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.     

Nitrate and sulfate in individual Asian dust-storm particles in Beijing,China in Spring of 1995 and 1996

Energy dispersive X-ray analysis of elements and reagent thin-film test of particulate nitrate and sulfate were carried out to examine individual dust particles collected in Beijing during five dust-storm events occurring in spring of 1995 and 1996. Dominant particles were electron-opaque and had irregular shapes during the dust-storm periods, and their size was frequently in the range larger than 1 μm (diameter). Besides, some mineral particles that showed regular cubic shapes were found in the range from 0.1 to 2 μm. Their X-ray spectrums indicated calcium was abundant and little or no other elements with atomic number larger than 11 existed in such particles. They were supposed to be emitted initially from construction sites, and then formed through crystallization in the atmosphere. Their most possible composition was CaO or Ca(OH)₂. It was estimated that 93% of the collected electron-opaque particles are dust particles and the cubic particles in term of number frequency. On reagent films, few dust particles reacted apparently with barium chloride suggesting there was no water-soluble sulfate on the surface of dust particles although X-ray spectrums of about 14.6% of dust particles showed peaks of sulfur. The frequency of nitrate-containing particles in dust particles was 10.8%, which was much smaller than that in mineral particles collected in non-dust-storm periods. These results suggest that almost no sulfate is formed and nitrate is hardly formed on the surface of dust particles during their transport from source areas to Beijing.     

Foreword

Fine particles have come to be recognized as being much more significant air pollutants than particles larger than several microns diameter. The removal of fine particles from an effluent gas stream is, unfortunately, more difficult than that of large particles. Because wet scrubbers are one of the major types of air pollution control equipment which can collect fine particles, it is important to define and exploit their potentialities.     

旋流场超细颗粒聚集实验研究

不同粒径分布和浓度的催化裂化(FCC)三旋回收超细催化剂颗粒在旋流场中经过50 h循环回流,颗粒中值粒径变化明显。物料中分散相越多、颗粒粒径越小时,颗粒碰撞越频繁,其聚集趋势越明显。颗粒聚集体在旋流场内不够稳定,通过对比不同进料速率下的旋流场聚集效果,得到最适合颗粒聚集的旋流场雷诺数为20 000。颗粒聚集体存在聚集极限粒径,其最佳聚集时间约为40 h,颗粒聚集后的旋流分离效率提高近5%。     

Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn

Groundwater and wastewater contaminated with chlorinated organic compounds (COCs) can be treated with zero-valent metals. The practicality of this treatment method depends on the reduction rates of the target compounds and their byproducts. In this study, nano-scale Fe and Fe/Ni particles were synthesized so that they could be used to rapidly degrade carbon tetrachloride (CT) and chloroform (CF). Their BET surface areas were around two orders higher than those of commercial micro-scale Fe and Zn particles. Batch reduction experiments carried out with a metal loading of 2.5 gl(-1) showed that complete reduction of CT by the nano-scale Fe/Ni and Fe particles could be achieved within 20 min and 60 min, respectively. With the commercial micro-scale Fe and Zn particles applied at 125 gl(-1), complete CT reduction could only be achieved after 4h and 1.5h, respectively. Reductions of CT and CF with the nano-scale particles followed pseudo-first-order kinetics, and the specific reaction rate constants with the nano-scale Fe/Ni particles were 2-8 times higher than those of the nano-scale Fe particles. CT was degraded through hydrogenolysis to CF, and subsequently via both complete reduction pathway to methane and hydrogenolysis pathway to dichloromethane (DCM). Significantly more methane was generated with the use of the nano-scale Fe/Ni particles than with the nano-scale Fe particles. While the commercial Zn particles were more reactive than the commercial Fe particles, they failed to transform CT directly into methane, causing accumulation of DCM in the aqueous phase.     

Soot particles and their impacts on the mass cycle in the Tibetan atmosphere

Atmospheric aerosol particles in urban and mountain areas around Lhasa city (29.65°N, 91.13°E) in the Tibetan Plateau were collected in the summers of 1998 and 1999. The particles were analyzed with electron microscopes and an energy dispersive X-ray spectrometer. Individual particle morphology, elemental composition and mixture of sulfate and nitrate were investigated. In the urban area, soot particles emitted from vegetation burning were dominant. These particles were characterized by chain or aggregate morphologies, and an elemental composition of potassium and sulfur. Such particles were frequently detected in mountain areas out of the city, where they formed droplets acting as condensation nuclei. Quantitative estimation indicated that sulfur was accumulated onto the soot particles during their dispersion from the urban area to mountain areas. Sulfate and nitrate detections indicated that soot particles collected in the urban area did not contain nitrate and BaCl₂-reactive sulfate, which revealed that the combination of sulfur and potassium in the particles was not K₂SO₄. In contrast, the particles dispersed to mountain areas contained BaCl₂-reactive sulfate and some contained nitrate, suggesting that soot particles emitted from the urban area could increase the buffering capacity of aerosol particles and enhance the formation of particulate sulfate through heterogeneous conversion in the Tibetan atmosphere.     

纳米颗粒的分散及其在水与废水处理中的应用

纳米颗粒由于其吸附活性而极易产生自身团聚 ,这不利于纳米颗粒在使用介质中的分散并影响其应用。本文综述了近年来有关纳米颗粒在水中的分散方法、原理及影响因素 ,归纳总结了分散的纳米颗粒在强化水处理中的若干应用。     

Scanning and transmission electron microscope of suspended lead-rich particles in the air of San Luis Potosi,Mexico

In the city of San Luis Potosi exists an important metallurgical plant and is known that in the adjacent urban zone, there is a high concentration of lead in the air, it is also supposed that most of the particles with lead have an anthropogenic origin because these particles show morphological characteristics and chemical composition very different in comparison with common lead minerals. In this work it was proved that most of the airborne particles with lead present in this urban zone, effectively came from the copper smelter. The airborne particles with lead were compared with particles with lead obtained starting from samples of slag and lead calcine of the copper smelter. To perform the comparative study, these particles were studied with energy dispersive X-ray microanalysis (EDS) in conjunction with scanning electron microscope to obtain chemical composition and associated morphological characteristics. Results suggest that these particles, composed of only one phase, are chemically distinct from any crustal lead mineral. Because of the complexity of the chemical composition of these particles (Pb, S, Cu, As, Fe, Zn, Cd, Sb, O), some of the airborne particles were analyzed by transmission microscopy in order to associate crystalline structure with any particular chemical phase.     

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.     

The composition of individual aerosol particle in the troposphere and stratosphere over Xianghe (39.45°N, 117.0°E), China

A balloon observation was carried out on 22 August in 1993 from Xianghe Scientific Balloon Base (39.75°N, 117.0°E) near Beijing in China. Individual aerosol particles in the five samples collected in the troposphere and lower stratosphere were analyzed by using a transmission electron microscope equipped with an energy-dispersive X-ray (EDX) analyzer. Types of particles were classified by the quantitative EDX analysis and particle morphology. Following results were obtained by the analyses of aerosol particles in the radius range of 0.1–0.5 μm: (1) Sulfate particles were dominant (80%) in aerosol particles collected between 4 and 6 km altitude. (2) Sulfuric acid particles were present in 74% of particles at ∼8 km altitude, 91% at 11 km, 95% at 17 km and 88% at 21.2 km. (3) “S-rich” particles with K were collected both in the troposphere and lower stratosphere. It was considered that the particles containing K found at ∼5, ∼8 km altitude could originate from burning processes in the continent including the Tibetan plateau and be transported to the middle troposphere. (4) Sulfuric acid particles with Fe were present in 20–30% of sulfuric acid particles in the lower stratosphere. (5) Particles mainly composed of minerals were present in 6, 11% of particles at ∼5, ∼8 km, indicating the vertical transport to the upper troposphere. (6) Mineral particles which contain sulfuric acid and sulfate suggest the formation of sulfuric acid and sulfate on mineral particles by heterogeneous processes in the troposphere. (7) Sea-salt particles with and without minerals were collected in the troposphere and lower stratosphere, suggesting the vertical transport by convective clouds.     

Particle size distribution and its relationship to black carbon in two urban and one rural site in Santiago de Chile

The size distribution of particles has been studied in three sites in the Metropolitan area of Santiago de Chile in the winter of 2009 and a comparison with black carbon was performed. Two sites are located near busy streets in Santiago and the other site is located in a rural area about 40 km west of Santiago with little influence from vehicles, but large influence from wood burning. The campaign lasted 1 or 2 weeks in each site. We have divided the particle size measurements into four groups (10–39 nm, 40–62 nm, 63–174 nm, and 175–700 nm) in order to compare with the carbon monitor. In the sites near the street, black carbon has a high correlation (R ? 0.85) with larger particles (175–700 nm). The correlation decreased when black carbon was compared with smaller particles, having very small correlation with the smallest sizes (10–39 nm). In the rural site, black carbon also has a high correlation (R = 0.86) with larger particles (175–700 nm), but the correlation between black carbon and the finest particles (10–39 nm) decreases to near 0. These measurements are an indication that wood burning does not generate particles smaller than ?50 nm. In the urban sites, particle size distribution is peaked toward smaller particles (10–39 nm) only during rush hours, but at other times, particles size distribution is peaked toward larger sizes. When solar radiation was high, evidence of secondary particle formation was seen in the rural site, but not in the urban sites. The correlation between the number of secondary particles and solar radiation was R² = 0.46, indicating that it there may be other variables that play a role in ultrafine particle formation.

Implications:A study of the size distribution of particles and black carbon concentration in two street sites and one rural site shows that in the last site the number of particles ultrafine particles (d < 40 nm) is 10 times lower but the number of larger particles is about 2 times lower. Thus, the rural site has less of the particles that are more dangerous to health. The number of ultrafine particles is mostly associated with traffic, while the number of larger particles is associated with wood burning and other sources. Wood burning does not generate particles smaller than ?50 nm.     

Improved identification of transition metals in airborne aerosols by SEM–EDX combined backscattered and secondary electron microanalysis

The SEM EDX backscattered electron (BSE) atomic number contrast has been largely used in this work, in combination with conventional secondary electron microanalysis, to investigate the presence of metal particles in airborne particulate collected at three sites (industrial, residential, and rural background) in the Po Valley (Italy). Individual particle x-ray microanalysis was used for this aim. In many cases, the presence of metal particles was not evident by secondary electron imaging and it was instead revealed by BSE detection. Metal particles were observed either as isolated (not clustered to other particles), or gathered together (homogeneous clusters). In addition, the BSE microanalysis put on evidence two main types of association of metals to other particulate components: heterogeneous clusters and metals embedded or enclosed in other materials. In this study, the first association (heterogeneous clusters) was observed mostly between Fe-bearing metallic particles and soot aggregates (or other carbonaceous particles) and it was found in the particulate matter (PM) of all studied sites. The second association, conversely, seems to be characterized by more selective relationships between composition/size of metal particles and type of other particulate components. These associations could be evidenced only when using the BSE Z-contrast and mainly concern three cases: (1) unusual silicate–carbonate mixed aggregates were observed at the industrial site only. In these aggregates, embedded Mn, Cr, Co, Bi, W, and Zr fine particles were selectively observed. (2) Ni and V rich ultrafine particles were only observed as embedded particles in the surface structure of carbon cenospheres. (3) Pb or Pb–Zn bearing fine and ultrafine particles were largely detected only in oxygenated organic aerosols in the ultrafine PM.     

Differences in surface properties of amorphous and crystalline metal sulfides may explain their toxicological potency

Crystalline NiS and CoS particles have considerably greater toxic and cell transforming activity than amorphous NiS and CoS particles. These differences in biological activities were attributable to the active phagocytosis of crystalline metal sulfides particles compared with low uptake of amorphous particles. An examination of the surface of crystalline and amorphous metal sulfide particles revealed that cry-stalline NiS and CoS have a net negative surface charge while the surface charge of the amorphous derivatives appears to be positive. Additionally, chemical reduction of NiS particles with LiAlH₄ enhanced their entry into cells. X-ray photoelectron spectroscopy analysis of amorphous and crystalline NiS showed that the outermost surface of the two compounds (1–4 nanometers) differed with respect to the Ni/S ratio and the sulfur oxidation state.     

SARA Title III,Section 313 —Looking Ahead

This study performed a workplace evaluation of emission control using available air sampling filters and characterized the emitted particles captured in filters. Characterized particles were contained in the exhaust gas released from carbon nanotube (CNT) synthesis using chemical vapor deposition (CVD). Emitted nanoparticles were collected on grids to be analyzed using transmission electron microscopy (TEM). CNT clusters in the exhaust gas were collected on filters for investigation. Three types of filters, including Nalgene surfactant-free cellulose acetate (SFCA), Pall A/E glass fiber, and Whatman QMA quartz filters, were evaluated as emission control measures, and particles deposited in the filters were characterized using scanning transmission electron microscopy (STEM) to further understand the nature of particles emitted from this CNT production. STEM analysis for collected particles on filters found that particles deposited on filter fibers had a similar morphology on all three filters, that is, hydrophobic agglomerates forming circular beaded clusters on hydrophilic filter fibers on the collecting side of the filter. CNT agglomerates were found trapped underneath the filter surface. The particle agglomerates consisted mostly of elemental carbon regardless of the shapes. Most particles were trapped in filters and no particles were found in the exhaust downstream from A/E and quartz filters, while a few nanometer-sized and submicrometer-sized individual particles and filament agglomerates were found downstream from the SFCA filter. The number concentration of particles with diameters from 5 nm to 20 µm was measured while collecting particles on grids at the exhaust piping. Total number concentration was reduced from an average of 88,500 to 700 particle/cm³ for the lowest found for all filters used. Overall, the quartz filter showed the most consistent and highest particle reduction control, and exhaust particles containing nanotubes were successfully collected and trapped inside this filter.

Implications: As concern for the toxicity of engineered nanoparticles grows, there is a need to characterize emission from carbon nanotube synthesis processes and to investigate methods to prevent their environmental release. At this time, the particles emitted from synthesis were not well characterized when collected on filters, and limited information was available about filter performance to such emission. This field study used readily available sampling filters to collect nanoparticles from the exhaust gas of a carbon nanotube furnace. New agglomerates were found on filters from such emitted particles, and the performance of using the filters studied was encouraging in terms of capturing emissions from carbon nanotube synthesis.     

Internally mixed sea salt, soot, and sulfates at Macao, a coastal city in South China

Direct observation of the mixing state of aerosol particles in a coastal urban city is critical to understand atmospheric processing and hygroscopic growth in humid air. Morphology, composition, and mixing state of individual aerosol particles from Macao, located south of the Pearl River Delta (PRD) and 100 km west of Hong Kong, were investigated using scanning electron microscopy (SEM) and transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX). SEM images show that soot and roughly spherical particles are prevalent in the samples. Based on the compositions of individual aerosol particles, aerosol particles with roughly spherical shape are classified into coarse Na-rich and fine S-rich particles. TEM/EDX indicates that each Na-rich particle consists of a Na-S core and NaNO3 shell. Even in the absence of heavy pollution, the marine sea salt particles were completely depleted in chloride, and Na-related sulfates and nitrates were enriched in Macao air. The reason could be that SO2 from the polluted PRD and ships in the South China Sea and NO2 from vehicles in the city sped up the chlorine depletion in sea salt through heterogeneous reactions. Fresh soot particles from vehicular emissions mainly occur near curbside. However, there are many aged soot particles in the sampling site surrounded by main roads 200 to 400 m away, suggesting that the fresh soot likely underwent a quick aging. Overall, secondary nitrates and sulfates internally mixed with soot and sea salt particles can totally change their surface hygroscopicity in coastal cities.     

An efficient venturi scrubber system to remove submicron particles in exhaust gas

An efficient venturi scrubber system making use of heterogeneous nucleation and condensational growth of particles was designed and tested to remove fine particles from the exhaust of a local scrubber where residual SiH4 gas was abated and lots of fine SiO2 particles were generated. In front of the venturi scrubber, normal-temperature fine-water mist mixes with high-temperature exhaust gas to cool it to the saturation temperature, allowing submicron particles to grow into micron sizes. The grown particles are then scrubbed efficiently in the venturi scrubber. Test results show that the present venturi scrubber system is effective for removing submicron particles. For SiO2 particles greater than 0.1microm, the removal efficiency is greater than 80-90%, depending on particle concentration. The corresponding pressure drop is relatively low. For example, the pressure drop of the venturi scrubber is approximately 15.4 +/- 2.4 cm H2O when the liquid-to-gas ratio is 1.50 L/m3. A theoretical calculation has been conducted to simulate particle growth process and the removal efficiency of the venturi scrubber. The theoretical results agree with the experimental data reasonably well when SiO2 particle diameter is greater than 0.1 microm.     

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments

The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM₁₀ emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.     

The assessment of particulate matter emitted from stone-crushing industry by correlating rock textures with particles generated after comminution and dispersed in air environment

The generation and emission of particulate matter from abrasion industry are subjects of the pollution monitoring by multidisciplinary study involving earth sciences and engineering disciplines. This work investigates the correlation between textural properties of in situ rock with class size distribution and morphology of particles generated after rock comminution and particles emitted in the air. A special comminution-dust sampling architecture was realised. The combined use of scanning electron microscopy and particle size analyser was considered in performing digital image analysis on both crushed products and airborne particles collected onto membrane filters. The results show that the size and morphology of crushed particles are linked to the petrographic rock properties. In particular, particles with fibrous morphology are prominent in rocks showing foliated textures where elongated minerals occurred, with implication for asbestos-bearing rocks. For what concerns the airborne particles, the results show that their aerodynamic diameters are independent of the crusher operating conditions. External parameters probably intervene in the distribution of the airborne particles emission, including the dynamic air fluxes, or environmental conditions. By applying mathematical models, the morphology and size range of airborne particles following the comminution processes can be predicted, and results has implication for pollutants contamination due to particulate matters emitted by crush stone industry.     

The size distribution of marine atmospheric aerosol with regard to primary biological aerosol particles over the South Atlantic Ocean

The marine atmosphere is characterized by particles which originate from the ocean and by those which reached the air by advection from the continent. The bubble-burst mechanism produces both sea salt as well as biological particles. The following article describes the determination of the size distribution of marine aerosol particles with special emphasis on the biological particles. Th data were obtained on three cruises with the German Research Vessel “METEOR” crossing the South Atlantic Ocean. The measurements showed that biological particles amount to 17% in number and 10% in volume concentration. Another type of particle became obvious in the marine atmosphere, the biologically contaminated particle, i.e. particles which consist partly (approximately up to one-third) of biological matter. Their concentration in the evaluated size class (r>2 μm) is higher than the concentration of the pure biological particles. The concentrations vary over about one to two orders of magnitude during all cruises.     

电凝并式空气净化单元对颗粒物和甲醛净化效果的实验

研究一种新型电凝并式空气净化单元对室内空气中颗粒物和甲醛的净化效果.实验结果表明,高压高频(HV-HF)电凝并装置能促使小粒子相互凝并为较大的电中性的粒子团,这些具有较高比表面积的电中性粒子团进入室内空间,能继续粘附空气中及物体表面上的颗粒,形成更大的粒子团,从而易于被净化单元中的中效过滤器捕集,而且该净化单元对于大粒子(粒径＞0.7μm)浓度较高的场所净化效果更加明显.另外,室内空气中吸附在颗粒物表面的甲醛也随之被高效去除.该净化单元的投入使用,起到了提高过滤效率、去除气溶胶小粒子、降低能耗、进一步改善室内空气品质等多重功效.