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[[File:Crude oil-fired power plant.jpg|thumb|right|225px|Industrial air pollution source]]
Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.  


'''Gasoline''' or '''petrol''' is derived from [[petroleum crude oil]]. It is a blended mixture of 200 or more [[hydrocarbon]] [[liquid]]s ranging from those containing 4 [[carbon]] [[atom]]s to those containing 11 or 12  carbon atoms. It has an initial [[boiling point]] at [[atmospheric pressure]] of about 35 °[[Celsius|C]] (95 °[[Fahrenheit|F]]) and a final boiling point of about 200 °C (395 °F). Gasoline is used as fuel for the [[internal combustion engine]]s in automotive vehicles as well in some small airplanes.  
Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.<ref>J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", ''JAPCA'', Vol. 21, No. 7, 1971.</ref> 


Some gasoline marketed in parts of the United States and elswhere also contains a significant amount of [[ethanol]].
Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.
In [[Canada]] and the [[United States]], the word "gasoline" is commonly used and it is often shortened to simply "gas" although it is a liquid rather than a [[gas]]. In fact, gasoline dispensing facilities are referred to as "gas stations".  


Most current or former [[Commonwealth of Nations|Commonwealth countries]] use the term "petrol" and dispensing facilities are referred to as "petrol stations". The term "petrogasoline" is also used sometimes.
The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:


In aviation, "mogas" (short for "motor gasoline") is used to distinguish automotive vehicle fuel from aviation fuel known as "avgas".
* Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
* The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
* Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
* The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).


== Amount of gasoline produced from a barrel of crude oil ==
Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.


{{Image|Refinery Products Barrel.png|right|250px|Average U.S. refinery product yields.}}
The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.


It is very difficult to quantify the amount of gasoline produced from a given amount of petroleum crude oil for  a number of reasons:
==Atmospheric layers==


* There are quite literally hundreds of different crude oil sources worldwide and each crude oil has its own unique mixture of thousands of hydrocarbons and other materials.  
Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the ''troposphere''. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The ''stratosphere'' is the next layer and extends from 18 km up to about 50 km. The third layer is the ''mesosphere'' which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.


* There are also hundreds of [[Petroleum refining processes|crude oil refineries]] worldwide and each of them is designed to process a specific crude oil or a specific set of crude oils. Furthermore, each refinery has its own unique configuration of [[petroleum refining processes]] that produces its own unique set of gasoline blend components.
The lowest part of the troposphere is called the ''atmospheric boundary layer (ABL)'' or the ''planetary boundary layer (PBL)'' and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the ''inversion layer'' (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the ''free troposphere'' and it extends up to the 18 km height of the troposphere.


* There are a great many different gasoline specifications that have been mandated by various local, state or national govermental agencies.  
The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the ''mixing layer''. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.


* In many geographical areas, the amount of gasoline produced during the summer season (i.e., the season of the greatest demand for automotive gasoline) varies significantly from the amount produced during the winter season.
In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as ''boundary layer models'' because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as ''mesoscale models'' have dispersion modeling capabilities that can extend horizontally as much as  a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.


 
==Gaussian air pollutant dispersion equation==


The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.<ref>C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", ''Trans. Faraday Soc.'', 32:1249, 1936.</ref> Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.


Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947<ref>O.G. Sutton, "The problem of diffusion in the lower atmosphere", ''QJRMS'', 73:257, 1947.</ref><ref>O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", ''QJRMS'', 73:426, 1947.</ref> which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.


Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the '''Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes''' shown below:<ref name=Beychok>{{cite book|author=M.R. Beychok|title=Fundamentals Of Stack Gas Dispersion|edition=4th Edition| publisher=author-published|year=2005|isbn=0-9644588-0-2}}.</ref><ref>{{cite book|author=D. B. Turner| title=Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling| edition=2nd Edition |publisher=CRC Press|year=1994|isbn=1-56670-023-X}}.</ref>


Gasoline is produced from petroleum crude oil in [[Petroleum refining processes|oil refineries]]. The liquid material that is initially separated directly from the crude oil by [[Continuous distillation|distillation]] is called "virgin" or "straight-run" [[Petroleum naphtha|naphtha]] and it does not have the [[octane rating]] (see below) that modern internal combustion engines require. The virgin naphtha must undergo further processing before it becomes part of the final gasoline blends produced in oil refineries.


<math>C = \frac{\;Q}{u}\cdot\frac{\;f}{\sigma_y\sqrt{2\pi}}\;\cdot\frac{\;g_1 + g_2 + g_3}{\sigma_z\sqrt{2\pi}}</math>


The various refinery process streams blended together to make gasoline all have different characteristics. Some important streams are:
{| border="0" cellpadding="2"
*''Reformate'', produced in a [[catalytic reformer]] with a high octane rating and high [[aromatic]] content, and very low olefins ([[alkene]]s).
|-
*''Cat Cracked Gasoline'' or ''Cat Cracked [[Naphtha]]'', produced from a [[Fluid catalytic cracking|catalytic cracker]], with a moderate octane rating, high [[olefin]]s (alkene) content, and moderate aromatics level. ''Here, "cat" is short for "[[catalyst|catalytic]]".''
|align=right|where:
*''Hydrocrackate'' (Heavy, Mid, and Light), produced from a hydrocracker, with medium to low octane rating and moderate aromatic levels.
|&nbsp;
*''Virgin or Straight-run Naphtha'' (has many names), directly from [[crude oil]] with low octane rating, low aromatics (depending on the [[crude oil]]), some [[naphthene]]s ([[cycloalkane]]s) and no olefins (alkenes).
|-
*''Alkylate'', produced in an [[alkylation]] unit, with a high octane rating and which is pure [[paraffin]] (alkane), mainly branched chains.
!align=right|<math>f</math> 
*''Isomerate'' (various names) which is obtained by isomerising the pentane and hexane{{Fact|date=October 2008}} in light virgin naphthas to yield their higher octane isomers.
|align=left|= crosswind dispersion parameter
|-
!align=right|&nbsp;
|align=left|= <math>\exp\;[-\,y^2/\,(2\;\sigma_y^2\;)\;]</math>
|-
!align=right|<math>g</math>
|align=left|= vertical dispersion parameter = <math>\,g_1 + g_2 + g_3</math>
|-
!align=right|<math>g_1</math>
|align=left|= vertical dispersion with no reflections
|-
!align=right|&nbsp;
|align=left|= <math>\; \exp\;[-\,(z - H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_2</math>
|align=left|= vertical dispersion for reflection from the ground
|-
!align=right|&nbsp;
|align=left|= <math>\;\exp\;[-\,(z + H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_3</math>
|align=left|= vertical dispersion for reflection from an inversion aloft
|-
!align=right|&nbsp;
|align=left|= <math>\sum_{m=1}^\infty\;\big\{\exp\;[-\,(z - H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z - H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]\big\}</math>
|-
!align=right|<math>C</math>
|align=left|= concentration of emissions, in g/m³, at any receptor located:
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; x meters downwind from the emission source point
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; y meters crosswind from the emission plume centerline
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; z meters above ground level
|-
!align=right|<math>Q</math>
|align=left|= source pollutant emission rate, in g/s
|-
!align=right|<math>u</math>
|align=left|= horizontal wind velocity along the plume centerline, m/s
|-
!align=right|<math>H</math>
|align=left|= height of emission plume centerline above ground level, in m
|-
!align=right|<math>\sigma_z</math>
|align=left|= vertical standard deviation of the emission distribution, in m
|-
!align=right|<math>\sigma_y</math>
|align=left|= horizontal standard deviation of the emission distribution, in m
|-
!align=right|<math>L</math>
|align=left|= height from ground level to bottom of the inversion aloft, in m
|-
!align=right|<math>\exp</math>
|align=left|= the exponential function
|}


(The terms used here are not always the correct chemical terms. They are the [[jargon]] normally used in the oil industry. The exact terminology for these streams varies by refinery and by country.)
The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.


Overall a typical gasoline is predominantly a mixture of paraffins ([[alkane]]s), naphthenes (cycloalkanes), and olefins (alkenes). The exact ratios can depend on
The sum of the four exponential terms in <math>g_3</math> converges to a final value quite rapidly. For most cases, the summation of the series with '''''m''''' = 1, '''''m''''' = 2 and '''''m''''' = 3 will provide an adequate solution.
*the oil refinery that makes the gasoline, as not all refineries have the same set of processing units.
*the [[crude oil]] feed used by the refinery.
*the grade of gasoline, in particular the octane rating.


Currently many countries set tight limits on gasoline [[aromatic]]s in general, [[benzene]] in particular, and olefin (alkene) content. This is increasing the demand for high octane pure paraffin (alkane) components, such as alkylate, and is forcing refineries to add processing units to reduce the benzene content.
<math>\sigma_z</math> and <math>\sigma_y</math> are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.


Gasoline can also contain some other [[organic compound]]s: such as [[organic ether]]s (deliberately added), plus small levels of contaminants, in particular [[sulfur]] compounds such as [[disulfides]] and [[thiophene]]s. Some contaminants, in particular [[thiol]]s and [[hydrogen sulfide]], must be removed because they cause corrosion in engines.
Whereas older models rely on stability classes for the determination of <math>\sigma_y</math> and <math>\sigma_z</math>, more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.


== Octane rating ==
==Briggs plume rise equations==
{{main|Octane rating}}
{{Image|Iso-octane and n-Heptane.png|right|250px|Simplified structure of 2,2,4-trimethylpentane and n-heptane.}}


An important characteristic of gasoline is its octane rating, which is a measure of how resistant gasoline is to the abnormal combustion phenomenon known as [[engine knocking|pre-detonation]] (also known as knocking, pinging, spark knock, and other names). [[Deflagration]] is the normal type of combustion.  Octane rating is measured relative to a mixture of [[2,2,4-Trimethylpentane|2,2,4-trimethylpentane]] (an [[isomer]] of [[octane]]) and n-[[heptane]].  There are a number of different conventions for expressing the octane rating; therefore, the same fuel may be labeled with a different number, depending upon the system used.
The Gaussian air pollutant dispersion equation (discussed above) requires the input of ''H'' which is the pollutant plume's centerline height above ground level. ''H'' is the sum of ''H''<sub>s</sub> (the actual physical height of the pollutant plume's emission source point) plus Δ''H'' (the plume rise due the plume's buoyancy).


The octane rating became important in the search for higher output powers from [[aero engine]]s in the late 1930s and the 1940s as it allowed higher [[compression ratio]]s to be used.
[[File:Gaussian Plume.png|thumb|right|333px|Visualization of a buoyant Gaussian air pollutant dispersion plume]]


== Additives ==
To determine Δ''H'', many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.<ref>G.A. Briggs, "A plume rise model compared with observations", ''JAPCA'', 15:433–438, 1965.</ref> In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.<ref>G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", ''Atmos. Envir.'', 2:228–232, 1968.</ref> In that same year, Briggs also wrote the section of the publication edited by Slade<ref>D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.</ref> dealing with the comparative analyses of plume rise models.  That was followed in 1969 by his classical critical review of the entire plume rise literature,<ref>G.A. Briggs, "Plume Rise", ''USAEC Critical Review Series'', 1969.</ref> in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations".  Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.<ref>G.A. Briggs, "Some recent analyses of plume rise observation", ''Proc. Second Internat'l. Clean Air Congress'', Academic Press, New York, 1971.</ref><ref>G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", ''Atmos. Envir.'', 6:507–510, 1972.</ref>


=== Tetra-ethyl lead (TEL) ===
Briggs divided air pollution plumes into these four general categories:
The mixture known as gasoline, when used in high [[Physical compression|compression]] internal combustion engines, has a tendency to autoignite (''detonation'') causing a damaging "[[engine knocking]]" (also called "pinging") noise. Early research into this effect was led by A.H. Gibson and [[Harry Ricardo]] in England and [[Thomas Midgley]] and Thomas Boyd in the United States. The discovery that [[lead]] additives modified this behavior led to the widespread adoption of the practice in the 1920s and therefore more powerful higher compression engines. The most popular additive was [[tetra-ethyl lead]]. However, with the discovery of the environmental and health damage caused by the lead, and the incompatibility of lead with [[catalytic converter]]s found on virtually all newly sold US automobiles since 1975, this practice began to wane (encouraged by many governments introducing differential tax rates) in the 1980s. Most countries are phasing out leaded fuel; different additives have replaced the lead compounds. The most popular additives include [[aromatic hydrocarbon]]s, [[ether]]s and [[alcohol as a fuel|alcohol]] (usually [[ethanol]] or [[methanol]]).
* Cold jet plumes in calm ambient air conditions
In the US, where lead had been blended with gasoline (primarily to boost octane levels) since the early 1920s, standards to phase out leaded gasoline were first implemented in 1973 - due in great part to studies conducted by [[Philip J. Landrigan]]. In 1995, leaded fuel accounted for only 0.6% of total gasoline sales and less than 2,000 [[short ton]]s of lead per year. From [[January 1]], [[1996]], the [[Clean Air Act]] banned the sale of leaded fuel for use in on-road vehicles. Possession and use of leaded gasoline in a regular on-road vehicle now carries a maximum $10,000 fine in the US. However, fuel containing lead may continue to be sold for off-road uses, including aircraft, racing cars, farm equipment, and marine engines.<ref>{{cite press release | title =  EPA Takes Final Step in Phaseout of Leaded Gasoline | date = 1996-01-29 | url = http://www.epa.gov/history/topics/lead/02.htm | publisher = [[U.S. Environmental Protection Agency]]}}</ref>  The ban on leaded gasoline led to thousands of tons of lead not being released in the air by automobiles. Similar bans in other countries have resulted in lowering levels of lead in people's [[blood]]streams.<ref>{{cite journal | title = Blood Lead Secular Trend in a Cohort of Children in Mexico City (1987–2002) | author = Lourdes Schnaas, Stephen J. Rothenberg, María-Fernanda Flores, Sandra Martínez, Carmen Hernández, Erica Osorio,1 and Estela Perroni | journal = [[Environ. Health. Perspect.]] | year = 2004 | volume = 112 | issue = 10 | pages = 1110–1115 | doi = 10.1289/ehp.6636 | url = http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=1247386 | format = [[Open-access]] full-text reprint | pmid = 15238286}}</ref><ref>{{cite journal | journal = [[Archives of Environmental Health: An International Journal]] | volume = 59 | issue = 4 | year = 2004 | pages = 182–187 | doi = 10.3200/AEOH.59.4.182-187 | title = Rapid Drop in Infant Blood Lead Levels during the Transition to Unleaded Gasoline Use in Santiago, Chile | author = Paulina Pino, Tomás Walter; Manuel J. Oyarzún A3, Matthew J. Burden; Betsy Lozoff}}</ref>
* Cold jet plumes in windy ambient air conditions
* Hot, buoyant plumes in calm ambient air conditions
* Hot, buoyant plumes in windy ambient air conditions


A side effect of the lead additives was protection of the [[poppet valve|valve]] seats from erosionMany [[classic car]]s' engines have needed modification to use lead-free fuels since leaded fuels became unavailable. However, "Lead substitute" products are also produced and can sometimes be found at auto parts stores. These were scientifically tested and some were approved by the Federation of British Historic Vehicle Clubs at the UK's Motor Industry Research Association (MIRA) in 1999. [http://www.fbhvc.co.uk/fuel/index.htm http://www.fbhvc.co.uk/fuel/index.htm]
Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportantAlthough Briggs proposed plume rise equations for each of the above plume categories, '''''it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes'''''.


Gasoline, as delivered at the pump, also contains additives to reduce internal engine carbon buildups, improve [[combustion]], and to allow easier starting in cold climates.
In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants.  Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).


In some parts of [[South America]], [[Asia]], Eastern [[Europe]] and the [[Middle East]], leaded gasoline is still in use. Leaded gasoline was phased out in [[sub-Saharan Africa]] effective [[1 January]], [[2006]]. A growing number of countries have drawn up plans to ban leaded gasoline in the near future.
A logic diagram for using the Briggs equations<ref name=Beychok/> to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:
[[Image:BriggsLogic.png|none]]
:{| border="0" cellpadding="2"
|-
|align=right|where:
|&nbsp;
|-
!align=right| Δh
|align=left|= plume rise, in m
|-
!align=right| F<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= buoyancy factor, in m<sup>4</sup>s<sup>−3</sup>
|-
!align=right| x
|align=left|= downwind distance from plume source, in m
|-
!align=right| x<sub>f</sub>
|align=left|= downwind distance from plume source to point of maximum plume rise, in m
|-
!align=right| u
|align=left|= windspeed at actual stack height, in m/s
|-
!align=right| s<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= stability parameter, in s<sup>−2</sup>
|}
The above parameters used in the Briggs' equations are discussed in Beychok's book.<ref name=Beychok/>


=== MMT ===
==References==
[[Methylcyclopentadienyl manganese tricarbonyl]] (MMT) has been used for many years in [[Canada]] and recently in [[Australia]] to boost octane. It also helps old cars designed for leaded fuel run on unleaded fuel without need for additives to prevent valve problems.
 
US Federal sources state that MMT is suspected to be a powerful neurotoxin and respiratory toxin,<ref>{{cite web | title = Comments of the Gasoline Additive MMT |url = http://www.epa.gov/otaq/regs/fuels/additive/mmt_cmts.htm | accessdate = 2008-08-10 }}</ref> and a large Canadian study concluded that MMT impairs the effectiveness of automobile emission controls and increases pollution from motor vehicles.<ref>{{cite web | title = Final Report: Effects of MMT in Gasoline on Emissions from On-Road Motor Vehicles in Canada | date = 2002-11-11 | publisher = Canadian Vehicle Manufacturers’ Association, and Association of International Automobile Manufacturers of Canada | url = http://cvma.ca/eng/publications/FinalMMTReport.pdf|format=PDF}}</ref>
 
In 1977 use of MMT was banned in the US by the Clean Air Act until the Ethyl Corporation could prove that the additive would not lead to failure of new car emissions-control systems. As a result of this ruling, the Ethyl Corporation began a legal battle with the EPA, presenting evidence that MMT was harmless to automobile emissions-control systems. In 1995 the US Court of Appeals ruled that the EPA had exceeded its authority, and MMT became a legal fuel additive in the US. MMT is nowadays manufactured by the Afton Chemical Corporation division of Newmarket Corporation.<ref>{{cite web | publisher = Afton Chemical | title = History of mmt | url = http://www.aftonchemical.com/Products/MMT/History+of+MMT%AE.htm | accessdate = 2008-02-22}}</ref>
 
=== Oxygenates ===
 
[[Oxygenate]] blending adds oxygen to the fuel in [[oxygen]]-bearing compounds such as [[MTBE]], [[ETBE]] and [[ethanol]], and so reduces the amount of [[carbon monoxide]] and unburned fuel in the exhaust gas, thus reducing smog. In many areas throughout the US oxygenate blending is mandated by EPA regulations to reduce smog and other airborne polutants. For example, in Southern California, fuel must contain 2% oxygen by weight, resulting in a mixture of 5.6% ethanol in gasoline.  The resulting fuel is often known as ''reformulated gasoline'' (RFG) or ''oxygenated gasoline''. The federal requirement that RFG contain oxygen was dropped [[May 6]], [[2006]] because the industry had developed VOC-controlled RFG that did not need additional oxygen.<ref>{{cite web | url = http://www.epa.gov/otaq/rfg_regs.htm#usage | title = Removal of Reformulated Gasoline Oxygen Content Requirement (national) and Revision of Commingling Prohibition to Address Non-0xygenated Reformulated Gasoline (national) | date = 2006-02-22 | publisher = [[U.S. Environmental Protection Agency]]}}</ref>
 
MTBE use is being phased out in some states due to issues with contamination of ground water. In some places, such as California, it is already banned. Ethanol and to a lesser extent the ethanol derived ETBE are a common replacements. Especially since ethanol derived from biomatter such as corn, sugar cane or grain is frequent, this will often be referred to as ''bio''-ethanol. A common ethanol-gasoline mix of 10% ethanol mixed with gasoline is called [[Ethanol fuel|gasohol]] or E10, and an ethanol-gasoline mix of 85% ethanol mixed with gasoline is called [[E85]]. The most extensive use of ethanol takes place in [[Brazil]], where the ethanol is derived from [[sugarcane]]. In 2004, over 3.4 billion US gallons (2.8&nbsp;billion imp&nbsp;gal/13 million m³) of ethanol was produced in the United States for fuel use, mostly from [[maize|corn]], and E85 is slowly becoming available in much of the United States. Unfortunately many of the relatively few stations vending E85 are not open to the general public.<ref>{{cite web | url = http://www.eere.energy.gov/afdc/fuels/stations_locator.html | title = Alternative Fueling Station Locator | publisher = [[U.S. Department of Energy]]}}</ref>  The use of [[bioethanol]], either directly or indirectly by conversion of such ethanol to ''bio''-ETBE, is encouraged by the European Union [[Directive on the Promotion of the use of biofuels and other renewable fuels for transport]]. However since producing bio-ethanol from fermented sugars and starches involves [[distillation]], ordinary people in much of Europe cannot legally ferment and distill their own bio-ethanol at present (unlike in the US where getting a [[BATF]] distillation permit has been easy since the 1973 oil crisis.)
 
 
=== Ethanol ===
In the United States, [[ethanol]] is sometimes added to gasoline but sold without an indication that it is a component. Chevron, 76, Shell, and several other brands market ethanol-gasoline blends.{{Fact|date=May 2007}}
 
In several states, ethanol is added by law to a minimum level which is currently 5.9%.  Most fuel pumps display a sticker stating that the fuel may contain up to 10% ethanol, an intentional disparity which allows the minimum level to be raised over time without requiring modification of the literature/labeling.  The bill which was being debated at the time the disclosure of the presence of ethanol in the fuel was mandated has recently passed.  This law ([[Energy Policy Act of 2005]]) will require all auto fuel to contain at least 10% ethanol. Many call this fuel mix [[gasohol]].
 
In the EU, 5% ethanol can be added within the common gasoline spec (EN 228). Discussions are ongoing to allow 10% blending of ethanol. Most countries (fuel distributors) today do not add so much ethanol.{{Fact|date=April 2008}} Most gasoline (petrol) sold in Sweden has 5% ethanol added.
 
In Brazil, the [[Brazilian National Agency of Petroleum, Natural Gas and Biofuels]] (ANP) requires that gasoline for automobile use has 23% of ethanol added to its composition.
 
== Stability ==
 
{{Image|E10 Water Tolerance.png|right|281px|Temperatures and associated water contents at which a blend of  gasoline and 10 volume % ethanol separates.<ref>[http://www.scribd.com/doc/1970087/Environmental-Protection-Agency-Ethanol-Workshop E10 & E85 and Other Alternate Fuels] Bruce Bauman, [[American Petroleum Institute]](API)</ref>}}
When gasoline is left for a period of time, gums and varnishes may build up and precipitate in the gasoline, causing "stale fuel." This will cause gums to build up in the fuel tank, lines, and carburetor or fuel injection components making it harder to start the engine. Motor gasoline may be stored up to 60 days in an approved container. If it is to be stored for a longer period of time, a fuel stabilizer may be used. This will extend the life of the fuel to about 1–2 years, and keep it fresh for the next uses. Fuel stabilizer is commonly used for small engines such as lawnmower and tractor engines to promote quicker and more reliable starting.  Users have been advised to keep gasoline containers and tanks more than half full and properly capped to reduce air exposure, to avoid storage at high temperatures,<ref>{{cite web|url=http://www.alpharubicon.com/altenergy/gasstoretg.htm|title=Fuel storage practices}}</ref> to run an engine for ten minutes to circulate the stabilizer through all components prior to storage, and to run the engine at intervals to purge stale fuel from the [[carburetor]].<ref>{{cite web|url=http://www.perr.com/tip1.html|title=PER Notebook}}</ref>
 
Gummy, sticky resin deposits result from [[oxidation|oxidative]] degradation of gasoline.  This degradation can be prevented through the use of [[antioxidant]]s such as [[phenylenediamine]]s, [[alkylenediamine]]s ([[diethylenetriamine]], [[triethylenetetramine]], etc), and [[alkylamine]]s ([[diethylamine]], [[tributylamine]], [[ethylamine]]).  Other useful additives include gum inhibitors such as N-substituted [[alkylaminophenol]]s and colour stabilizers such as N-(2-aminoethyl)piperazine, N,N-diethylhydroxylamine, and triethylenetetramine.<ref name=EP0534668>{{patent|EP|0534668|Stabilization of gasoline mixtures}}</ref>
 
Improvements in refinery techniques have generally reduced the reliance on the catalytically or thermally cracked stocks most susceptible to oxidation.<ref>{{patent|US|3994698| Gasoline additive concentrate composition}}</ref>  Gasoline containing acidic contaminants such as [[naphthenic acid]]s can be addressed with additives including strongly basic organo-amines such as [[N,N-diethylhydroxylamine]], preventing metal corrosion and breakdown of other antioxidant additives due to acidity.  Hydrocarbons with a [[bromine number]] of 10 or above can be protected with the combination of unhindered or partially hindered phenols and oil soluble strong amine bases such as [[monoethanolamine]], N-(2-aminoethyl)piperazine, [[cyclohexylamine]], 1,3-cyclohexane-bis(methylamine), 2,5-[[dimethylaniline]], 2,6-dimethylaniline, [[diethylenetriamine]] and [[triethylenetetramine]].<ref name=EP0534668 />
 
== References ==
{{reflist}}
{{reflist}}


== Further reading==


== External links ==
*{{cite book | author=M.R. Beychok| title=Fundamentals Of Stack Gas Dispersion | edition=4th Edition | publisher=author-published | year=2005 | isbn=0-9644588-0-2}}
 
* [http://cta.ornl.gov/data/index.shtml Transportation Energy Data Book]
 
 
==References==
*{{cite book|author=David S.J. Jones and Peter P.Pujado (Editors)|title=Handbook of Petroleum Processing|edition=First Edition|publisher=Springer|year=2006|id=ISBN 1-4020-2819-9}}
 
*{{cite book|author=John McKetta (Editor)|title=Petroleum Processing Handbook|edition=|publisher=CRC Press|year=1992|id=ISBN 0-8247-8681-5}}


*[http://www.faqs.org/faqs/autos/gasoline-faq/part4/ Gasoline FAQ - Part2 of 4], Bruce Hamilton, Industrial Research Ltd. (IRL), a [[Crown Research Institute]] of [[New Zealand]].
*{{cite book | author=K.B. Schnelle and P.R. Dey| title=Atmospheric Dispersion Modeling Compliance Guide  | edition=1st Edition| publisher=McGraw-Hill Professional | year=1999 | isbn=0-07-058059-6}}


*[http://hqweb.unep.org/pcfv/PDF/JordanWrkshp-Unleaded-Rafat.pdf The Relation Between Gasoline Quality, Octane Number and the Environment], Rafat Assi, National Project Manager of Jordan’s Second National Communications on Climate Change, Presented at Jordan National Workshop on Lead Phase-out, [[United Nations]] Environment Programme, July 2008, [[Amman]], [[Jordan]].
*{{cite book | author=D.B. Turner| title=Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling | edition=2nd Edition | publisher=CRC Press | year=1994 | isbn=1-56670-023-X}}


*[http://www.med.govt.nz/templates/Page____10323.aspx Questions and Answers Relating to the Review of the Existing Fuel Quality Regulations], New Zealand Ministry of Economic Development, December 2005.
*{{cite book | author= S.P. Arya| title=Air Pollution Meteorology and Dispersion | edition=1st Edition | publisher=Oxford University Press | year=1998 | isbn=0-19-507398-3}}


*[http://www.eia.doe.gov/bookshelf/brochures/gasoline/index.html Where Does My Gasoline Come from?], [[U.S. Department of Energy]], [[Energy Information Administration]], April 2008.
*{{cite book | author=R. Barrat| title=Atmospheric Dispersion Modelling | edition=1st Edition | publisher=Earthscan Publications | year=2001 | isbn=1-85383-642-7}}


*[http://techni.tachemie.uni-leipzig.de/otto/otto_g0_eng.html Otto Cycle] (About the [[Internal combustion engine|internal combustion engine]] [[Four-stroke cycle|four-stroke cycle]] invented by [[Nicolaus August Otto|Nicolaus A. Otto]])
*{{cite book | author=S.R. Hanna and R.E. Britter| title=Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites  | edition=1st Edition | publisher=Wiley-American Institute of Chemical Engineers | year=2002 | isbn=0-8169-0863-X}}


*[http://www.scribd.com/doc/1537932/US-Air-Force-rl31361 CRS Report For Congress] ''"Boutique Fuels" and Reformulated Gasoline: Harmonization of Fuel Standards'' (May 10, 2006) , Brent D. Yacobucci, Congressional Research Service, [[Library of Congress]]
*{{cite book | author=P. Zannetti| title=Air pollution modeling : theories, computational methods, and available software | edition= | publisher= Van Nostrand Reinhold | year=1990 | isbn=0-442-30805-1 }}

Latest revision as of 04:25, 22 November 2023


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Industrial air pollution source

Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.

Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.[1]

Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.

The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:

  • Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
  • The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
  • Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
  • The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).

Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.

The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.

Atmospheric layers

Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the troposphere. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The stratosphere is the next layer and extends from 18 km up to about 50 km. The third layer is the mesosphere which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.

The lowest part of the troposphere is called the atmospheric boundary layer (ABL) or the planetary boundary layer (PBL) and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the inversion layer (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the free troposphere and it extends up to the 18 km height of the troposphere.

The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the mixing layer. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.

In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as boundary layer models because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as mesoscale models have dispersion modeling capabilities that can extend horizontally as much as a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.

Gaussian air pollutant dispersion equation

The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.[2] Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.

Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947[3][4] which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.

Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes shown below:[5][6]


where:  
= crosswind dispersion parameter
  =
= vertical dispersion parameter =
= vertical dispersion with no reflections
  =
= vertical dispersion for reflection from the ground
  =
= vertical dispersion for reflection from an inversion aloft
  =
           
           
           
= concentration of emissions, in g/m³, at any receptor located:
            x meters downwind from the emission source point
            y meters crosswind from the emission plume centerline
            z meters above ground level
= source pollutant emission rate, in g/s
= horizontal wind velocity along the plume centerline, m/s
= height of emission plume centerline above ground level, in m
= vertical standard deviation of the emission distribution, in m
= horizontal standard deviation of the emission distribution, in m
= height from ground level to bottom of the inversion aloft, in m
= the exponential function

The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.

The sum of the four exponential terms in converges to a final value quite rapidly. For most cases, the summation of the series with m = 1, m = 2 and m = 3 will provide an adequate solution.

and are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.

Whereas older models rely on stability classes for the determination of and , more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.

Briggs plume rise equations

The Gaussian air pollutant dispersion equation (discussed above) requires the input of H which is the pollutant plume's centerline height above ground level. H is the sum of Hs (the actual physical height of the pollutant plume's emission source point) plus ΔH (the plume rise due the plume's buoyancy).

Visualization of a buoyant Gaussian air pollutant dispersion plume

To determine ΔH, many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.[7] In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.[8] In that same year, Briggs also wrote the section of the publication edited by Slade[9] dealing with the comparative analyses of plume rise models. That was followed in 1969 by his classical critical review of the entire plume rise literature,[10] in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations". Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.[11][12]

Briggs divided air pollution plumes into these four general categories:

  • Cold jet plumes in calm ambient air conditions
  • Cold jet plumes in windy ambient air conditions
  • Hot, buoyant plumes in calm ambient air conditions
  • Hot, buoyant plumes in windy ambient air conditions

Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportant. Although Briggs proposed plume rise equations for each of the above plume categories, it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes.

In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants. Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).

A logic diagram for using the Briggs equations[5] to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:

BriggsLogic.png
where:  
Δh = plume rise, in m
F  = buoyancy factor, in m4s−3
x = downwind distance from plume source, in m
xf = downwind distance from plume source to point of maximum plume rise, in m
u = windspeed at actual stack height, in m/s
s  = stability parameter, in s−2

The above parameters used in the Briggs' equations are discussed in Beychok's book.[5]

References

  1. J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", JAPCA, Vol. 21, No. 7, 1971.
  2. C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", Trans. Faraday Soc., 32:1249, 1936.
  3. O.G. Sutton, "The problem of diffusion in the lower atmosphere", QJRMS, 73:257, 1947.
  4. O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", QJRMS, 73:426, 1947.
  5. 5.0 5.1 5.2 M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. .
  6. D. B. Turner (1994). Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. .
  7. G.A. Briggs, "A plume rise model compared with observations", JAPCA, 15:433–438, 1965.
  8. G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", Atmos. Envir., 2:228–232, 1968.
  9. D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.
  10. G.A. Briggs, "Plume Rise", USAEC Critical Review Series, 1969.
  11. G.A. Briggs, "Some recent analyses of plume rise observation", Proc. Second Internat'l. Clean Air Congress, Academic Press, New York, 1971.
  12. G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", Atmos. Envir., 6:507–510, 1972.

Further reading

  • M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. 
  • K.B. Schnelle and P.R. Dey (1999). Atmospheric Dispersion Modeling Compliance Guide, 1st Edition. McGraw-Hill Professional. ISBN 0-07-058059-6. 
  • D.B. Turner (1994). Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. 
  • S.P. Arya (1998). Air Pollution Meteorology and Dispersion, 1st Edition. Oxford University Press. ISBN 0-19-507398-3. 
  • R. Barrat (2001). Atmospheric Dispersion Modelling, 1st Edition. Earthscan Publications. ISBN 1-85383-642-7. 
  • S.R. Hanna and R.E. Britter (2002). Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites, 1st Edition. Wiley-American Institute of Chemical Engineers. ISBN 0-8169-0863-X. 
  • P. Zannetti (1990). Air pollution modeling : theories, computational methods, and available software. Van Nostrand Reinhold. ISBN 0-442-30805-1.