Lower atmosphere pollution

In 1966, the Los Angeles Air Pollution Control Board designated trichloroethylene as a photochemically reactive solvent that decomposes in the lower atmosphere, contributing to air pollution. In 1970 all states were requited to submit pollution control plans to EPA to meet national air quaUty standards. These plans, known as State Implementation Plans (SIPS), controlled trichloroethylene as a volatile organic compound (VOC). They were designed to have each state achieve the National Ambient Air QuaUty Standard (NAAQS) for ozone. The regulations were estabUshed to control the emission of precursors for ozone, of which trichloroethylene is one. 

Taylor and Marsh (7) investigated the long-term characteristics of temperature inversions and mixed layers in the lower atmosphere to produce an inversion climatology for the Los Angeles basin. In this area the cooler ocean currents produce an elevated inversion that is nearly always present and traps the pollutants released over the area within a layer seldom deeper than 1200 m and frequently much shallower. 

Environmental Fate. A portion of releases of toluene to land and water will evaporate. Toluene may also be degraded by microorganisms. Once volatilized, toluene in the lower atmosphere will react with other atmospheric components contributing to the formation of ground-level ozone and other air pollutants. 

Environmental Fate. Most of the MEK released to the environment will end up in the atmosphere. MEK can contribute to the formation of air pollutants in the lower atmosphere. It can be degraded by microorganisms living in water and soil. 

If the sphere of air mass moves upward in an adiabatic process but in an atmosphere with a subadiabatic lapse rate, the sphere follows a temperature change given by the adiabatic slope but when it arrives at point Zj, it is at a lower temperature than its surroundings, but at the same pressure. As a result, it is heavier than the surroundings and tends to fall back to its original position. This condition is called stable. In a stable atmosphere pollutants will only slowly disperse, and turbulence is suppressed. 

Other factors to account for topography with regard to valley or hillside sites should include possible inversion and failure to disperse pollutants. Temperature inversion occurs when the temperature at a certain layer of the atmosphere stays constant, or even increases with height, as opposed to decreasing with height, which is the norm for the lower atmosphere. Inversions may occur on still, clear nights when the earth and adjacent air cools more rapidly than the free atmosphere. They may also occur when a layer of high turbulence causes rapid vertical convection so that the top of the turbulent layer may be cooler than the next layer above it at the interface. 

A reaction of ozone provides an example of concentration effects. Ozone in the atmosphere near the Earth s surface is a serious pollutant that damages soft tissues such as the lungs. In major urban areas, smog alerts are issued whenever there are elevated concentrations of ozone in the lower atmosphere. Nitmgen oxide, another component of photochemical smog, is a colorless gas produced in a side reaction in automobile engines. One reaction that links these species is the reaction of NO and O3 to produce O2 and NO2 ... 

Ozone is a very reactive compound present in the upper atmosphere (stratosphere) and the lower atmosphere (troposphere). Whilst ozone is vital in the stratosphere, its presence at ground levels is a danger to human health and contributes to the formation of other pollutants. 

The European Commission has adopted a Proposal for a Directive on national emissions ceilings for certain atmospheric pollutants and a Proposal for a Directive relating to ozone in ambient air. The national emissions ceilings Directive will set individual limits for each Member State s total emissions in 2010 of the four pollutants responsible for acidification, eutrophication and ozone formation in the lower atmosphere sulphur dioxide, nitrogen oxides, VOCs and ammonia. The EU Solvents Directive has been formally adopted by the Commission. 

The different greenhouse gases can have complicated interactions. Carbon dioxide may cool the stratosphere which slows the process that destroys ozone. Stratospheric cooling can also create high altitude clouds which interact with chlorofluorocarbons to destroy ozone. Methane may be produced or destroyed in the lower atmosphere at various rates, which depend on the pollutants that are present. Methane can also affect chemicals that control ozone formation. 

Photochemically-generated radicals are encountered as reactive intermediates in many important systems, being a major driving force in the photochemistry of ozone in the upper atmosphere (stratosphere) and the polluted lower atmosphere (troposphere). The photochemistry of organic carbonyl compounds is dominated by radical chemistry (Chapter 9). Photoinitiators are used to form radicals used as intermediates in the chain growth and cross-linking of polymers involved in the production of electronic circuitry and in dental treatment. 

In moderately high concentrations ozone is very toxic when inhaled, and in lesser concentrations, it is irritating to the nose and eyes. Ozone in the lower atmosphere contributes to air pollution and smog. It can cause damage to rubber, plastics, and paints. These low concentrations can cause headaches, burning eyes, and respiratory irritation. It is particular harmful to asthmatics and the elderly with respiratory problems. 

The relationship of particle size to molecular composition is highly significant. (2). Particles below 1-3 fun (submicron size class) in diameter are considered respirable by animals, in that this material can reach the lower alveoli of the lung. Particle size information may be used to determine the sources of various atmospheric pollutants. Particulate matter formed from gaseous pollutants tends to be found in the less than the 1-3 /nm particle diameter size range. Supermicron sized particles (particles greater than 1- 3 typically originate from primary emission sources, (i.e., stack emissions, vehicles, soil). 

It is also doubtful that the industry will be in a position for many years to come to undertake sulfur removal from residual fuels solely to improve product quality. A number of consumer industries demand low sulfur fuel oils, but these special requirements can at present be met more appropriately by selection of crude rather than by adoption of desulfurization processes. In general industrial use, it is corrosion and atmospheric pollution that are the main disadvantages of high sulfur content. But there is no sign yet of the development of a cheap desulfurization process, the cost of which can be substantially offset by the gain in efficiency resulting from permissible lower stack temperatures or by the elimination of flue gas scrubbing equipment previously necessary for reduction of sulfur dioxide content. 

Gaseous hydrogen peroxide is a key component and product of the earth s lower atmospheric photochemical reactions, in both clean and polluted atmospheres. Atmospheric hydrogen peroxide is believed to be generated exclusively by gas-phase photochemical reactions (lARC, 1985). Low concentrations of hydrogen peroxide have been measured in the gas-phase and in cloud water in the United States (United States National Library of Medicine, 1998). It has been found in rain and surface water, in human and plant tissues, in foods and beverages and in bacteria (lARC, 1985). 

Stable aerosols of fine particulates as well as vapors constitute the greatest health risk because of the likelihood of pulmonary absorption. Correlations between trace element pollution and their concentrations in biological fluids or tissue are not uncommon and have been documented for arsenic (62) and lead (63). Man can absorb 75-85% of inhaled mercury vapor at concentrations of 50-350 pg/M3 (64) and even more at lower concentrations (65). Certain aerosols like vanadium, iron, manganese, and lead may contribute to the formation of secondary atmospheric pollutants (52, 66). 

Singlet molecular oxygen is of interest in connection with atmospheric chemistry with respect both to its mode of excitation and to the consequences of its presence in the upper or lower atmosphere. The first part of this section deals with processes of importance in normal, unpolluted atmospheres, while the second part examines the possibility, only recently appreciated, that singlet molecular oxygen may play a part in the chemistry of polluted urban atmospheres. 

In the lower atmosphere, nitric oxide is probably the most important pollutant in urban air it is produced in internal-combustion engines and is ejected into the atmosphere in the exhaust gases. Pollution from this source is certain to be augmented by the increase in the number of automobiles. The NO eventually is converted to NOz, although the details of the conversion are not clear. The obvious reaction with 02... 

Ozone is an extremely reactive chemical. Its reaction with alkenes was discussed in Section 11.11. Although it is considered a pollutant in the lower atmosphere, its presence in the upper atmosphere has beneficial health effects due to its absorption of ultraviolet light. 

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