An economic air pollution control model-application : photochemical smog in Los Angeles County in 1975

An economic air pollution control model, which determines the least cost of reaching various air quality levels, is formulated. The model takes the form of a general, nonlinear, mathematical programming problem. Primary contaminant emission levels are the independent variables. The objective function is the cost of attaining various emission levels and is to be minimized subject to constraints that given air quality levels be attained.

The model is applied to a simplified statement of the photochemical smog problem in Los Angeles County in 1975 with emissions specified by a two-dimensional vector, total reactive hydrocarbon, (RHC), and nitrogen oxide, (NO_x), emissions. Air quality, also two-dimensional, is measured by the expected number of days per year that nitrogen dioxide, (NO₂), and mid-day ozone, (O₃), exceed standards in Central Los Angeles.

The minimum cost of reaching various emission levels is found by a linear programming model. The base or "uncontrolled" emission levels are those that will exist in 1975 with the present new car control program and with the degree of stationary source control existing in 1971. Controls, basically "add-on devices", are considered here for used cars, aircraft, and existing stationary sources. It is found that with these added controls, Los Angeles County emission levels [(1300 tons/day RHC, 1000 tons /day NO_x) in 1969] and [(670 tons/day RHC, 790 tons/day NO_x) at the base 1975 level], can be reduced to 260 tons/day RHC (minimum RHC program) and 460 tons/day NO_x (minimum NO_x program).

"Phenomenological" or statistical air quality models provide the relationship between air quality and emissions. These models estimate the relationship by using atmospheric monitoring data taken at one (yearly) emission level and by using certain simple physical assumptions, (e. g., that emissions are reduced proportionately at all points in space and time). For NO₂, (concentrations assumed proportional to NO_x emissions), it is found that standard violations in Central Los Angeles, (55 in 1969), can be reduced to 25, 5, and 0 days per year by controlling emissions to 800, 550, and 300 tons /day, respectively. A probabilistic model reveals that RHC control is much more effective than NO_x control in reducing Central Los Angeles ozone. The 150 days per year ozone violations in 1969 can be reduced to 75, 30, 10, and 0 days per year by abating RHC emissions to 700, 450, 300, and 150 tons/day, respectively, (at the 1969 NO_x emission level).

The control cost-emission level and air quality-emission level relationships are combined in a graphical solution of the complete model to find the cost of various air quality levels. Best possible air quality levels with the controls considered here are 8 O₃ and 10 NO₂ violations per year (minimum ozone program) or 25 O₃ and 3 NO₂ violations per year (minimum NO₂ program) with an annualized cost of $230,000,000 (above the estimated $150,000,000 per year for the new car control program for Los Angeles County motor vehicles in 1975).

Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

Health effects of ozone and other photochemical oxidants in the Chicago area /

Includes bibliographical references.

Atmospheric nutrient input to coastal areas: reducing the uncertainties

A significant fraction of the total nitrogen entering coastal and estuarine ecosystems along the eastern U.S. coast arises from atmospheric deposition; however, the exact role of atmospherically derived nitrogen in the decline of the health of coastal, estuarine, and inland waters is still uncertain. From the perspective of coastal ecosystem eutrophication, nitrogen compounds from the air, along with nitrogen from sewage, industrial effluent, and fertilizers, become a source of nutrients to the receiving ecosystem. Eutrophication, however, is only one of the detrimental impacts of the emission of nitrogen containing compounds to the atmosphere. Other adverse effects include the production of tropospheric ozone, acid deposition, and decreased visibility (photochemical smog). Assessments of the coastal eutrophication problem indicate that the atmospheric deposition loading is most important in the region extending from Albemarle/Parnlico Sounds to the Gulf of Maine; however, these assessments are based on model outputs supported by a meager amount of actual data. The data shortage is severe. The National Research Council specifically mentions the atmospheric role in its recent publication for the Committee on Environmental and Natural Resources, Priorities for Coastal Ecosystem Science (1994). It states that, "Problems associated with changes in the quantity and quality of inputs to coastal environments from runoff and atmospheric deposition are particularly important [to coastal ecosystem integrity]. These include nutrient loading from agriculture and fossil fuel combustion, habitat losses from eutrophication, widespread contamination by toxic materials, changes in riverborne sediment, and alteration of coastal hydrodynamics. "

An Investigation of Ozone Related Data and Development of a Model to Evaluate Ozone Episodes for Exceptional Event Criteria

The EPA promulgated the Exceptional Events Rule codifying guidance regarding exclusion of monitoring data from compliance decisions due to uncontrollable natural or exceptional events. This capstone examines documentation systems utilized by agencies requesting data be excluded from compliance decisions due to exceptional events. A screening tool is developed to determine whether an event would meet exceptional event criteria. New data sources are available to enhance analysis but evaluation shows many are unusable in their current form. The EPA and States must collaborate to develop consistent evaluation methodologies documenting exceptional events to improve the efficiency and effectiveness of the new rule. To utilize newer sophisticated data, consistent, user-friendly translation systems must be developed.

Lifetime and distribution of ozone and related pollutants in the eastern United States

Most major cities in the eastern United States have air quality deemed unhealthy by the EPA under a set of regulations known as the National Ambient Air Quality Standards (NAAQS). The worst air quality in Maryland is measured in Edgewood, MD, a small community located along the Chesapeake Bay and generally downwind of Baltimore during hot, summertime days. Direct measurements and numerical simulations were used to investigate how meteorology and chemistry conspire to create adverse levels of photochemical smog especially at this coastal location. Ozone (O3) and oxidized reactive nitrogen (NOy), a family of ozone precursors, were measured over the Chesapeake Bay during a ten day experiment in July 2011 to better understand the formation of ozone over the Bay and its impact on coastal communities such as Edgewood. Ozone over the Bay during the afternoon was 10% to 20% higher than the closest upwind ground sites. A combination of complex boundary layer dynamics, deposition rates, and unaccounted marine emissions play an integral role in the regional maximum of ozone over the Bay. The CAMx regional air quality model was assessed and enhanced through comparison with data from NASA’s 2011 DISCOVER-AQ field campaign. Comparisons show a model overestimate of NOy by +86.2% and a model underestimate of formaldehyde (HCHO) by –28.3%. I present a revised model framework that better captures these observations and the response of ozone to reductions of precursor emissions. Incremental controls on electricity generating stations will produce greater benefits for surface ozone while additional controls on mobile sources may yield less benefit because cars emit less pollution than expected. Model results also indicate that as ozone concentrations improve with decreasing anthropogenic emissions, the photochemical lifetime of tropospheric ozone increases. The lifetime of ozone lengthens because the two primary gas-phase sinks for odd oxygen (Ox ≈ NO2 + O3) – attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate – weaken with decreasing pollutant emissions. This unintended consequence of air quality regulation causes pollutants to persist longer in the atmosphere, and indicates that pollutant transport between states and countries will likely play a greater role in the future.

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

Photochemical design of stimuli-responsive nanoparticles prepared by supramolecular host–guest chemistry

We introduce the design of a thermoresponsive nanoparticle via sacrificial micelle formation based on supramolecular host–guest chemistry. Reversible addition–fragmentation chain transfer (RAFT) polymerization was employed to synthesize well-defined polymer blocks of poly(N,N-dimethylacrylamide) (poly(DMAAm)) (Mn,SEC = 10 700 g mol–1, Đ = 1.3) and poly(N-isopropylacrylamide) (poly(NiPAAm)) (Mn,SEC = 39 700 g mol–1, Đ = 1.2), carrying supramolecular recognition units at the chain termini. Further, 2-methoxy-6-methylbenzaldehyde moieties (photoenols, PE) were statistically incorporated into the backbone of the poly(NiPAAm) block as photoactive cross-linking units. Host–guest interactions of adamantane (Ada) (at the terminus of the poly(NiPAAm/PE) chain) and β-cyclodextrin (CD) (attached to the poly(DMAAm chain end) result in a supramolecular diblock copolymer. In aqueous solution, the diblock copolymer undergoes micellization when heated above the lower critical solution temperature (LCST) of the thermoresponsive poly(NiPAAm/PE) chain, forming the core of the micelle. Via the addition of a 4-arm maleimide cross-linker and irradiation with UV light, the micelle is cross-linked in its core via the photoinduced Diels–Alder reaction of maleimide and PE units. The adamantyl–cyclodextrin linkage is subsequently cleaved by the destruction of the β-CD, affording narrowly distributed thermoresponsive nanoparticles with a trigger temperature close to 30 °C. Polymer chain analysis was performed via size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and dynamic light scattering (DLS). The size and thermoresponsive behavior of the micelles and nanoparticles were investigated via DLS as well as atomic force microscopy (AFM).

Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Photochemical reactions of organic crystals

Abstract is not available.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

A comparative study of the photochemical hydrogen-abstraction reactions of a ketone and a thione

A perturbation treatment was developed for the comparative study of the abstraction of hydrogen from methane by formaldehyde and thioformaldehyde in their nπ* and ππ* states. Both in-plane and perpendicularplane reactions are considered. Results are qualitative but reveal clearly the prominent distinguishing features of these two photochemical processes in agreement with the experimental observations.