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.     

Platinum emission rate of automobiles with catalytic converters

Inconsistent data presently available on the platinum emission rate of cars in Germany equipped with catalytic converters are evaluated. Automobile sources of Pt other than autocatalysts are quantified and found to be 1–6 orders of magnitudes lower than the Pt emissions attributed to catalytic converters. A transfer of emission rates derived from test stand experiments to more realistic street conditions reaches 0.8 μg Pt/km. In this manner, data from test stand experiments and from environmental investigations meet in the range of 0.5–0.8 μg Pt/km.     

Biological Effects of Carbon Monoxide vs. Whole Emissions from Engine with Catalyst

The introduction of oxidizing catalytic converters in the exhaust system of automobiles has been found to be effective in reducing carbon monoxide, total hydrocarbons, and some other components of tailpipe emissions. The utilization of these converters, however, has also caused further oxidation of sulfur compounds producing an increased amount of sulfur trioxide (SO₃) which yields sulfuric acid and sulfates.¹ Studies on the biological effects of these sulfur compounds are in progress in our laboratory and preliminary findings are reported separately. This paper compares the biological effects of exposure to whole emissions from engines with and without converter and exposure to carbon monoxide alone.     

Long-term efficiency of catalytic converters operating in Mexico City

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones. The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NOx emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure FTP-75. Our results suggest that the replacement of old catalytic converters with new ones will have little effect on decreasing polluting emissions because these vehicles were in very bad mechanical condition. Results of catalytic activity as a function of mileage indicated inefficient catalyst performance for the fleets tested. All pollutant conversions were below 90% efficiency, and they deteriorated by an average of 30% after the vehicles were run for 100,000 km.     

Anthropogenic platinum fluxes: Quantification of sources and sinks, and outlook

Employing the data available to date, anthropogenic Pt fluxes are calculated for Germany with special emphasis on the Pt emitted by cars equipped with catalytic converters. Pt fluxes are quantified using five different methods (street deposition, automobile emission rate, sewage sludges, atmospheric load, industrial consumption). During the first and the second methods, approx. 100 kg of emitted Pt are seen to result for both for the mid 1990’s. Up to the year 2018, a total of 2100 kg of Pt will be emitted by cars equipped with catalytic converters. The diffuse atmospheric Pt deposition amounts to 0.73 – 4.4 μg/m²y or 260 kg Pt/year. Industrial sources emitting Pt into the atmosphere are likely but difficult to quantify. The enrichment of Pt in soils during agriculture fertilization with sewage sludges and during diffuse atmospheric deposition result in a level of 46 – 460 ng/kg up to the year 2018. Although this is slightly below the geogenic background, a comparison with the pollution history of Pb implies that forthcoming environmental Pt enrichment should not be neglected.     

车用催化转化器的数值模拟与实验研究

采用数值模拟和实验相结合的方法比较了常规结构和一种特殊结构双载体三效催化转化器的性能。数值模拟的结果表明,安装环形片的催化转化器流动均匀性优于常规结构的催化转化器。实验结果表明,安装环形片可以提高催化器的转化效率。     

Long-Term Efficiency of Catalytic Converters Operating in Mexico City

ABSTRACT

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones.

The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NO_x emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure     

Application of a Chemical Mass Balance Receptor Model to Respirable Particulate Matter in Mexico City

Mexico City frequently experiences high levels of air pollution. This is due mainly to its topography and meteorology that suppress pollutant diffusion and dispersion. The atmospheric mixing is extremely poor, especially during the dry winter months. The levels of certain pollutants, such as particulate matter, are of concern since they have severe effects on public health. Visibility deterioration

is one of the most noticeable effects in large cities. Biological effects of particulate matter on man and animals, ranging from mild eye irritation to death, have been reported. The effects depend on the size of the particles, their solubility, and toxicity. The main objective of this paper is to present the results of a chemical mass balance receptor model applied to a well-characterized data set of particulate matter collected in the Mexico City Metropolitan Area (MCMA). Samples of particulate matter were collected using a denuder and a Hi-Vol system for the respirable fraction and total suspended particles, respectively.

In this paper the analysis of a database consisting of the chemical composition of 33 samples of respirable particulate matter (aerosols with diameter less than 2.5 μm) is presented. The 12-hour samples were acquired during day and night periods in a typical medium-income neighborhood from December 19, 1989 through February 5, 1990.

The results show that the main contributors to suspended particles are vehicles without catalytic converters and heavy-duty diesel vehicles. The contribution of refineries, smelters, cement plants, resuspended dust, natural sources, and secondary aerosols were taken into account. In particular, the vehicles without catalytic converters represent the major contribution to PM2.5. They contribute with 50% during the day and 38% at night. Most of the source profiles were taken from the model library SPECIATE EPA. However, native profiles for soil, vehicles, and refinery were designed.     

Studies on reactions of ozone with alkenes

In the last years, a continuous increase of the O3 concentration has been recorded in the lower atmospheric layers. Photochemical reactions with NO(x), CO and organic compounds are the main sources of O3 in the troposphere. In this work, an attempt was made to determine the impact of alkenes on the O3 concentration in the troposphere. A study on the gas-phase reactions of 03 with 1-hexene, 1-heptene and 1-nonene was made. The reactions were carried out at room temperature under atmospheric pressure. Ozone was formed by the ultraviolet radiation emitted by a mercury lamp, in order to simulate the atmospheric conditions. The changes with time in the concentration of O3, 1-alkenes and formed aldehydes were investigated. Qualitative and quantitative analyses were done by means of the gas chromatography and colorimetry. The following products were identified: pentanal from 1-hexene; hexanal from 1-heptene; oktanal from 1-nonene. For each of the reactions, HCHO was also determined as a product. The reaction rate constants were calculated and obtained in units of 10(-17) cm(-3) molecule(-1) s(-1): 1.94-0.99 for 1-hexene, 5.54-4.51 for 1-heptene and 1.54-0.76 for 1-nonene. Based on the results obtained, an explanation of O3 concentration variations in the planetary boundary layer can be given. Last year a considerable increase of O3 concentration on the roads of Western Europe was recorded. This increase could have resulted from the decrease of alkene concentration in the air due to common use of the catalytic converters in cars. The unsaturated hydrocarbons rapidly oxidize on the catalyst. In Eastern Europe, where the amount of cars equipped with catalytic converters is smaller than in Western Europe, the alkene content in the exhaust fumes results in a decrease of the O3 concentration in the troposphere.     

Monitoring of air pollution in Indian metropolitan cities: modelling and quality indexing

Air quality in cities is the result of a complex interaction between natural and anthropogenic environmental conditions. Delhi, as well as many other cities in India, is facing problems concerning air pollution. The increase in industrialisation and the vehicle fleet, poor control on emissions and little use of catalytic converters, produce a great amount of particulate and toxic gases. Data on air pollutants and meteorological variables were collected in the metropolitan cities Delhi, Kolkata, Mumbai and Chennai for the period July–August, 2001. Data were treated with the bivariate regression model to explore the influence of the meteorological variables on air pollutant concentrations, and were also used to compute an Air Quality Index, using the weighted arithmetic mean method. The proposed index seems to be applicable in the assessment of overall air quality with respect to air pollutants.     

Some aspects of air pollution in Córdoba,Argentina

Córdoba, as well as many other Latin American cities, is facing problems concerning air pollution. The increase in the number of cars, the poor control on emissions and the little use of catalytic converters, produce a great amount of toxic gases and particulate. Many cities have started air quality measurement programs being the size of the network strongly dependent on the available funds. In 1995, Córdoba started a measurement campaign with two mobile stations. A major part of the city has been characterized, mostly the city center and the suburban zone. Lack of data at the prevailing wind direction is the major shortcoming, but this is mainly a political decision. In this work, we review the air quality measurements performed, and we attempt to explain the causes for the low ozone values found.     

Influence of micro-organisms on the dissolution of metallic platinum emitted by automobile catalytic converters

Platinum emitted by automotive catalyst converters mainly exists in the metallic form, which is not bioavailable. Several investigations showed that finely dispersed metallic platinum is dissolved in organic matrices to a significantly high degree [1,2]. In an exclusion experiment, observations were made as to whether the transformation of Pt(0) and other platinum compounds is mainly of a chemical nature or is influenced by micro-organisms. A previous experiment [2], concerning the interaction of several platinum compounds with a clay-like humic soil was repeated under sterile conditions to rule out the influence of micro-organisms. During the time of interaction (3–60 d), no significant differences were observed between the sterile and non-sterile modes. Thus, the dissolution of metallic platinum into soluble species, observed previously within this time period [2], seems to be mainly of a chemical nature. On leave from Liaoning University, Department of Chemistry, 110036 Shenyang, PR China     

Monuments as sampling surfaces of recent traffic pollution

Background, aim and scope  

A new approach towards monuments, considering them as a passive sampler of pollution, is presented. Cultural Heritage objects suffer daily the damages of environmental pollution, especially in those areas interested by heavy traffic. Since monuments undergo only periodic conservation or maintenance works, surfaces are able to accumulate atmospheric deposit and to record changes in its composition. An optimised analytical protocol was developed in order to quantify platinum and rhodium at trace level on surfaces. The two elements have become tracers of automobile emissions in recent years, since the introduction of catalytic converters, and could have catalytic effects on the decay reactions of natural and artificial stone materials. As a first case study, the cement mortar surfaces of a twentieth century monument, the Camerlata Fountain, in Como (Italy) were investigated.     

Development of a Method for the Analysis of NO2 and NH3 by NO-Measuring Instruments

Adaptation of available instruments to the analysis of NO₂ and NH₃ became important with the introduction of the Federal Constant Volume Sampling procedure for exhaust analysis in 1970. Two instruments, the NO optical detector (NOOD) and the non-dispersive infrared analyzer (ND1R), are both fast and accurate. The use of a system of two converters in conjunction with either of these instruments permits the analysis of a gas stream for NO, NO₂, and NH₃. NO is measured on the gas stream before conversion; NO₂ is determined after the gas stream has passed over a C-Mo converter at 475°C; and NH₃ is determined after the gas has been conducted over a C-Cu converter.     

Trends of exhaust emissions from gasoline motor vehicles in the metropolitan area of Mexico city

Light duty gasoline vehicles account for most of CO, hydrocarbons and NO_x emissions to the urban environment in the metropolitan area of Mexico City. In order to ameliorate air pollution, several control measures have been imposed in the last decade, such as: up-grade of gasoline's quality, stringent environmental standards, and catalytic converters. On the other hand and from the beginning of 2001, Tier I emission standards became mandatory for all new model year sold in the country. Car manufacturers in Mexico do not guarantee the performance of their exhaust emissions systems for a given mileage. In this work, we present results on brand new vehicles that indicate that NO_x emission factors, though they are within the Tier I standard, deteriorate rapidly with the travelled distance (mileage).     

A Laboratory Method for the Simulation of Automobile Exhaust and Studies of Catalyst Poisoning

The expected use of catalytic converters on automobiles to meet the legislated automotive emission standards makes desirable a laboratory method that permits realistic testing of these catalysts. Such a method should be versatile enough to simulate a wide range of conditions which are applicable for catalysts designed to oxidize hydrocarbons and carbon monoxide, or to reduce nitric oxide, as the case may be. For this purpose, we have modified a pulse-flame combustor, based on a design by Meguerian. The output of this simulator very closely resembles engine exhaust with respect to composition, space velocity, and contaminants. The durability of a monolithic or pelleted catalyst can be evaluated by long term exposure to the simulated exhaust and by periodic measurement of the catalyst activity as a function of temperature. The apparatus and the range of conditions that can be achieved are described in detail. Poisoning of a Pt catalyst by fuels containing low concentrations of lead was studied with this exhaust simulator and compared with results obtained in engine dynamometer tests; a satisfactory correlation of catalyst deterioration was established.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg⁻¹ were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg⁻¹ were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.     

Pd-nanoparticles cause increased toxicity to kiwifruit pollen compared to soluble Pd(II)

In the present study, endpoints including in vitro pollen performance (i.e., germination and tube growth) and lethality were used as assessments of nanotoxicity. Pollen was treated with 5-10 nm-sized Pd particles, similar to those released into the environment by catalytic car exhaust converters. Results showed Pd-nanoparticles altered kiwifruit pollen morphology and entered the grains more rapidly and to a greater extent than soluble Pd(II). At particulate Pd concentrations well below those of soluble Pd(II), pollen grains experienced rapid losses in endogenous calcium and pollen plasma membrane damage was induced. This resulted in severe inhibition and subsequent cessation of pollen tube emergence and elongation at particulate Pd concentrations as low as 0.4 mg L⁻¹. Particulate Pd emissions related to automobile traffic have been increasing and are accumulating in the environment. This could seriously jeopardize in vivo pollen function, with impacts at an ecosystem level.     

Assessing the real-world performance of modern pollutant abatement systems on motorcycles

The present statutory pollutant emission limits Euro-3 for motorcycles imply the use of modern emission abatement systems such as three-way catalytic converters. Determining the quality of implementation of these new systems in different driving situations such as real-world driving is important, since motorcycles are commonly used for personal transportation in urban areas. For this reason, a test bench series was carried out with a sample of 10 motorcycles of state-of-the-art certification category Euro-3. Emission factors of regulated pollutants and CO₂ are presented on the basis of the statutory driving cycle, the latest version of the real-world Worldwide Motorcycle Test Cycle (WMTC) and the real-world Common Artemis Driving Cycle (CADC).The results of the statutory driving cycle show that 7 out of 10 motorcycles fail to comply with the present emission limits. The results of both real-world driving cycles confirm notable emissions of HC in urban and NO_x in motorway driving conditions. CO emissions of motorcycles with small displacement increase significantly in the urban and extra-urban sections of the CADC, which has a more dynamic velocity profile than the equivalent WMTC. Although pollutant emissions of motorcycles show a marked improvement compared with earlier certification classes, they clearly exceed the emission levels of modern light gasoline passenger cars, especially for CO and HC.