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The sulfur cycle is very important in the environment, in plant and animal chemistry and in the atmosphere. We will focus on its role as a key driving force in our atmosphere. You will come to appreciate just how important sulfur is for our future as you learn more of how it cools our atmosphere, creates cloud formations and causes lightning, thunderstorms, tornadoes and hurricanes. Sulfur is one of the basic elements of the earth's early formation and as such has played an important role in our planets early formation. Below is a video that describes our atmosphere and a scientific article that shows how aerosols effect our climate. Aerosols are tiny particles that allow clouds to form. Throughout this document you will find that many use aerosols, dust, sulfate, CCN's, sulfur oxides (SOx) and particles synonymously to mean the same thing. However, we will show why they are not synonymous with each other, but instead have different affects on clouds.
Cloud Formation
Have Australian Rainfall and Cloudiness Increased Due to the Remote Effects of Asian Anthropogenic Aerosols?
(in press, 23/10/2006)
Leon D. Rotstayn,1 Wenju Cai,1 Martin R. Dix,1 Graham D. Farquhar,2 Yan Feng,3 Paul Ginoux,4 Michael Herzog,3 Akinori Ito,3 Joyce E. Penner,3 Michael L. Roderick,2 and Minghuai Wang3
Abstract. There is ample evidence that anthropogenic aerosols have important effects on climate in the Northern Hemisphere, but little such evidence in the Southern Hemisphere. Observations of Australian rainfall and cloudiness since 1950 show increases over much of the continent. We show that including anthropogenic aerosol changes in 20th Century simulations of a global climate model gives increasing rainfall and cloudiness over Australia during 1951– 1996, whereas omitting this forcing gives decreasing rainfall and cloudiness. The pattern of increasing rainfall when aerosols are included is strongest over northwestern Australia, in agreement with the observed trends. The strong impact of aerosols is primarily due to the massive Asian aerosol haze, as confirmed by a sensitivity test in which only Asian anthropogenic aerosols are included. The Asian haze alters the meridional temperature and pressure gradients over the tropical Indian Ocean, thereby increasing the tendency of monsoonal winds to flow towards Australia. Anthropogenic aerosols also make the simulated pattern of surface-temperature change in the tropical Pacific more like La Ni˜na, since they induce a cooling of the surface waters in the extratropical North Pacific, which are then transported to the tropical eastern Pacific via the deep ocean. Transient climate model simulations forced only by increased greenhouse gases have generally not reproduced the observed rainfall increase over northwestern and central Australia. Our results suggest that a possible reason for this failure was the omission of forcing by Asian aerosols. Further research is essential to more accurately quantify the role of Asian aerosols in forcing Australian climate change.
Clouds form in the atmosphere as condensed water cools and becomes visible, however, water in the atmosphere needs something to condense on. This works much the same way the mirror in your bathroom does. Moist air will not spontaneously condense until it is almost -40C degrees but it will collect on a cold surface like your mirror. In the atmosphere this cold surface is sulfate (SO4-2), a naturally forming crystalline salt of sulfuric acid. In the cold atmosphere, water collects on this sulfate particle and forms an ice crystal. Billions of these together in a small area will reflect and refract light to form what we see as a cloud and which is really billions of sulfur oxide particles in a concentrated area. Every Cloud has a Filthy Lining is a NASA article that explains this in detail. In this very important video below see how effective these salts create clouds, please ignore the commercial at the start, couldn't eliminate it.
Sulphur oxide (SOx) is any sulfur and oxygen molecule combination (e.g. SO3, SO4-2, SO2, SO3-2 and so on) and in the atmosphere sulfur oxide quickly combines with water to create sulphuric acid, (H2SO4), occurring because of their hygroscopic nature. If this acid is in a high enough concentration, acid rain may fall to the ground (as rain or snow). Cloud chemistry is a very complex science and it has been simplified here for easy explanation. The attached links show some of the chemistry in detail as understood by science today. The diagram below shows how the process works in the atmosphere. One of the little known facts about sulfuric acid as this study below shows, as it approaches -40 degrees C in a magnetic field it will ionize, we believe if the pressure is also reduced this process occurs almost 100% of the time.
Raman Study of Sulfuric Acid at Low Temperature
Koichi Tomikawa and Hitoshi Kanno
*Department of Chemistry, National Defense Academy, Yokosuka 239, Japan
A Raman spectroscopic study has been carried out for aqueous sulfuric acid of various concentrations at room temperature and in the glassy state. Temperature dependence of the Raman spectra was also investigated from 44 to −40 °C. Anomalous Tg (glass transition temperature) behavior of the aqueous sulfuric acid solution at 86 wt % H2SO4 is interpreted in terms of ionic species involved in Raman spectral changes. It is shown that ionization of sulfuric acid increases exponentially with decreasing temperature. Complete ionization was attained up to 50 wt % H2SO4 concentration in glassy aqueous H2SO4 solution.
The term EPC Ionization refers to these promoters of the reaction, electromagnetic, pressure and cold (temperature), these are the three criteria for gas phase ionization. While this study shows the ionization process in the aqueous phase in the gas or vapour phase we believe sulfuric acid will ionize as shown below.
Scientifically trained minds will want to stop here and say this can not occur because the net result of the reaction is the dissociation of water in the atmosphere and this can not occur. All we can do is explain, yes this is true and refer to the Hydrogen Charging Cycle page, which illustrates why this isn't an issue, as water is both created and dissociate every second of the day in our environment. This process is fundamental to the energy balance of our planet and we believe, every planet. It is becoming more understood today that most planetary bodies have had water at one time and not all were hit by icy comets, there must, therefore, be a natural process that creates water.
Clouds will not form without an aerosol, CCN (cloud condensing nuclei) or a supercooled particle for the water to form on. As stated above, super cooled water will remain invisible until it is well below its freezing point. In our atmosphere sulfur forms the CCN the vast majority of the time in the form of sulphate (SO4-2). This process is exhibited below in a typical cloud. While we show the ratio of water to sulfate here as 3:1 for illustration purposes, this would be a highly acidic rain drop. A normal ratio today may be1000 : 1, and acid rain from the 1970's may be 500 : 1.
Natural sources that produce sulfur oxides (SOx), and thus sulfate, include volcanoes, phytoplankton in the oceans, bacteria in decaying plant and animal material and many others. SOx in the environment is also produced from man-made (anthropogenic) sources such as from the burning of coal, diesel oil, gasoline and from oil refining. SO2 flaring from refinery upsets are a leading cause of SO3 in the atmosphere and the stats on this are alarming, making it one of the largest sources of volatile SOx in our environment.
Some of these sulphur oxides, (SO3) in particular, when mixed with water, generate heat in an exothermic reaction. This, in turn, generates a low-pressure area, thermal or updraft. As this occurs, the air rises, cools and forms a cloud until it dissipates as rain or snow. In Classical Atmospheric Thermodynamics this process is explained by the IR (infrared) heating of parcels of air that move upwards as a result of instabilities in the air mass. But science does not clearly define how this occurs; only that it does.
In a thunderstorm this process takes place millions of times a second and is enhanced by the energy that is contained in each inter-cloud lightning event which generates heat in the storm. This process will be described in greater detail in the section on thunderstorms and again in the section on lightning.
The chemical process shown below is fundamental to the atmospheric sulphur cycle, cloud formation and therefore, to storm formation. As we see, two sulfur dioxide (SO2) molecules combine in the atmosphere with oxygen (O2) and along with heat, create two sulfur trioxide (SO3) molecules. The SO3, in turn, combines with a water molecule (H20) to create sulfuric acid (H2SO4) and heat. As the H2S04 rises in the atmosphere, it cools and as it is exposed to electromagnetic promoters, breaks down into two positively charged hydrogen ions (2H+) and an offsetting negatively charged sulfate (SO4-2) molecule that itself, breaks down into sulfur trioxide (SO3) and negatively charged oxygen (O-2). At this point, we have positive hydrogen (H+) and negative oxygen (O-2) in the atmosphere.
2 SO2 + O2 + Heat = 2 SO3
SO3 + H2O = H2SO4 + Heat
H2SO4 + Cooling + Electromagnetic Promoters = 2H+ and SO4-2
SO4-2 + heat = SO3 + O-2
(once enough ionized gas builds up electrons will move and it is this movement of electrons that creates lightning)
X amount of O-2 + X amount 2H+ = X amount of (2-e) electrons
As the H+ leaves the upper atmosphere, it removes mass and therefore, energy from the environment. Science is currently studying this process and may soon discover, using advanced scientific equipment like the THEMIS Satellite, that the amount of H+ leaving the atmosphere is far more then expected. Furthermore, it may be found that the connection between the Sun and the Earth is much greater than current scientific theory comprehends. Present day theory holds that H+ mixes with nitrogen and oxygen to reform only water through a long chain of chemical reactions. However, this has never been shown scientifically because of the difficulty in measuring these natural processes in the atmosphere and the challenge of reproducibility.
The Atmosphere - A Battery
We can compare the atmospheric chemical reactions to the everyday car battery. Our atmosphere has, in fact, often been described as a battery and there is good reason for this.
"The lead-acid battery used in automobiles, consists of a series of six identical cells assembled in series. Each cell has a lead anode and a cathode made from lead dioxide packed in a metal plaque. Cathode and anode are submerged in a solution of sulfuric acid acting as the electrolyte.
Lead-acid battery half cell reactions are shown below:
Under standard conditions, each cell may produce a potential of 2 volts and therefore, overall voltage produced is 12 volts. Differing from mercury and zinc-carbon batteries, lead-acid batteries are rechargeable. If an external voltage is supplied to the battery it will produce an electrolysis of the products in the overall reaction (discharge), thus recovering initial components which made the battery work."
Extracted from Wikipedia.org
When a battery is initially filled with sulfuric acid there is no need to charge the battery as the immediate chemical reaction that occurs charges the battery's plates until you use it to start your car. If you could drain the acid and refill it with more acid you would never need to charge the battery, this is the principle behind the redox Flow Battery. This is also exactly what occurs in the atmosphere. The acid is constantly replenished, allowing the atmosphere to act like a battery. To see an animated version of this process click on Lead Accumulator or Battery Cycle.
Hybird Sulfur Cycle
The Hybird Sulfur Cycle is being used in conjunction with waste heat from nuclear power as a method to produce hydrogen on a large scale. This proven reaction cycle shows the process that occurs in the atmosphere in a thunderstorm.
The two reactions in the HyS cycle are as follows:
2 H2SO4 → 2 H2O + 2 SO2 + O2 (thermochemical 800 - 900 °C)
The above process occurs in the atmosphere due to the heat generated by inter-cloud lightning.
SO2 + 2 H2O → H2SO4 + H2 (electrochemical 80 - 120 °C)
The above process occurs in the atmosphere due to the electron flow of lightning.
Net reaction: 2 H2O → 2 H2 + O2
Sulfur dioxide acts as a depolarizer on the anode. This results in a significant decrease of voltage (and thus electrical energy) required for reaction (2). The reversible voltage of reaction (2) is about 0.17 V, compared to 1.23 V required for electrolysis of water (with oxygen evolution as the anodic reaction).
For a detailed explanation of this process and experimental project see, The Hybird Sulfur Cycle.
The Sulfur-Iodine Cycle
Another example of a process that produces hydrogen is the Sulfur-Iodine Cycle described below in an excerpt from Wikipedia.org.
The three reactions that produce hydrogen are as follows:
I 2 + SO2 + 2 H2O → 2 HI + H2SO4 (120°C)
The HI is then separated by distillation. Note that concentrated H2SO4 may react with HI, giving I2, SO2 and H2O (backward reaction). Many chemical processes are reversible reactions, such as ammonia production from N2 and H2, but removing the desired product will shift equilibrium to the right. This reaction is sometimes referred to as Bunsen Reaction.
2 H2SO4 → 2 SO2 + 2 H2O + O2 (830°C)
The water, SO2 and residual H2SO4 must be separated from the oxygen byproduct by condensation. See Sulfur dioxide Temperature dependence of aqueous solubility for temperatures.
2 HI → I2 + H2 (450°C)
Iodine and any accompanying water or SO2 are separated by condensation, and the hydrogen product remains as a gas.
Net reaction: 2 H2O → 2 H2 + O2
The sulfur and iodine compounds are recovered and reused, hence the consideration of the process as a cycle. This S-I process is a chemical heat engine. Heat enters the cycle in high temperature endothermic chemical reactions 2 and 3, and heat exits the cycle in the low temperature exothermic reaction 1. The difference between the heat entering the cycle and the heat leaving the cycle exits the cycle in the form of the heat of combustion of the hydrogen produced.
Extracted from Wikipedia.org
