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haze Figure 10.

To understand visibility degradation, basic principles of light scattering in the atmosphere should be known. Solar radiation passing through atmosphere is both absorbed and

scattered by gases and particles.

Visibility is related with the absorbtion of visible part of the electromagnetic radition The change in the intensity of light when it travels a given distance is due to these absorption and scattering processes. This reduction in intensity is generally given by a general extinction relation:

I/Io = e-bext L
I: the intensity of the light after it traverses the distance L, Io: the intensity at the beginning point of L, bext: the extinction coefficient. Figure 10.3 shows a beam of light transmitted through the atmosphere.

Extinction coefficient consists of two terms:

(1) extinction due to gases,

(2) extinction due to particles bext = bg + bp Each of these two terms are in turn consist of two terms; (a)extinction due to absorption, (b)extinction due to scattering. Then the total extinction coefficient can be written as: bext = bag + bsg + bap + bsp

Absorption of light in the atmosphere is well characterized and mostly occurs as the absorption of UV light at stratosphere by O3 molecules and absorption of IR in the troposphere by greenhouse gases. !!! But, since we are talking of visible light when we talk about visibility degradation, these absorptions are not important. The only molecule that absorbs visible radiation in the troposphere is

the NO2 molecule. (see Figure 10.4 and 10.5)

Gases scatter visible light by a process called Rayleigh scattering. Scattering of light by gas molecules; the principles are well known but will not be discussed. Absorption and scattering of radiation by particles are more complex process.

Figure 10.6 shows four forms of particle light interaction.

The scattering of visible light by particles occurs by three different

mechanisms depending on the size of particles.

For very small particles (D wavelength) the scattering is similar to that of gases (Rayleigh scattering)

For particle diameters comparable to wavelength the scattering

occurs through Mie scattering For large particles (where D >> wavelength) the scattering occurs through geometric scattering and can be treated by classical optics. Each of these scattering mechanisms have different treatments which will not be discussed.

Since the wavelength of visible

radiation is about 400 - 500 nm, and since most of the particles in the atmosphere is mode in the with accumulation

Hot vapor Coagulation Primary particles Coagulation Chain aggregates

Chemical conversion Of gases to low Volatility vapors Low Volatality vapor Homogeneous nucleation Condensation growth Of nuclei Wind blown dust + Emissions + Sea spray + Volcanos + Plant particles

diameters comparable to the wavelength of the visible light, then one would to be expect the Mie most
0.002 0.01

Droplets Coagulation Coagulation

Coagulation Rainout And washout

scattering atmosphere.

important mechanism in polluted

0.1 Transient nuclei or Aitken nuclei range Fine particles


1 2 PArticle diameter (m) Accumulation range

10 Mechanically generated Aerosol range Coarse particles








radiation and cause visibility degradation;

absorption and scattering of light by particles

are the most important parameters.

In a study made in Denver photochemical smog conditions, the contribution of gases on the total light attenuation is found to be 7% and the rest being due to absorption and scattering of particles.


Back to visibility degradation. In haze visual range decrease. The visual range is defined as the distance at which a black object can be distinguished against the horizon. During daytime, light coming from the object to the observes eye is scattered out of sight of the observer. Also, sunlight which is normally out of sight is scattered into the sight, resulting in dark object appear lighter (reducing the contrast).


Typical visual ranges are few hundred kms in clean atmosphere and few
kms in pollutes atmosphere. In urban atmosphere most of the visibility loss is due to scattering of radiation by particles. Light scattering is dominated by particles in the accumulation mode. This is shown in the Figure 10a where light scattering coefficient per unit

volume is plotted against particles diameter. The highest value of bsp is

found in the accumulation mode (0.1 - 1 m range).


This is also supported in Figure 10b where bsp is plotted against particle volume. The slope of the line given in this figure depends on the history of air mass (chemical constituents in it).


Since mass and volume are related through density, values of bsp is
expected to be related with the mass as well as volume. The Figure 10c shows the relation between fine and coarse particle mass and bsp. There is a good correlation between the bsp and fine mass. But coarse mass is not correlated with the bsp.

This also confirms that light scattering is dominated by fine particles.

This is purely an optical effect.


The bsp also depends on the chemical composition of particles. Because the Mie scattering depends on the refractive index of particles. The refractive index in turn is related to chemical composition. Since the chemical composition of coarse and fine particles is different, this would also contribute to observed difference in the correlation of fine mass

with bsp, but lack of similar correlation between coarse mass and bsp.


The light scattering coefficients of SO4-2, NO3- and carbonaceous particles

were found to be the highest indicating that the light scattering is mostly
due these components of the fine mass. Although these ions scatter light, they must be in the correct size range, which scatters light most efficiently (0.1 to few m) (see Figure 10a). E.g., in a study in Los Angeles, although the carbonaceous mass accounted for most of the aerosol mass, bsp did not correlate well with carbonaceous mass. This was attributed to the presence of carbon as very fine particles, which does not scatter light effectively.











characteristics of aerosols. Most of the aerosols are hydroscopic, so they take up water depending the relative humidity. Water vapor increase the size and mass of particles and reduce the refractive index. The net result is increase in the light scattering.

This is shown in Figure 10d where liquid water content of aerosols are plotted
against bscat.


Particles not only scatter, but also absorb visible light.

The most important contributor to light absorption is black or elemental carbon which is produced in combustion processes.

The contribution of light absorption by carbon on total light extinction

changes geographically depending on the distribution of combustion sources.

Wood-burning and diesels are the main sources of elemental carbon. In

urban industrial areas bap is 50 - 100% of bsp. In rural areas bap <15% of bsp.


Since black carbon both absorbs and scatter visible radiation, it tends to play a proportionally much greater role in the light extinction than its

contribution to particulate mass suggest.

E.g., in Denver elemental carbon accounts for about 15% of the particle mass, but accounts for about 35% of total light extinction.


FORMATION OF ATMOSPHERIC HAZE Haze: Reduced visibility caused by the presence of particles and NO2 in the atmosphere. For haze to occur sizes of particles should be between 0.1 m and 1.0 m. Sources of such particles can be natural as in the case of blue haze over the mountains in morning hours, or anthropogenic as in the case of pollution over urban areas. The main components of atmospheric haze is the sulfate (mostly (NH4)2SO4 particles) and nitrate particles.


In polluted atmosphere, SO4/NO3 was approximately 3/2 in 1970s and 80s. But with actions taken to reduce SO2 emissions in late 80s, SO4 concentrations in the atmosphere also decreased (and decreasing). Currently the ratio is approximately equal to 1.0 Other components in the atmospheric haze are the soot carbon, fine fly ash particles and organic aerosols.


These are anthropogenic particles and dominate atmospheric haze in urban areas. But their role is limited in the haze in the regional scale. Since anthropogenic particles such as soot carbon can both scatter and absorb radiation, if their concentration increase and they become important in the regional and global scales, they may have significant

effect on the climate and earth energy balance.


Particle Formation in the Atmosphere Primary particles directly emitted from sources. But secondary particles formed in the atmosphere from their precursors. How?


In the formation of secondary particles molecules in the gas phase has to

transform into solid particles. This process can occur by three processes:


Involves dissolution of gaseous molecules in liquid (in the atmosphere, mostly water).
Chemical process that convert gas molecule into another one with much less vapor pressure

Then droplet evaporates leaving behind a particle.

One important mechanism of SO4 formation is called liquid phase oxidation of SO2. In this mechanism, SO2 first dissolve in water droplets such as cloud or fog droplets In the droplet it oxidizes to SO4 by H2O2 Then when cloud or fog droplet evaporates, SO4 particle is left behind (either in the form of H2SO4, or (NH4)2SO4). This mechanism depends on the solubility of the precursor gas in water (SO2 is highly soluble).


Molecules in the gas phase grow into clusters and clusters grow into particles. The condensable species that will eventually form into particles are formed from gas precursors and they are in the gas phase initially. If the product has sufficiently low vapor pressure they can saturate quickly and start to form molecular aggregates called clusters. For these clusters to form and grow a condition called supersaturation has to be reached. The saturation ratio (S) is the ratio of the actual pressure of the gas to its equilibrium vapor pressure. described as supersaturation.

If S>1 the situation is

E.g., The situation is analogous to the supersaturation in solutions. If you dissolve sugar (or salt) in hot water you can dissolve more than you can at room temperature, because solubility increase with temperature. After you dissolve sugar in hot water if you cool the water to room temperature, you expect excess dissolved sugar to crystallize and stay at the bottom. But, crystallization does not occur immediately and solution stays at the supersaturation state until you add a apiece of something or stir it. During supersaturation the ratio of sugar concentration to that of solubility of sugar is >1.

The situation is the same in atmosphere, except instead of concentration you use vapor pressure.


Substances with low vapor pressure favor nucleation, because their equilibrium vapor pressure is low and supersaturation can be reached easily. Example of this type of particles is the sulfate generated by gas phase photochemical oxidation of SO2.


Particle formation by condensation occurs when molecules formed after reaction collides with the existing particles and droplets. For condensation to occur supersaturation should be reached (S>1) Since condensation can occur at lower supersaturation levels than

nucleation, it is the dominating mechanism when there are particles.



Ankara- August 2003

Characteristics of the observer Psycophysica (eye-brain) response to incoming light tresholds of perception for contrast and color change

Optical Charactersitics of illumination source Sun angle, spectrum, intensity as altered by cloud cover and atmosphere

Sensivity to size, pattern distribution of color

Subjective judgement of percived images

Optical Charactersitics of viewed targets Inherent contrast, spectral reflectance (color), size, shape distance pattern, hoerizon, brightness

Figure 10.1. Factors determining visibility in the atmosphere.


Characteristics of the observer Psycophysica (eye-brain) response to incoming light tresholds of perception for contrast and color change Sensivity to size, pattern distribution of color Subjective judgement of percived images

Optical Charactersitics of illumination source

Sun angle, spectrum, intensity as altered by cloud cover and atmosphere

Optical Charactersitics of intervening atmosphere

Optical Charactersitics of viewed targets Inherent contrast, spectral reflectance (color), size, shape distance pattern, hoerizon, brightness


Figure 10.3. (a) a diagram of extinction of light from a source such as an electric light in a reflector, illustrating (i) transmitted, (ii) scattered, and (iii) absorbed light.

(b) A diagram of daylight visibility illustrating (I) residual light from a target reaching an observer, (ii) light from a target scattered out of an observers line of sight, (iii) air light from the intervening atmosphere and, (iv) air light constituting horizon sky. 34

Figure 10.4. Absorption spectrum of NO2.


Figure 10.5. Comparison of bext for 0.1 ppm NO2 and Rayleigh scattering by air. 36

Figure 10.6. Four forms of particle light interaction.


Figure 10.7. Scattering and absorption cross-section per unit volumes as a function of particle diameter. 38

Figure 10.8. Single particle scattering to mass ratio for particles of four different compositions.


Figure 10.10. Historic trens in hours of reduced visibility at Phoenix and Tuscon, Arizona, compared to trends in Sox emissions from Arizona smelters. 40

Figure 10a. Light scattering coefficient per unit volume vs. particles diameter


Figure 10a. Light scattering coefficient per unit volume vs. particles diameter


Figure 10b. bsp vs. particle volume


Figure 10c. Relation between fine and coarse particle mass and bsp.


Figure 10d. liquid water content of aerosols are plotted against bscat


The reduction in contrast is given by Koschimieder equation: C/Co = e-bextL similar to Beers law. Co is the contrast of an object against horizon at the L = 0 and C is the contrast at distance L. The contrast is given by: C = (Bo/BH) - 1 where Bo is the brightness of the object and BH is the brightness of the horizon (or background).


Observers can typically differentiate objects on the horizon if C/Co is 0.02 0.05.

If the contrast is 0.02 than the visual range would be

Lv = (ln C/Co)/bext = 3.9/bext For a contrast of 0.05 the visual range is Lv = 3.0/bext