Nitrogen Compounds other than NO in Automobile Exhaust Gas

Recent studies of organic pyrolyses in the presence of nitric oxide have shown that various nitogen compounds, such as hydrogen cyanide (HCN) and aceto-nitrile (CH₃CN) are formed. This suggests the possibility that such compounds will be found in internal combustion processes, and may be present in automobile exhaust gases. The present paper describes some gas-chromatographic and wet analyses of exhaust gases. It is concluded that the amounts of hydrogen cyanide are less than 1 ppm, but that various organic nitrogen compounds may reach a level of about 100 ppm. The significance of these results is discussed.     

Microwave Plasma Conversion of Volatile Organic Compounds

Abstract

A microwave-induced, steam/Ar/O₂ , plasma “torch” was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N₂ can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NO_x ) is avoided in the plasma.

The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O₂ and steam.The O₂ was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500–600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O₂ was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Extraction and identification of volatile organic substances (VOS) from Scottish peat cores

The degradation of organic matter in peat bogs is complex and not yet well understood. Recent investigations of the trace gases CO₂ and CH₄ focussed on the impact of these greenhouse gases on global warming. However, there have to be metabolic intermediates between complex organic structures (i.e., humic acids) and gaseous end products (CH₄, CO₂, N₂, NO_x and H₂S) other than water-soluble substances (i.e., aromatic acids, amino acids, fatty acids). Deoxygenation during microbial decomposition of plant material also produces anoxic conditions that favor the formation of kinetically stable hydrocarbons. In this study, volatile organic substances (VOS) in peat bogs were investigated using two techniques: purge-and-trap and closed-loop stripping. Coupled gas chromatography–mass spectroscopy analysis revealed mainly branched hydrocarbons (C₈H₁₈) in concentrations up to 260 nM in peat pore-water. Additionally, alkylated benzenes were found in concentrations of up to 464 nM, in the peat pore-water, and up to 23 pptv in the headspace of peat cores. However, one-third of all the compounds in the complex VOS-fraction extracted from the peat system remain to be identified, especially those substances containing oxygen.     

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.     

有机废气吸附净化处理的新型工艺研究

简要介绍了挥发性有机废气的来源、分类及其对人体和环境的危害，以及盐城市部分企业近年来的产生和排放状况。较详细地论述了吸附净化处理技术用于废气中挥发性有机化合物的去除和回收研究工艺与特点，阐明了目前有机废气的净化处理方向。     

Standard Reference Gases and Analytical Procedures for Use in Gas Turbine Exhaust Measurements

This paper is directed to people who are involved in the measurement of gas turbine exhaust emissions and as a consequence in the establishment of standard reference gases and attendant analytical procedures.

Several problems exist in connection with the establishment of these standards:

A number of standard reference gases have been developed by the National Bureau of Standards for use in the automotive industry which are also suitable for gas turbine exhaust measurements. However, there is a need for additional standard reference materials such as NO in nitrogen, intermediate levels of CO₂ in air, and higher concentrations of CO in nitrogen and propane in air.

There is difficulty in maintaining certain reference materials with confidence in assay, particularly due to instability in the cylinder.

Instrumental operational problems with flame ionization detector type units exist. Of particular importance is the difference in response per carbon atom in different organic molecules and the difference in response of a test sample as a function of the oxygen content of the sample.

Instrumental method problems such as converter efficiency in chemiluminescence units measuring NO₂ and calibration techniques involving CO to CH₄ conversion, also must be considered.

A number of problems occur in the use of wet chemical reference methods such as the phenoldisulfonic acid method for the determination of NO_x. These include both efficiency of collection, conversion of NO to NO₂, and subsequent analysis.

This paper considers the development of standards for the measurement of NO_x, CO, CO₂, total hydrocarbons, and O₂ and reviews the state-of-the-art with respect to these problems and their resolution.     

Characterisation of single particles from in-port ship emissions

Emissions from shipping traffic may impact severely upon air quality in port cities. In this study, the size and composition of freshly emitted individual ship exhaust particles has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS) co-located with a suite of real-time instrumentation at a site in the Port of Cork, Ireland. The collected spectra were clustered using the K-means algorithm and a unique ship exhaust class containing internally mixed elemental and organic carbon, sodium, calcium, iron, vanadium, nickel and sulfate was identified. Over twenty sharp emission events were observed for this particle type during the three week measurement period in August 2008. Coincident increases in mass concentrations of sulfate, elemental carbon and particles below 2.5 μm in diameter (PM_2.5) were also observed during these events. Simultaneous scanning mobility particle sizer (SMPS) measurements indicate that the vast majority of freshly emitted ship exhaust particles lie in the ultrafine mode (<100 nm diameter). A second particle class consisted of internally mixed organic carbon, elemental carbon, ammonium and sulfate, and is tentatively attributed to aged or regionally transported ship exhaust. The results suggest that ATOFMS single particle mass spectra, when used in conjunction with other air quality monitoring instrumentation, may be useful in determining the contribution of local shipping traffic to air quality in port cities.     

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

Characterization of organic aerosol in Big Bend National Park,Texas

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was conducted in Big Bend National Park, Texas, July through October 1999. Daily PM_2.5 organic aerosol samples were collected on pre-fired quartz fiber filters. Daily concentrations were too low for detailed organic analysis by gas chromatography-mass spectrometry (GC-MS) and were grouped based on their air mass trajectories. A total of 12 composites, each containing 3–10 daily samples, were analyzed. Alkane carbon preference indices suggest primary biogenic emissions were small contributors to primary PM_2.5 organic matter (OM) during the first 3 months, while in October air masses advecting from the north and south were more strongly influenced by biogenic sources. A series of trace organic compounds previously shown to serve as particle phase tracers for various carbonaceous aerosol source types were examined. Molecular tracer species were generally at or below detection limits, except for the wood smoke tracer levoglucosan in one composite, so maximum possible source influences were calculated using the detection limit as an upper bound to the tracer concentration. Wood smoke was found not to contribute significantly to PM_2.5 OM, with contributions for most samples at <1% of the total organic particulate matter. Vehicular exhaust also appeared to make only minor contributions, with maximum possible influences calculated to be 1–4% of PM_2.5 OM. Several factors indicate that secondary organic aerosol formation was important throughout the study, and may have significantly altered the molecular composition of the aerosol during transport.     

生活污水不同进水C/N比负荷对垂直潜流式人工湿地排放温室气体的影响

人工湿地处理的生活污水含氮量或者有机物含量很高时,可能会造成人工湿地在处理污水的过程中排放大量温室气体。研究了垂直潜流式人工湿地在人工合成的生活污水不同污染物进水C/N负荷条件下污水处理效果和温室气体(CO2和CH4)的排放量,利用现场测量和碳平衡模型估算分析了可以达到最佳污水净化效果和最少温室气体排放量的污染物进水C/N负荷条件。结果显示,在进水C/N负荷为C/N=6∶1~9∶1时可以得到最佳的污染物去除率。温室气体CH4排放量较CO2排放量可以忽略不计,而在进水C/N负荷为C/N=3∶1~6∶1时可以实现最少的温室气体排放。综上所述,最优的进水C/N负荷确定为C/N=6∶1,此时人工湿地可以得到较高的污染物去除率而排放较少的温室气体。     

A Portable Fiber-Optic Chemical Device for the Quantitative Determination of Carbon Monoxide from Automobile Exhaust Emissions

ABSTRACT

A colorimetxic method for the quantitative determination of CO by diffuse reflectance is described. This method is based on the reduction by CO of Mo (VI) from the indicator reagent molybdosilicic acid (H₈Si[Mo₂O₇]₆). The reduction yielded a change of color from clear yellow to dark green on white disk filter chart paper wetted with reagent indicator solution. The gaseous mixture containing CO was forced to pass through this chart paper, initiating the reaction. The intensity of the color produced, measured by diffuse reflectance, was proportional to the CO concentration present in exhaust gases in the range from 0.02 to 12% volume/volume (v/v). A 650-nm light-emitting diode was used as a light source. A two-fiber-optic system carried the light from the source to the detection system, which was composed of a photodiode, an amplification circuit, and a digital display. The method was applied with success in field measurements for automobiles in the Otto cycle. In a previous paper, this method was used for the quantitative determination of exhaust emissions from diesel-fueled vehicles.¹     

Development of a High-Temperature Subtractive Analyzer for Hydrocarbons

This paper discusses the development of a high-temperature subtractive analyzer for separating the hydrocarbons present in gaseous mixtures into two categories— reactive hydrocarbons and unreactive hydrocarbons. The analyzer utilizes the ability of selected substances to absorb certain groups of hydrocarbons and their derivatives from a gas mixture and is designed for operation with a flame ion-ization detector. The body of information presented in this paper is directed to individuals concerned with the analysis of the exhaust gases of gas turbine engines or other combustion sources as stationary power plants. The analyzer grew out of an investigation of a previously reported subtractive analyzer system which operates at ambient temperature. Current state-of-the-art requirements for the accurate determination of total hydrocarbons at the concentrations present in turbine exhaust gases necessitate that sampling and measurements be conducted at elevated temperatures (325-375°F), rather than ambient temperature, to reduce or eliminate condensation and wall adsorption sampling errors. To fulfill this requirement, the sampling lines and flame ionization detector must be heated. After tests determined that the previously reported scrubber system would not remove the same hydrocarbons at elevated temperature levels as it did at ambient temperatures, an investigation of the effectiveness of various absorbents at elevated temperatures was conducted. This led to the development and test of the high-temperature subtractive analyzer concept discussed in this report. In its final form, one path of this unit contains no absorbent, the second contains a column of concentrated H₂SO₄ on Ultraport and a column containing PdSO₄ and H₂SO₄ on Ultraport. The two columns are connected in series. The absorbents remove olefins, aromatics, acetylene, and oxygenated hydrocarbons but pass paraffins. As the final step in this program, a comparison of the two subtractive analyzers was made using the exhaust from a gas turbine combustion system.     

Rapid measurement of emissions from military aircraft turbine engines by downstream extractive sampling of aircraft on the ground: Results for C-130 and F-15 aircraft

Aircraft emissions affect air quality on scales from local to global. More than 20% of the jet fuel used in the U.S. is consumed by military aircraft, and emissions from this source are facing increasingly stringent environmental regulations, so improved methods for quickly and accurately determining emissions from existing and new engines are needed. This paper reports results of a study to advance the methods used for detailed characterization of military aircraft emissions, and provides emission factors for two aircraft: the F-15 fighter and the C-130 cargo plane. The measurements involved outdoor ground-level sampling downstream behind operational military aircraft. This permits rapid change-out of the aircraft so that engines can be tested quickly on operational aircraft. Measurements were made at throttle settings from idle to afterburner using a simple extractive probe in the dilute exhaust. Emission factors determined using this approach agree very well with those from the traditional method of extractive sampling at the exhaust exit. Emission factors are reported for CO₂, CO, NO, NO_x, and more than 60 hazardous and/or reactive organic gases. Particle size, mass and composition also were measured and are being reported separately. Comparison of the emissions of nine hazardous air pollutants from these two engines with emissions from nine other aircraft engines is discussed.     

Emission of specific pollutants from a compression ignition engine. Influence of fuel hydrotreatment and fuel/air equivalence ratio

A compression ignition engine is used for the study of the fuel (one reference and one hydrotreated) and the fuel/air equivalence ratio influence on the exhaust emissions of specific pollutants. Under the experimental conditions used, seven hydrocarbons, nine aldehydes and three organic acids are detected in the exhaust gas. No alcohols are detected under these conditions, indicating that these compounds are emitted only if they (or probably other oxygenated compounds) are introduced in the fuel. Fuel hydrotreatment decreases most of the exhaust pollutants, the four toxics and also the quantity of the ozone that could be formed from the exhaust gas. It also changes the composition of exhaust gas: it increases the proportion of methane, benzene, formaldehyde, acetaldehyde, acroleine, and propionic acid, while it decreases the proportion of all other pollutants detected. Fuel/air equivalence ratio also decreases most of the exhaust emissions, the emission of the total toxics and the quantity of the ozone that could be formed. It also changes the proportion of each pollutant in exhaust gas: the percentages of methane, benzene, acetone and acetic acid increase, while those of the other pollutants detected decrease. The majority of the specific pollutants detected corresponds to organic acids, followed by hydrocarbons and aldehydes.     

The Distribution of Particle-Phase Organic Compounds in the Atmosphere and Their Use for Source Apportionment during the Southern California Children’s Health Study

Abstract

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children’s Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), ho-panes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM₁₀ organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Characterisation of particulate matter and gaseous emissions from a large ship diesel engine

Composition of exhaust from a ship diesel engine using heavy fuel oil (HFO) was investigated onboard a large cargo vessel. The emitted particulate matter (PM) properties related to environmental and health impacts were investigated along with composition of the gas-phase emissions. Mass, size distribution, chemical composition and microphysical structure of the PM were investigated. The emission factor for PM was 5.3 g (kg fuel)^?1. The mass size distribution showed a bimodal shape with two maxima: one in the accumulation mode with mean particle diameter D_P around 0.5 μm and one in the coarse mode at D_P around 7 μm. The PM composition was dominated by organic carbon (OC), ash and sulphate while the elemental carbon (EC) composed only a few percent of the total PM. Increase of the PM in exhaust upon cooling was associated with increase of OC and sulphate. Laser analysis of the adsorbed phase in the cooled exhaust showed presence of a rich mixture of polycyclic aromatic hydrocarbon (PAH) species with molecular mass 178–300 amu while PM collected in the hot exhaust showed only four PAH masses.Microstructure and elemental analysis of ship combustion residuals indicate three distinct morphological structures with different chemical composition: soot aggregates, significantly metal polluted; char particles, clean or containing minerals; mineral and/or ash particles. Additionally, organic carbon particles of unburned fuel or/and lubricating oil origin were observed. Hazardous constituents from the combustion of heavy fuel oil such as transitional and alkali earth metals (V, Ni, Ca, Fe) were observed in the PM samples.Measurements of gaseous composition in the exhaust of this particular ship showed emission factors that are on the low side of the interval of global emission factors published in literature for NO_x, hydrocarbons (HC) and CO.     

Identification of a potential source of chloroform in urban air: Preliminary Communication

A new potential source of elevated chloroform (CHCl₃) concentrations in urban air is reported. The exhaust gases from gasoline internal combustion engines operated on conventional “leaded” fuel and not equipped with catalytic converters contain parts-per-billion concentrations of chloroform which can, in congested urban areas, contribute significantly to the ambient concentration of chloroform. Exhaust gases from engines burning conventional “leaded” gasoline contain much higher levels of chloroform than do exhaust gases from engines equipped with catalytic converters and operating on “nonleaded” gasoline.     

Capturing the lost phosphorus

Minable phosphorus (P) reserves are being depleted and will need to be replaced by recovering P that currently is lost from the agricultural system, causing water-quality problems. The largest two flows of lost P are in agricultural runoff and erosion (∼46% of mined P globally) and animal wastes (∼40%). These flows are quite distinct. Runoff has a very high volumetric flow rate, but a low P concentration; animal wastes have low flow rates, but a high P concentration together with a high concentration of organic material. Recovering the lost P in animal wastes is technically and economically more tractable, and it is the focus for this review of promising P-capture technologies. P capture requires that organic P be transformed into inorganic P (phosphate). For high-strength animal wastes, P release can be accomplished in tandem with anaerobic treatment that converts the energy value in the organic matter to CH₄, H₂, or electricity. Once present as phosphate, the P can be captured in a reusable form by four approaches. Most well developed is precipitation as magnesium or calcium solids. Less developed, but promising are adsorption to iron-based adsorbents, ion exchange to phosphate-selective solids, and uptake by photosynthetic microorganisms or P-selective proteins.     

铁盐和铝盐混凝对印染废水生化出水中溶解性有机污染物的去除特性

以三氯化铁和硫酸铝为混凝剂,印染废水二级生化出水为研究对象,并利用XAD-8/XAD-4吸附树脂联用技术将印染废水生化出水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,通过小试实验探讨了2种混凝剂对生化出水中各类溶解性有机物的去除效果及特点。实验结果表明,对于该印染废水的生化出水,溶解性有机物的主要成分是疏水性物质,以DOC表征时占总DOC的75%,其中疏水酸约占41%,疏水性物质也是引起色度的主要物质,所占比例以ADMI7.6表征时为89%,其中以非酸疏水物质的贡献最大,达到52%,并且非酸疏水物质中不饱和双键或芳香环有机物的含量较高。在三氯化铁和硫酸铝各自最佳的混凝条件下,均能够有效去除由疏水性物质（疏水酸和非酸疏水物质）引起的色度,但三氯化铁对弱疏水性物质以及亲水物质的去除率高于硫酸铝,这使得三氯化铁对印染废水生化出水中的溶解性有机物的去除效果优于硫酸铝。并且三氯化铁和硫酸铝混凝工艺均能明显降低生化出水的毒性。