utah Test and Training Range (UTTR) include both operational readiness test firing of intercontinental ballistic missile motors as well as the destruction of obsolete or otherwise unusable intercontinental ballistic missile motors through open burn/open detonation (OB/ OD). Within the Utah Division of Air Quality, these activities have been identified as having the potential to generate unacceptable noise levels, as well as significant amounts of hazardous air pollutants. Hill Air Force Base, UT, has completed a series of field tests at the UTTR in which sound-monitoring surveillance of OB/OD activities was conducted to validate the Sound Intensity Prediction System (SIPS) model. Using results generated by the SIPS model to support the decision to detonate, the UTTR successfully disposed of missile motors having an aggregate net explosive weight (NEW) of 56,500 lbs without generating adverse noise levels within populated areas. These results suggest that, under appropriate conditions, missile motors of even larger NEW may be detonated without exceeding regulatory noise limits. In conjunction with collecting noise monitoring data, air quality data was collected to support the development of air emission factors for both static missile motor firings and OB/OD activities. Through the installation of 15 ground-based air samplers, the generation of combustion fixed gases, hazardous air pollutants, and chlorides were monitored during the 56,500-lb NEW detonation event. Comparison of field measurements to predictions generated from the U.S. Navy’s energetic combustion pollutant formation model, POLU4WN, indicated that, as the detonation fireball expanded from ground zero, organic compounds as well as carbon monoxide continued to oxidize as the hot gases reacted with ambient air. Hazardous air pollutant analysis of air samplers confirmed the presence of chloromethane, benzene, toluene, 1,2-propadiene, and 2-methyl-1-propene, whereas the absence of hydrogen chloride gas suggested that free chlorine is not generated during the combustion process.     

TiO_2光催化对微滤去除腐殖酸的膜污染控制研究

着重研究了不同紫外灯光源和照射时间条件下,TiO_2光催化(PCO)对微滤去除腐殖酸过程中的膜污染控制,并探讨了膜污染的控制机理。研究结果表明,TiO_2光催化能有效提高微滤对腐殖酸的去除,同时降低膜通量的下降,起到有效控制膜污染的作用。进一步的实验分析表明,TiO_2光催化控制膜污染的主要机理在于将腐殖酸降解为易于被TiO_2吸附的小分子量物质,吸附腐殖酸降解产物后的TiO_2聚合颗粒粒径增大,易于在膜表面形成更为松散的沉积层,并使膜污染从以膜孔堵塞和沉积层污染为主转化为以沉积层污染为主的可逆性污染。     

Dry deposition of particles and canopy exchange: Comparison of wet,bulk and throughfall deposition at five forest sites in Italy

The contribution of dry deposition to the total atmospheric input of acidifying compounds and base cations is of overwhelming importance. Throughfall measurements provide an estimate of the total deposition to forest soils, including dry deposition, but some uncertainties, related to the canopy interaction processes, affect this approach. We compared the concentrations and the fluxes of the main ions determined in wet-only, bulk and throughfall samples collected at five forest sites in Italy. The contribution of coarse particles deposited onto the bulk samplers was of prime importance for base cations, representing on average from 16% to 46% of the bulk deposition. The extent of this dry deposition depended on some geographical features of the sites, such as the distance from the sea and the annual rainfall. The possibility of applying specific bulk/wet ratios to estimate the wet deposition proved to be limited by the temporal variability of these ratios, which must be considered together with the spatial variability. A direct comparison of the dry contribution deriving from the bulk–wet and the throughfall–wet demonstrated that an extensive natural surface (forest canopy) performs better than a small synthetic surface (funnel of the bulk sampler) in collecting dry deposition of SO₄²⁻, NO₃⁻ and Na⁺. The canopy exchange model was applied to both bulk and wet data to estimate the contribution of dry deposition to the total input of base cations, and the uncertainty associated to the model discussed. The exclusive use of bulk data led to a considerable underestimation of base cation dry deposition, which varies among the study sites.     

Closing Comments

Fine particles are those which penetrate into the respiratory system where they may act as a carcinogen, may contribute to blockage of the alveoli, or may accommodate pulmonary pathogens . Mr. Harrington observed that fine particles are not a single pollutant but a large category of pollutants. It is therefore difficult to agree on a general definition of fine particles as a pollutant. However, it has been shown that particles with diameters smaller than 5 µm do penetrate past the nasal cavity and nasopharynx into the lungs and that particles with diameters as small as 0.01 µm are deposited in the lungs. Other problems associated with submicron particles are that they are slow in settling out of the atmosphere and they create haze and adverse weather modification.