In Situ Measurement of Hydrochloric Acid in Rocket Exhaust Clouds Using a Remotely Piloted Aircraft

Abstract

An instrumentation system employing an RPV (remotely piloted vehicle) platform was developed for temporally and spatially resolved air pollution measurements, and was used to measure the evolution of gas-phase HC1 in exhaust clouds from a solid rocket motor firing and fuel pit burns. A thermistor and a sensitive (ppmv-level), rapid-response (<0.1 sec) infrared absorption sensor for HC1 were mounted in a flow channel in the RPV, permitting concentration and temperature measurements to be made in the cloud on a several-meter scale. The RPV system was flown in a series of field tests at Thiokol Corporation’s Elkton, MD division to evaluate the HC1 content of the exhaust products of a new Mg-based fuel formulation. Measurements were made in the clouds from Al-based and Mg-based solid fuel pit burns and a Mg-fueled motor firing over periods of several minutes. Elevated temperatures and HC1 concentrations were found to be temporally correlated with video images of the particulate cloud. Cl originating from the ammonium perchlorate oxidizer appeared in the exhaust as HC1 in each of the tests. Both the macroscopic and local cloud parameters indicate that the Mg-based fuel may provide some reduction in HC1 concentration compared to the standard Al-based fuel.     

Methyl Tertiary Hexyl Ether and Methyl Tertiary Octyl Ether as Gasoline Oxygenates: Assessing Risks from Atmospheric Dispersion and Deposition

Abstract

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10^?3 and 10^?2 for MtHxE and MtOcE, respectively, in Boston, and 10^?2 and 10^?1 in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.     

Atmospheric Deposition and Ionic Input in Adirondack Forests

Major mechanisms for input of ions to forest ecosystems in the central Adirondack Mountains of New York State were studied. Precipitation and throughfall in adjacent northern hardwood and lake margin coniferous forests were continuously sampled from May 2, 1979 to May 7, 1980. Important mechanisms for transport of ions from atmosphere to forest floor were identified using regression analyses and the assumption that deciduous and coniferous forests capture particulates and aerosols with differing efficiencies. Sodium was delivered in precipitation and dry-fall and interacted little with the forest canopies. Hydrogen, potassium, and magnesium were also deposited primarily by bulk precipitation but hydrogen was retained by foliage while additional quantities of potassium and magnesium were leached from tree canopies. Impaction of suspended particulates and/or aerosols on forest vegetation was an important source of additional sulfate and nitrate, and these ions contributed to the leaching of calcium from foliage.     

Effects of Aerosol Species on Atmospheric Visibility in Kaohsiung City,Taiwan

Abstract

Visibility data collected from Kaohsiung City, Taiwan, for the past two decades indicated that the air pollutants have significantly degraded visibility in recent years. During our study period, the seasonal mean visibilities in spring, summer, fall, and winter were only 5.4, 9.1, 8.2, and 3.4 km, respectively. To ascertain how urban aerosols influence the visibility, we conducted concurrent visibility monitoring and aerosol sampling in 1999 to identify the principal causes of visibility impairments in the region. In this study, ambient aerosols were sampled and analyzed for 11 constituents, including water-soluble ions and carbon materials, to investigate the chemical composition of Kaohsiung aerosols. Stepwise regression method was used to correlate the impact of aerosol species on visibility impairments. Both seasonal and diurnal variation patterns were found from the monitoring of visibility. Our results showed that light scattering was attributed primarily to aerosols with sizes that range from 0.26 to 0.90 μm, corresponding with the wavelength region of visible light, which accounted for ～72% of the light scattering coefficient. Sulfate was a dominant component that affected both the light scattering coefficient and the visibility in the region. On average, (NH₄)₂SO₄, NH₄NO₃, total carbon, and fine particulate matter (PM_2.5)-remainder contributed 53%, 17%, 16%, and 14% to total light scattering, respectively. An empirical regression model of visibility based on sulfate, elemental carbon, and humidity was developed, and the comparison indicated that visibility in an urban area could be properly simulated by the equation derived herein.     

Source-Receptor Relationships for Acid Deposition: Pure and Simple

The Critical Review entitled Source-Receptor Relationships for Acid Deposition: Pure and Simple? was presented by George M. Hidy at the 77th APCA Annual Meeting and Exhibition in San Francisco, California. Dr. Hidy spoke on his paper which had been published in the May 1984 issue of JAPCA. Prepared discussions presented at the Critical Review Session in San Francisco are reproduced here. In addition, discussion initiated from the floor and comments received through the mail have been formalized and are published along with closing remarks by Dr. Hidy. Dr. Paul J. Lioy, Critical Review Committee chairman, served as moderator for the 1984 Critical Review Session.     

A Critical Assessment of Atmospheric Visibility and Aerosol Measurements in the Eastern United States

As part of a study examining the technical basis for a secondary national ambient air quality standard for fine particulate matter to protect visibility, we reviewed available data on atmospheric aerosol and visibility in the eastern U.S. This paper presents the results of that visibility and aerosol characterization.

Analysis of airport visibility data indicates that the annual median visual ranges in the East are in the 16-25 km range. In the absence of a "reference method," limited measurements of visibility using various types of instruments provide data generally in agreement with the airport visibility estimates when a contrast threshold of 0.05 is assumed in calculating visual range from the instrumental measurements.

Both long- and short-term aerosol measurements have yielded consistent results; however, because of the differences in instrumentation and laboratory analytical techniques among various studies, data often are not directly comparable. The measured annual average fine particulate matter mass concentration is about 18 μg/m³ in the rural East; during summer it increases to about 23 μg/m³. If all the sulfur in the fine mass is assumed to exist as ammonium sulfate, it would constitute 46 percent of the annual mean and about 60 percent of the summer mean fine mass concentrations. Carbon and volatiles, including water, are believed to constitute significant fractions of the fine mass; however, there are little data quantifying their contributions to fine mass and visibility impairment. Additional long-term measurements of visibility and fine aerosol and its various components are necessary to completely characterize visibility and aerosol in the East.     

机动车尾气VOCs排放特征及减排措施研究

分析了机动车尾气挥发性有机物(VOCs)的排放特征,发现尾气VOCs排放具有明显的日变化和季节变化特征。不同区域不同车型机动车尾气VOCs成分谱略有差异,轻型汽油车尾气VOCs中芳香烃和烷烃含量较高,柴油车烷烃含量较高。尾气排放受机动车保有量、行驶里程、维护保养水平、行驶速度和燃油标准、排放标准等因素影响。从优先控制汽油车、加快机动车更新、采取本地化减排措施、加强多元管理措施、提高科研水平等方面提出了针对性的减排措施。     

江苏省大气污染和酸雨的现状及预测

利用区域酸沉降模式模拟了江苏省197年和2000年大气污染物浓度和酸沉降的空间分布，根据未来的能源规划，进一步预测了该省2005年和2010年的大气环境发展状况。研究表明，江苏1997年SO2和S沉降污染较为严重的为苏北徐州、淮阴和苏南镇江、常州一带，而苏中地区尚不严重。SO2年均地面质量浓度最大值出现在镇江，为55μg/m^3，全省SO2排放140万t，折合成S为70万t，造成本地区S沉降46万t。未来的大气SO2浓度和S沉降呈现增加态势，考虑能源结构调整条件下的大气环境污染状况比不考虑的情形有所改善。     

Acid Rain Emission Allowances and Future Capacity Growth in the Electric Utility Industry

While the new source emission offset provision contained in recent acid rain proposals would result in increasing utility costs over time, the demand for emission offsets from new powerplant units should be satisfied even under conditions of high future growth in electrical generating capacity. This is because the amount of emissions from new generating units will be small relative to the quantity of offsets that could be made available in the emission “allowance” market.

Under the President’s July 1989 proposal, most utilities would be able to reduce their emissions well below their allowance levels via fuel switching, the installation of control technology, or the use of other emission reduction techniques, in order to create more “headroom” for the construction of new generating units. Retirements and decreasing utilization of existing power plants over time would liberate other emission allowances for use by new units. Industrial sources could “opt in” to the acid rain program and provide allowances for new generating units as well. A number of provisions in the recently passed Senate and House bills would make still further sources of allowances available to offset emissions from new generating capacity.

Hoarding of allowances by utilities is unlikely to be a problem since allowances would be distributed to at least 88 utilities in 34 states, and many of these utilities would have the ability to cost-effectively free up more allowances through “overcontrol” than they would need to cover their own future growth. Even a relatively small number of utilities in a limited number of states would have the ability to supply all of the allowances needed to cover new capacity growth from those entities that could not otherwise provide their own offsets. At projected prices of up to $800/ton, the incentives for utilities to sell allowances would be considerable. Moreover, if hoarding did begin to occur, the price of allowances would respond by rising to higher levels and the incentives for utilities to sell allowances would become even more compelling, as greater opportunities would develop for reducing costs (and electricity rates).     

Effects of Acid Rain and Gaseous Pollutants on Forest Productivity: A Regional Scale Approach

Increased industrialization of the eastern U.S. over the past several decades has led to regional scale buildup of atmospheric pollutants and concern over possible losses in forest productivity within this region. This paper describes the rationale, methodology, and some preliminary results of a large regional scale study designed to characterize and quantify forest growth impacts attributable to atmospheric stress from both gaseous pollutants and acid rainfall. This research employs a variety of dendroecological techniques to examine the influence of climatic factors, tree age, soil type, competition, and air pollution on tree growth. This broadly collaborative project involves twelve government and university research stations working with a common experimental protocol to examine ≥50 year ringwidth series from approximately 6000 trees distributed over an area extending from Maine to North Carolina and as far west as Missouri. Principal objectives of this research are to determine whether a systematic pattern of decreasing forest growth has occurred, to define its temporal, spatial, and quantitative characteristics, to determine its relationship to differences in soil quality and tree species, and to evaluate its correlation with present and past indices of atmospheric deposition.     

Characterization of Several Integrative Sampling Methods for Nitric Acid,Sulphur Dioxide and Atmospheric Particles

Laboratory and field experiments were performed to evaluate integrative measurement methods for atmospheric nitrates, sulphate and sulphur dioxide. Denuder tubes and several filter media were tested under laboratory and field conditions. Effects of sampling variables such as temperature and relative humidity, flow rates, concentration, loading capacity and artifacts due to NO, NO₂ and SO₂ were also evaluated. The integrative filter sampling method and the ion chromatographic analytical procedure gave a measurement precision (relative standard deviation) of ±11.5 percent for particulate NO₃ ^? on Teflon and ±15.6 percent for gaseous HNO₃ on nylon; for both these constituents, the detection limit was about 0.1 μ m^?3.     

Evaluation of Saltzman and Phenoldisulfonic Acid Methods for Determining NOx in Engine Exhaust Gases

The two methods normally used for the analysis of NO_x are the Saltzman and the phenoldisulfonic acid technique. This paper describes an evaluation of these wet chemical methods to determine their practical application to engine exhaust gas analysis. Parameters considered for the Saltzman method included bubbler collection efficiency, NO to NO₂ conversion efficiency, masking effect of other contaminants usually present in exhaust gases and the time-temperature effect of these contaminants on stored developed solutions. Collection efficiency and the effects of contaminants were also considered for the phenoldisulfonic acid method. Test results indicated satisfactory collection and conversion efficiencies for the Saltzman method, but contaminants seriously affected the measurement accuracy particularly if the developed solution was stored for a number of hours at room temperature before analysis. Storage at 32°F minimized effect. The standard procedure for the phenoldisulfonic acid method gave good results, but the process was found to be too time consuming for routine analysis and measured only total NO_x.     

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites.Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.     

A Comparison of Phenoldisulfonic Acid,Nondispersive Infrared,and Saltzman Methods for the Determination of Oxides of Nitrogen in Automotive Exhaust

The Saltzman Phenoldisulfonic Acid and Nondispersive Infrared methods have been compared for the determination of oxides of nitrogen in automobile exhaust. The main purpose of this investigation was to determine whether the Nondispersive Infrared method could be used as a possible replacement for the Saltzman method. Results show that the Nondispersive Infrared analyzer can be used to measure NO_x in exhaust gases with advantages over both the Saltzman and Phenoldisulfonic Acid methods. These advantages include simplicity, speed, less complicated analytical technique, and the fact that it is better adapted to be carried out by technicians at the test site.     

Economic Benefits of Improvements in Visibility: Acid Rain Provisions of the 1990 Clean Air Act Amendments

The Acid Rain Provisions (Title IV) of the Clean Air Act Amendments of 1990 call for about a 10 million ton reduction in annual SO₂ emissions in the United States. Although the provisions apply nationwide, most of the reduction will occur in the eastern half of the country, where use of high-sulfur coal for electricity generation is most common. One potentially large benefit of Title IV is the expected improvement in visibility conditions in the eastern United States due to the reductions in secondary sul-fate aerosols. This paper combines available economic estimates of willingness to pay for improvements in visibility with current estimates of the difference between expected visibility conditions in the eastern United States with and without Title I V, to estimate the expected visibility benefits of Title IV. The results suggest an annual value of $2.3 billion (in 1994 dollars) in the year 2010, as a result of visibility improvements due to Title IV in residential areas of the eastern United States. The results also suggest a possible additional annual value for eastern U.S. residents of as much as $1-2 billion for visibility improvements at national parks in the Southeast.     

Contributions of Acid Deposition and Natural Processes to Cation Leaching from Forest Soils: A Review

Methods of quantifying the roles of atmospheric acid inputs and internal acid generation by carbonic, organic, and nitric acids are illustrated by reviewing data sets from several intensively studied sites in North America. Some of the sites (tropical, temperate deciduous, and temperate coniferous) received acid precipitation whereas others (northern and subalpine) did not. Natural leaching by carbonic acid dominated soil leaching in the tropical and temperate coniferous sites, nitric acid (caused by nitrification) dominated leaching In an N-fixing temperate deciduous site, and organic acids dominated surface soil leaching in the subalpine site and contributed to leaching of surface soils in several other sites. Only at the temperate deciduous sites did atmospheric acid input play a major role in soil leaching. In no case, however, are the annual net losses of cations regarded as alarming as compared to soil exchangeable cation capital.

These results were used to illustrate the methods of quantifying the effects of atmospheric inputs and internal processes on soil leaching rates, not to draw broad generalizations as to acid rain effects on soils. However, there are predictable patterns in natural soil leaching processes which relate to climate, soil properties, and vegetation that may help in predicting the relative importances of natural vs. atmospheric acid inputs to soil leaching.     

Red Spruce Decline in the Northeastern U.S.: Hypotheses Regarding the Role of Acid Rain

Red spruce have died in abnormal numbers in the high elevation forests of New York and New England during the past two decades while spruce in the southern Appalachians remain healthy. Investigations of insect damage, fungal pathogens, successional dynamics, competitive status, climate and weather patterns and possible pollutant effects indicate that the decline was triggered by abiotic stress during the dry years of the 1960s. Tree response, as recorded in the pattern of annual rings, and the wide range of soil conditions in which spruce are declining, suggest drought or dry summers as key factors. Hypotheses regarding the role of acid deposition induced stress have been offered, but at present there is not evidence which clearly links acid deposition to spruce decline. Indirect effects of acid deposition on soils, direct effects of acid deposition on foliage, and interactions of acid deposition and drought stress are possible but unproven pathways by which acid deposition could be involved.