Kinetics of the tropospheric formaldehyde loss onto mineral dust and urban surfaces

The kinetics of the heterogeneous reaction between gaseous HCHO and TiO₂/SiO₂ mineral coatings were investigated using a coated-wall flow tube to mimic HCHO loss on mineral aerosol and TiO₂ coated depolluting urban surfaces. The measured uptake kinetics were strongly enhanced when the flow tube was irradiated with 340–420 nm UV light with an irradiance of 1.45 mW cm^?2. The associated BET uptake coefficients ranged from (3.00 ± 0.45) × 10^?9 to (2.26 ± 0.34) × 10^?6 and were strongly dependent on HCHO initial concentration, relative humidity, temperature, and TiO₂ content in the mineral coating, which ranged from 3.5 to 32.5 ppbv, 6–70%, 278–303 K, and 1–100 %wt, respectively. The measured kinetics were well described using a Langmuir–Hinshelwood type formalism. The estimated uptake coefficients were used to discuss the importance of heterogeneous HCHO surface loss, in terms of deposition lifetimes, as compared to major homogeneous gas-phase losses such as OH reaction and photolysis. It is found that deposition may compete with gas-phase removal of HCHO in a dense urban environment if more than 10% of the urban surface is covered with TiO₂ treated material.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

Development of an aggregate Air Quality Index for an urban Mediterranean agglomeration: relation to potential health effects

It is very useful for the authorities and the people to have daily easy understandable information about the levels of air pollution and the proper measures to be taken for the protection of human health. In this paper we develop an aggregate Air Quality Index (AQI) based on the combined effects of five criteria pollutants (CO, SO2, NO2, O3 and PM10) taking into account the European standards. We evaluate it for each monitoring station and for the whole area of Athens, Greece, an area with serious air pollution problems. A comparison was made with a modified version of Environmental Protection Agency/USA (USEPA) maximum value AQI model adjusted for European conditions. Hourly data of air pollutants from 4 monitoring stations, available during 1983-1999, were analysed for the development of the proposed index. The analysis reveals the Athenian population exposure reaches high levels and during last years a gradual increase of days with unhealthy conditions was detected. The proposed aggregate model estimates more effectively the exposure of citizens comparing with the modified USEPA maximum value model, because counts the impact of all the pollutants measured. Towards the informing and protection of the citizens in an urban agglomeration this model advantages as a political and administrative tool for the design of abatement strategies and effective measures of intervention.     

Comparison of quartz sand, anthracite, shale and biological ceramsite for adsorptive removal of phosphorus from aqueous solution

The choice of substrates with high phosphorus adsorption capacity is vital for sustainable phosphorus removal from waste water in constructed wetlands. In this study, four substrates were used： quartz sand, anthracite, shale and biological ceramsite. These substrate samples were characterized by X- ray diffractometry and scanning electron microscopy studies for their mineral components （chemical components） and surface characteristics. The dynamic experimental results revealed the following ranking order for total phosphorus （TP） removal efficiency： anthracite 〉 biological ceramsite 〉 shale 〉 quartz sand. The adsorptive removal capacities for TP using anthracite, biological ceramsite, shale and quartz sand were 85.87, 81.44, 59.65, and 55.98 mg/kg, respectively. Phosphorus desorption was also studied to analyze the substrates＇ adsorption efficiency in wastewater treatment as well as the substrates＇ ability to be reused for treatment. It was noted that the removal performance for the different forms of phosphorus was dependent on the nature of the substrate and the adsorption mechanism. A comparative analysis showed that the removal of particulate phosphorus was much easier using shale. Whereas anthracite had the highest soluble reactive phosphorus （SRP） adsorptive capacity, biological ceramsite had the highest dissolved organic phosphorus （DOP） removal capacity. Phosphorus removal by shale and biological ceramsite was mainly through chemical adsorption, precipitation or biological adsorption. On the other hand, phosphorus removal through physical adsorption （electrostatic attraction or ion exchange） was dominant in anthracite and quartz sand.     

Formalising informal solid waste recycling at the Pomona dumpsite in Harare,Zimbabwe

The role of informal recycling in poverty alleviation and solid waste management in cities in developing countries has been receiving increased attention. This study explores the integration of the informal recycling sector with the Harare City Council's solid waste management system, focusing on the Pomona dumpsite. The extent of this integration was compared with interventions proposed in InteRa, a new way of evaluating the integration of informal recyclers with the waste management systems of cities in developing countries. Our results suggest that the Harare City Council, which had the vision of transforming itself into a world‐class city, failed to fully integrate the informal recycling sector. We suggest to policymakers that complete integration of the informal sector will not necessarily prevent cities from achieving such visions. Rather, addressing the neglected interventions may help in achieving their visions.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.     

Wild tomato leaf extracts for spider mite and cowpea aphid control

Glandular trichomes on the leaves of wild tomato, L. hirsutum f. hirsutum Mull, also known as Solanum habrochaites (Solanaceae), synthesize and accumulate high levels of methyl ketones (MKs). L. hirsutum accession LA 407, having high concentration of MKs, was grown from seeds under greenhouse conditions. Four MKs (2-undecanone, 2-dodecanone, 2-tridecanone, and 2-pentadecanone) were screened for their toxicity to spider mites, Tetranychus urticae Koch and cowpea aphids, Aphis craccivora Koch. The objectives of this investigation were to: (1) develop a bioassay for testing MKs on spider mite and cowpea aphid mortality and (2) compare the efficacies of wild tomato leaf crude extracts and pure standard materials of MKs against spider mite and cowpea aphid mortality. Our results revealed that spider mites are most sensitive to 2-tridecanone (LC₅₀ = 0.08 μmole cm^?2 of treated leaf surface) and least sensitive to 2-undecanone (LC₅₀ = 1.5 μmole cm^?2 of treated leaf surface) 4 h after treatment. Similarly, 2-tridecanone caused greatest mortality (LC₅₀ = 0.2 μmole cm^?2 of treated leaf surface), whereas 2-undecanone caused the lowest morality (LC₅₀ = 0.48 μmole cm^?2 of treated surface) of cowpea aphid. We concluded that all MKs tested in this investigation are toxic to spider mites and aphids. 2-Tridecanone is more effective in killing mites and aphids compared to other MKs. Toxicity of crude extracts, prepared from the leaves of L. hirsutum accession LA 407, to spider mites and cowpea aphids revealed greater mortality compared to a combined mixture of MKs standard material (used at the same concentration as found on LA 407 leaves). This indicates that in addition to MKs, other unidentified compounds in LA 407 leaf extract also have pesticidal properties. Accordingly, leaf extracts of LA 407 could be explored in crop protection, and they might open a new area of MK formulations and discovery of biorational alternatives for pest control in agricultural fields.     

Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

Jet Aircraft Operations: Impact on the Air Environment

This paper is directed to those concerned with the air environment and its degradation by the burden of pollution from jet aircraft operations. A summary is presented of the results of a comprehensive air pollution study of jet aircraft operations at the Los Angeles International Airport (LAX). Included in the data obtained from this study are jet engine exhaust measurements for currently used turboprop, turbojet and turbofan engines; measurements of specific contaminants in the atmosphere inside and outside of passenger terminals and ticketing areas, and in aircraft cabins during ground operations including passenger loading and taxiing prior to takeoff; also presented are ambient air measurements in a two-mile radius of the airport. An evaluation is made of the emissions of contaminants from air transport operations and all related ground activities including motor vehicles, that contribute to the total atmospheric contaminant burden at the airport.