Hydrogen sulfide
Encyclopedia
Hydrogen sulfide is the chemical compound
with the formula
. It is a colorless, very poisonous, flammable gas
with the characteristic foul odor of expired egg
s perceptible at concentrations as low as 0.00047 parts per million. It often results from the bacterial breakdown of organic matter
in the absence of oxygen
, such as in swamps and sewers; this process is commonly known as anaerobic digestion
. It also occurs in volcanic
gases, natural gas
, and some well waters. The human body
produces small amounts of and uses it as a signaling molecule
.
burn with a blue flame to form sulfur dioxide
and water. In general, hydrogen sulfide acts as a reducing agent
.
At high temperature or in the presence of catalysts, sulfur dioxide can be made to react with hydrogen sulfide to form elemental sulfur
and water
. This is exploited in the Claus process
, the main way to convert hydrogen sulfide into elemental sulfur.
Hydrogen sulfide is slightly soluble in water and acts as a weak acid
, giving the hydrosulfide ion HS− (pKa
= 6.9 in 0.01-0.1 mol/litre solutions at 18 °C) and the sulfide
ion S2− (pKa = 11.96). A solution of hydrogen sulfide in water, known as sulfhydric acid or hydrosulfuric acid, is initially clear but over time turns cloudy. This is due to the slow reaction of hydrogen sulfide with the oxygen dissolved in water, yielding elemental sulfur, which precipitates out.
Hydrogen sulfide reacts with metal ions to form metal sulfides, which may be considered the salts of hydrogen sulfide. Some ores
are sulfides. Metal sulfides often have a dark color. Lead(II) acetate
paper is used to detect hydrogen sulfide because it turns grey in the presence of the gas as lead(II) sulfide
is produced. Reacting metal sulfides with strong acid liberates hydrogen sulfide.
If gaseous hydrogen sulfide is put into contact with concentrated nitric acid
, it explodes.
Hydrogen sulfide reacts with alcohols to form thiols.
, which is natural gas with high content of . It can also be produced by reacting hydrogen
gas with molten elemental sulfur at about 450 °C. Hydrocarbons can replace hydrogen in this process.
Sulfate-reducing bacteria
(resp. sulfur-reducing bacteria
) generate usable energy under low-oxygen conditions by using sulfates (resp. elemental sulfur) to oxidize
organic compounds or hydrogen; this produces hydrogen sulfide as a waste product.
The standard lab preparation is to react ferrous sulfide
(FeS) with a strong acid in a Kipp generator.
A less well-known and more convenient alternative is to react aluminium sulfide
with water:
This gas is also produced by heating sulfur with solid organic compounds and by reducing sulfurated organic compounds with hydrogen.
Hydrogen sulfide is also a byproduct of some reactions and caution should be taken when production is likely as exposure can be fatal.
Hydrogen sulfide production can be costly because of the dangers involved in production.
Small amounts of hydrogen sulfide occur in crude petroleum, but natural gas
can contain up to 90%. Volcano
es and some hot spring
s (as well as cold springs
) emit some , where it probably arises via the hydrolysis
of sulfide minerals, i.e. MS + → MO + .
About 10% of total global emissions of is due to human activity. By far the largest industrial route to occurs in petroleum refineries
: The hydrodesulfurization
process liberates sulfur from petroleum
by the action of hydrogen. The resulting is converted to elemental sulfur by partial combustion via the Claus process
, which is a major source of elemental sulfur. Other anthropogenic sources of hydrogen sulfide include coke
ovens, paper mill
s (using the sulfate method), and tanneries
. arises from virtually anywhere where elemental sulfur comes in contact with organic material, especially at high temperatures.
Hydrogen sulfide can be present naturally in well water. In such cases, ozone
is often used for its removal; an alternative method uses a filter with manganese dioxide. Both methods oxidize sulfides to much less toxic sulfates.
are produced using hydrogen sulfide. These include methanethiol
, ethanethiol
, and thioglycolic acid
.
bases, hydrogen sulfide converts to alkali hydrosulfides such as sodium hydrosulfide
and sodium sulfide
, which are used in the degradation of biopolymers. The depilation of hides and the delignification of pulp by the Kraft process
both are effected by alkali sulfides.
, in the qualitative inorganic analysis
of metal ions. In these analyses, heavy metal (and nonmetal
) ions (e.g., Pb(II), Cu(II), Hg(II), As(III)) are precipitated from solution upon exposure to . The components of the resulting precipitate redissolve with some selectivity.
For small-scale laboratory use in analytic chemistry, the use of thioacetamide
has superseded as a source of sulfide ions.
by flotation
, mineral powders are often treated with hydrogen sulfide to enhance the separation. Metal parts are sometimes passivated with hydrogen sulfide. Catalysts used in hydrodesulfurization
are routinely activated with hydrogen sulfide, and the behavior of metallic catalysts used in other parts of a refinery
is also modified using hydrogen sulfide.
, from normal water via the Girdler Sulfide process
.
, biogas
, and LPG. It can be removed in a number of ways.
, which combines with hydrogen sulfide.
In order to regenerate iron(III) oxide, the container must be taken out of service, flooded with water and aerated.
On completion of the regeneration reaction the container is drained of water and can be returned to service.
The advantage of this system is that it is completely passive during the extraction phase.
is a more complex method of removing sulfur from fuels.
: 4.3–46%). Being heavier than air, it tends to accumulate at the bottom of poorly ventilated spaces. Although very pungent at first, it quickly deadens the sense of smell, so potential victims may be unaware of its presence until it is too late. For safe handling procedures, a hydrogen sulfide material safety data sheet (MSDS) should be consulted.
In 1975, a hydrogen sulfide explosion in Denver City
, located in Yoakum and Gaines counties, Texas
, caused the state legislature to focus on the deadly hazards of the gas. State Representative
E L Short
of Tahoka
in Lynn County, took the lead in endorsing an investigation by the Texas Railroad Commission
and urged that residents be warned "by knocking on doors if necessary" of the imminent danger stemming from the gas. One may die from the second inhalation of the gas, and a warning itself may be too late.
is most affected. The toxicity of is comparable with that of hydrogen cyanide. It forms a complex bond with iron
in the mitochondrial cytochrome
enzyme
s, thus preventing cellular respiration
.
Since hydrogen sulfide occurs naturally in the body, the environment and the gut, enzymes exist in the body capable of detoxifying it by oxidation to (harmless) sulfate. Hence, low levels of hydrogen sulfide may be tolerated indefinitely.
At some threshold level, believed to average around 300–350 ppm, the oxidative enzymes become overwhelmed. Many personal safety gas detectors, such as those used by utility, sewage and petrochemical workers, are set to alarm at as low as 5 to 10 ppm and to go into high alarm at 15 ppm.
An interesting diagnostic clue of extreme poisoning by is the discoloration of copper
coins in the pockets of the victim. Treatment involves immediate inhalation of amyl nitrite
, injections of sodium nitrite
, inhalation of pure oxygen, administration of bronchodilator
s to overcome eventual bronchospasm
, and in some cases hyperbaric oxygen therapy
(HBO). HBO therapy has anecdotal support and remains controversial.
Exposure to lower concentrations can result in eye
irritation, a sore throat and cough
, nausea, shortness of breath, and fluid in the lung
s. These effects are believed to be due to the fact that hydrogen sulfide combines with alkali
present in moist surface tissues to form sodium sulfide
, a caustic. These symptoms usually go away in a few weeks.
Long-term, low-level exposure may result in fatigue
, loss of appetite, headaches, irritability, poor memory, and dizziness
. Chronic exposure to low level (around 2 ppm) has been implicated in increased miscarriage and reproductive health issues among Russian and Finnish wood pulp workers, but the reports have not (as of circa 1995) been replicated.
Although respiratory paralysis may be immediate, it can also be delayed up to 72 hours.
Hydrogen sulfide was used by the British as a chemical agent during World War I
. It was not considered to be an ideal war gas, but, while other gases were in short supply, it was used on two occasions in 1916.
A dump of toxic waste containing hydrogen sulfide is believed to have caused 17 deaths and thousands of illnesses in Abidjan, on the West Africa coast, in the 2006 Côte d'Ivoire toxic waste dump.
wave in 2008 in Japan. The wave prompted staff at Tokyo's suicide prevention
center to set up a special hot line during "Golden Week", as they received an increase in calls from people wanting to kill themselves during the annual May holiday.
As of 2010, this phenomenon has occurred in a number of US cities (and in Putney West London, England), prompting warnings to those arriving at the site of the suicide. These first responders, such as emergency services workers or family members are at risk of death from inhaling lethal quantities of the gas, or by fire. Local governments have also initiated campaigns to prevent such suicides.
ian body and has a number of biological signaling functions. (Only two other such gases are currently known: nitric oxide
(NO) and carbon monoxide
(CO).)
The gas is produced from cysteine
by the enzyme
s cystathionine beta-synthase and cystathionine gamma-lyase
. It acts as a relaxant of smooth muscle
and as a vasodilator and is also active in the brain
, where it increases the response of the NMDA receptor
and facilitates long term potentiation, which is involved in the formation of memory.
Eventually the gas is converted to sulfite in the mitochondria by thiosulfate reductase, and the sulfite is further oxidized to thiosulfate
and sulfate
by sulfite oxidase
. The sulfates are excreted in the urine.
Due to its effects similar to nitric oxide
(without its potential to form peroxides by interacting with superoxide
), hydrogen sulfide is now recognized as potentially protecting against cardiovascular disease. The cardioprotective role effect of garlic
is caused by catabolism
of the polysulfide group in allicin to , a reaction that could depend on reduction mediated by glutathione
.
Though both nitric oxide
and hydrogen sulfide have been shown to relax blood vessels, their mechanisms of action are different: while NO activates the enzyme guanylyl cyclase, activates ATP-sensitive potassium channel in smooth muscle cells. Researchers are not clear how the vessel-relaxing responsibilities are shared between nitric oxide and hydrogen sulfide. However there exists some evidence to suggest that nitric oxide does most of the vessel-relaxing work in large vessels and hydrogen sulfide is responsible for similar action in smaller blood vessels.
Like nitric oxide, hydrogen sulfide is involved in the relaxation of smooth muscle that causes erection
of the penis, presenting possible new therapy opportunities for erectile dysfunction
.
In Alzheimer's disease
the brain's hydrogen sulfide concentration is severely decreased. In trisomy 21 (the most common form of Down syndrome) the body produces an excess of hydrogen sulfide. Hydrogen sulfide is also involved in the disease process of type 1 diabetes
. The beta cells of the pancreas
in type 1 diabetes produce an excess of the gas, leading to the death of beta cells and to a reduced production of insulin by those that remain.
-like hypothermia
by applying a low dosage of hydrogen sulfide (81 ppm ) in the air. The breathing rate of the animals sank from 120 to 10 breaths per minute and their temperature fell from 37 °C to just 2 °C above ambient temperature (in effect, they had become cold-blooded
). The mice survived this procedure for 6 hours and afterwards showed no negative health consequences. In 2006 it was shown that the blood pressure
of mice treated in this fashion with hydrogen sulfide did not significantly decrease.
A similar process known as hibernation
occurs naturally in many mammal
s and also in toad
s, but not in mice. (Mice can fall into a state called clinical torpor
when food shortage occurs). If the -induced hibernation can be made to work in humans, it could be useful in the emergency management of severely injured patients, and in the conservation of donated organs. In 2008, hypothermia induced by hydrogen sulfide for 48 hours was shown to reduce the extent of brain damage caused by experimental stroke
in rats.
As mentioned above, hydrogen sulfide binds to cytochrome oxidase
and thereby prevents oxygen from binding, which leads to the dramatic slowdown of metabolism
. Animals and humans naturally produce some hydrogen sulfide in their body; researchers have proposed that the gas is used to regulate metabolic activity and body temperature, which would explain the above findings.
Two recent studies cast doubt that the effect can be achieved in larger mammals. A 2008 study failed to reproduce the effect in pigs, concluding that the effects seen in mice were not present in larger mammals. Likewise a paper by Haouzi et al. noted that there is no induction of hypometabolism in sheep, either.
However, at a February 2010 TED
conference, Mark Roth
announced that hydrogen sulfide induced hypothermia had completed Phase I clinical trials. He estimated that further trials would take 'a few years.'
, the biogeochemical cycle
of sulfur
on Earth.
In the absence of oxygen
, sulfur-reducing
and sulfate-reducing bacteria
derive energy from oxidizing
hydrogen or organic molecules by reducing elemental sulfur or sulfate
to hydrogen sulfide. Other bacteria liberate hydrogen sulfide from sulfur-containing amino acid
s; this gives rise to the odor of rotten eggs and contributes to the odor of flatulence
.
As organic matter decays under low-oxygen (or hypoxic
) conditions (such as in swamps, eutrophic lakes or dead zones
of oceans), sulfate-reducing bacteria will use the sulfates present in the water to oxidize the organic matter, producing hydrogen sulfide as waste. Some of the hydrogen sulfide will react with metal ions in the water to produce metal sulfides, which are not water soluble. These metal sulfides, such as ferrous sulfide
FeS, are often black or brown, leading to the dark color of sludge.
Several groups of bacteria can use hydrogen sulfide as fuel, oxidizing it to elemental sulfur or to sulfate by using dissolved oxygen, metal oxides (e.g., Fe oxyhydroxides and Mn oxides) or nitrate as oxidant.
The purple sulfur bacteria
and the green sulfur bacteria
use hydrogen sulfide as electron donor
in photosynthesis
, thereby producing elemental sulfur. (In fact, this mode of photosynthesis is older than the mode of cyanobacteria, algae
, and plant
s, which uses water as electron donor and liberates oxygen.)
that have occurred in the Earth's past. In particular, a buildup of hydrogen sulfide in the atmosphere may have caused the Permian-Triassic extinction event
252 million years ago.
Organic residues from these extinction boundaries indicate that the oceans were anoxic (oxygen-depleted) and had species of shallow plankton that metabolized . The formation of may have been initiated by massive volcanic eruptions, which emitted carbon dioxide
and methane
into the atmosphere, which warmed the oceans, lowering their capacity to absorb oxygen that would otherwise oxidize . The increased levels of hydrogen sulfide could have killed oxygen-generating plants as well as depleted the ozone layer, causing further stress. Small blooms have been detected in modern times in the Dead Sea
and in the Atlantic ocean off the coast of Namibia.
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...
with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....
. It is a colorless, very poisonous, flammable gas
Gas
Gas is one of the three classical states of matter . Near absolute zero, a substance exists as a solid. As heat is added to this substance it melts into a liquid at its melting point , boils into a gas at its boiling point, and if heated high enough would enter a plasma state in which the electrons...
with the characteristic foul odor of expired egg
Egg
-Biology/food:*Egg , an organic vessel in which an embryo first begins to develop*Ovum, a female egg cell*Egg , the egg of a fowl or fish consumed as food-Places:*Egg Island *Egg, Switzerland, a Swiss municipality...
s perceptible at concentrations as low as 0.00047 parts per million. It often results from the bacterial breakdown of organic matter
Organic matter
Organic matter is matter that has come from a once-living organism; is capable of decay, or the product of decay; or is composed of organic compounds...
in the absence of oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
, such as in swamps and sewers; this process is commonly known as anaerobic digestion
Anaerobic digestion
Anaerobic digestion is a series of processes in which microorganisms break down biodegradable material in the absence of oxygen. It is used for industrial or domestic purposes to manage waste and/or to release energy....
. It also occurs in volcanic
Volcano
2. Bedrock3. Conduit 4. Base5. Sill6. Dike7. Layers of ash emitted by the volcano8. Flank| 9. Layers of lava emitted by the volcano10. Throat11. Parasitic cone12. Lava flow13. Vent14. Crater15...
gases, natural gas
Natural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
, and some well waters. The human body
Human body
The human body is the entire structure of a human organism, and consists of a head, neck, torso, two arms and two legs.By the time the human reaches adulthood, the body consists of close to 100 trillion cells, the basic unit of life...
produces small amounts of and uses it as a signaling molecule
Signaling molecule
A signaling molecule is a chemical involved in transmitting information between cells. Such molecules are released from the cell sending the signal, cross over the gap between cells by diffusion, and interact with specific receptors in another cell, triggering a response in that cell by activating...
.
Properties
Hydrogen sulfide is slightly heavier than air; a mixture of and air is explosive. Hydrogen sulfide and oxygenOxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
burn with a blue flame to form sulfur dioxide
Sulfur dioxide
Sulfur dioxide is the chemical compound with the formula . It is released by volcanoes and in various industrial processes. Since coal and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide unless the sulfur compounds are removed before burning the fuel...
and water. In general, hydrogen sulfide acts as a reducing agent
Reducing agent
A reducing agent is the element or compound in a reduction-oxidation reaction that donates an electron to another species; however, since the reducer loses an electron we say it is "oxidized"...
.
At high temperature or in the presence of catalysts, sulfur dioxide can be made to react with hydrogen sulfide to form elemental sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
and water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
. This is exploited in the Claus process
Claus process
The Claus process is the most significant gas desulfurizing process, recovering elemental sulfur from gaseous hydrogen sulfide. First patented in 1883 by the scientist Carl Friedrich Claus, the Claus process has become the industry standard....
, the main way to convert hydrogen sulfide into elemental sulfur.
Hydrogen sulfide is slightly soluble in water and acts as a weak acid
Weak acid
A weak acid is an acid that dissociates incompletely. It does not release all of its hydrogens in a solution, donating only a partial amount of its protons to the solution...
, giving the hydrosulfide ion HS− (pKa
Acid dissociation constant
An acid dissociation constant, Ka, is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction known as dissociation in the context of acid-base reactions...
= 6.9 in 0.01-0.1 mol/litre solutions at 18 °C) and the sulfide
Sulfide
A sulfide is an anion of sulfur in its lowest oxidation state of 2-. Sulfide is also a slightly archaic term for thioethers, a common type of organosulfur compound that are well known for their bad odors.- Properties :...
ion S2− (pKa = 11.96). A solution of hydrogen sulfide in water, known as sulfhydric acid or hydrosulfuric acid, is initially clear but over time turns cloudy. This is due to the slow reaction of hydrogen sulfide with the oxygen dissolved in water, yielding elemental sulfur, which precipitates out.
Hydrogen sulfide reacts with metal ions to form metal sulfides, which may be considered the salts of hydrogen sulfide. Some ores
Orés
Orés is a municipality in the Cinco Villas, in the province of Zaragoza, in the autonomous community of Aragon, Spain. It belongs to the comarca of Cinco Villas. It is placed 104 km to the northwest of the provincial capital city, Zaragoza. Its coordinates are: 42° 17' N, 1° 00' W, and is...
are sulfides. Metal sulfides often have a dark color. Lead(II) acetate
Lead(II) acetate
Lead acetate , also known as lead acetate, lead diacetate, plumbous acetate, sugar of lead, lead sugar, salt of Saturn, and Goulard's powder, is a white crystalline chemical compound with a sweetish taste. It is made by treating lead oxide with acetic acid. Like other lead compounds, it is toxic...
paper is used to detect hydrogen sulfide because it turns grey in the presence of the gas as lead(II) sulfide
Lead(II) sulfide
Lead sulfide is an inorganic compound with the formula Pb. It finds limited use in electronic devices. PbS, also known as galena, is the principal ore and most important compound of lead....
is produced. Reacting metal sulfides with strong acid liberates hydrogen sulfide.
If gaseous hydrogen sulfide is put into contact with concentrated nitric acid
Nitric acid
Nitric acid , also known as aqua fortis and spirit of nitre, is a highly corrosive and toxic strong acid.Colorless when pure, older samples tend to acquire a yellow cast due to the accumulation of oxides of nitrogen. If the solution contains more than 86% nitric acid, it is referred to as fuming...
, it explodes.
Hydrogen sulfide reacts with alcohols to form thiols.
Production
Hydrogen sulfide is most commonly obtained by its separation from sour gasSour gas
Sour gas is natural gas or any other gas containing significant amounts of hydrogen sulfide . Natural gas is usually considered sour if there are more than 5.7 milligrams of H2S per cubic meter of natural gas, which is equivalent to approximately 4 ppm by volume...
, which is natural gas with high content of . It can also be produced by reacting hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...
gas with molten elemental sulfur at about 450 °C. Hydrocarbons can replace hydrogen in this process.
Sulfate-reducing bacteria
Sulfate-reducing bacteria
Sulfate-reducing bacteria are those bacteria and archaea that can obtain energy by oxidizing organic compounds or molecular hydrogen while reducing sulfate to hydrogen sulfide...
(resp. sulfur-reducing bacteria
Sulfur-reducing bacteria
Sulfur-reducing bacteria get their energy by reducing elemental sulfur to hydrogen sulfide. They couple this reaction with the oxidation of acetate, succinate or other organic compounds....
) generate usable energy under low-oxygen conditions by using sulfates (resp. elemental sulfur) to oxidize
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
organic compounds or hydrogen; this produces hydrogen sulfide as a waste product.
The standard lab preparation is to react ferrous sulfide
Iron(II) sulfide
Iron sulfide or ferrous sulfide is a chemical compound with the formula . In practice, iron sulfides are often non-stoichiometric. Powdered iron sulfide is pyrophoric Iron(II) sulfide or ferrous sulfide (Br.E. sulphide) is a chemical compound with the formula . In practice, iron sulfides are...
(FeS) with a strong acid in a Kipp generator.
- FeS + 2 HCl → FeCl2 + H2S
A less well-known and more convenient alternative is to react aluminium sulfide
Aluminium sulfide
Aluminium sulfide or aluminium sulphide is a chemical compound with the formula Al2S3. This colorless species has an interesting structural chemistry, existing in several forms. The material is sensitive to moisture, hydrolyzing to hydrated aluminium oxides/hydroxides. This can begin when the...
with water:
- 6 H2O + Al2S3 → 3 H2S + 2 Al(OH)3
This gas is also produced by heating sulfur with solid organic compounds and by reducing sulfurated organic compounds with hydrogen.
Hydrogen sulfide is also a byproduct of some reactions and caution should be taken when production is likely as exposure can be fatal.
Hydrogen sulfide production can be costly because of the dangers involved in production.
Occurrence
Natural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
can contain up to 90%. Volcano
Volcano
2. Bedrock3. Conduit 4. Base5. Sill6. Dike7. Layers of ash emitted by the volcano8. Flank| 9. Layers of lava emitted by the volcano10. Throat11. Parasitic cone12. Lava flow13. Vent14. Crater15...
es and some hot spring
Hot spring
A hot spring is a spring that is produced by the emergence of geothermally heated groundwater from the Earth's crust. There are geothermal hot springs in many locations all over the crust of the earth.-Definitions:...
s (as well as cold springs
Mineral spring
Mineral springs are naturally occurring springs that produce water containing minerals, or other dissolved substances, that alter its taste or give it a purported therapeutic value...
) emit some , where it probably arises via the hydrolysis
Hydrolysis
Hydrolysis is a chemical reaction during which molecules of water are split into hydrogen cations and hydroxide anions in the process of a chemical mechanism. It is the type of reaction that is used to break down certain polymers, especially those made by condensation polymerization...
of sulfide minerals, i.e. MS + → MO + .
About 10% of total global emissions of is due to human activity. By far the largest industrial route to occurs in petroleum refineries
Oil refinery
An oil refinery or petroleum refinery is an industrial process plant where crude oil is processed and refined into more useful petroleum products, such as gasoline, diesel fuel, asphalt base, heating oil, kerosene, and liquefied petroleum gas...
: The hydrodesulfurization
Hydrodesulfurization
Hydrodesulfurization is a catalytic chemical process widely used to remove sulfur from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils...
process liberates sulfur from petroleum
Petroleum
Petroleum or crude oil is a naturally occurring, flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling...
by the action of hydrogen. The resulting is converted to elemental sulfur by partial combustion via the Claus process
Claus process
The Claus process is the most significant gas desulfurizing process, recovering elemental sulfur from gaseous hydrogen sulfide. First patented in 1883 by the scientist Carl Friedrich Claus, the Claus process has become the industry standard....
, which is a major source of elemental sulfur. Other anthropogenic sources of hydrogen sulfide include coke
Coke (fuel)
Coke is the solid carbonaceous material derived from destructive distillation of low-ash, low-sulfur bituminous coal. Cokes from coal are grey, hard, and porous. While coke can be formed naturally, the commonly used form is man-made.- History :...
ovens, paper mill
Paper mill
A paper mill is a factory devoted to making paper from vegetable fibres such as wood pulp, old rags and other ingredients using a Fourdrinier machine or other type of paper machine.- History :...
s (using the sulfate method), and tanneries
Tanning
Tanning is the making of leather from the skins of animals which does not easily decompose. Traditionally, tanning used tannin, an acidic chemical compound from which the tanning process draws its name . Coloring may occur during tanning...
. arises from virtually anywhere where elemental sulfur comes in contact with organic material, especially at high temperatures.
Hydrogen sulfide can be present naturally in well water. In such cases, ozone
Ozone
Ozone , or trioxygen, is a triatomic molecule, consisting of three oxygen atoms. It is an allotrope of oxygen that is much less stable than the diatomic allotrope...
is often used for its removal; an alternative method uses a filter with manganese dioxide. Both methods oxidize sulfides to much less toxic sulfates.
Production of thioorganic compounds
Several organosulfur compoundsOrganosulfur compounds
Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odours, but many of the sweetest compounds known are organosulfur derivatives. Nature abounds with organosulfur compounds—sulfur is essential for life. Two of the 20 common amino acids are...
are produced using hydrogen sulfide. These include methanethiol
Methanethiol
Methanethiol is a colorless gas with a smell like rotten cabbage. It is a natural substance found in the blood and brain of humans and other animal as well as plant tissues. It is disposed of through animal feces. It occurs naturally in certain foods, such as some nuts and cheese...
, ethanethiol
Ethanethiol
Ethanethiol is an organic compound with the formula CH3CH2SH. It consists of an ethyl group, CH3CH2, attached to a thiol group, SH. Its structure parallels that of ethanol, but with S instead of O. The presence of S leads to many different properties, most notably the infamous odour of EtSH...
, and thioglycolic acid
Thioglycolic acid
Thioglycolic acid is the organic compound HSCH2CO2H. It contains both a thiol and a carboxylic acid. It is a clear liquid with a strong unpleasant odor...
.
Alkali metal sulfides
Upon combining with alkali metalAlkali metal
The alkali metals are a series of chemical elements in the periodic table. In the modern IUPAC nomenclature, the alkali metals comprise the group 1 elements, along with hydrogen. The alkali metals are lithium , sodium , potassium , rubidium , caesium , and francium...
bases, hydrogen sulfide converts to alkali hydrosulfides such as sodium hydrosulfide
Sodium hydrosulfide
Sodium hydrosulfide is the chemical compound with the formula NaHS. This compound is the product of the half neutralization of hydrogen sulfide with sodium hydroxide. NaHS is a useful reagent for the synthesis of organic and inorganic sulfur compounds. It is a colorless solid that typically smells...
and sodium sulfide
Sodium sulfide
Sodium sulfide is the name used to refer to the chemical compound Na2S, but more commonly it refers to the hydrate Na2S·9H2O. Both are colorless water-soluble salts that give strongly alkaline solutions...
, which are used in the degradation of biopolymers. The depilation of hides and the delignification of pulp by the Kraft process
Kraft process
The kraft process describes a technology for conversion of wood into wood pulp consisting of almost pure cellulose fibers...
both are effected by alkali sulfides.
Analytical chemistry
For well over a century, hydrogen sulfide was important in analytical chemistryAnalytical chemistry
Analytical chemistry is the study of the separation, identification, and quantification of the chemical components of natural and artificial materials. Qualitative analysis gives an indication of the identity of the chemical species in the sample and quantitative analysis determines the amount of...
, in the qualitative inorganic analysis
Qualitative inorganic analysis
Classical qualitative inorganic analysis is a method of analytical chemistry which seeks to find elemental composition of inorganic compounds. It is mainly focused on detecting ions in an aqueous solution, so that materials in other forms may need to be brought into this state before using standard...
of metal ions. In these analyses, heavy metal (and nonmetal
Nonmetal
Nonmetal, or non-metal, is a term used in chemistry when classifying the chemical elements. On the basis of their general physical and chemical properties, every element in the periodic table can be termed either a metal or a nonmetal...
) ions (e.g., Pb(II), Cu(II), Hg(II), As(III)) are precipitated from solution upon exposure to . The components of the resulting precipitate redissolve with some selectivity.
For small-scale laboratory use in analytic chemistry, the use of thioacetamide
Thioacetamide
Thioacetamide is an organosulfur compound with the formula C2H5NS. This white crystalline solid is soluble in water and serves as a source of sulfide ions in the synthesis of organic and inorganic compounds. It is a prototypical thioamide....
has superseded as a source of sulfide ions.
Precursor to metal sulfides
As indicated above, many metal ions react with hydrogen sulfide to give the corresponding metal sulfides. This conversion is widely exploited. For example, gases or waters contaminated by hydrogen sulfide can be cleaned with metal sulfides. In the purification of metal oresOrés
Orés is a municipality in the Cinco Villas, in the province of Zaragoza, in the autonomous community of Aragon, Spain. It belongs to the comarca of Cinco Villas. It is placed 104 km to the northwest of the provincial capital city, Zaragoza. Its coordinates are: 42° 17' N, 1° 00' W, and is...
by flotation
Flotation
Flotation involves phenomena related to the relative buoyancy of objects. The term may refer to:* Flotation, any material added to the hull of a watercraft to keep the hull afloat...
, mineral powders are often treated with hydrogen sulfide to enhance the separation. Metal parts are sometimes passivated with hydrogen sulfide. Catalysts used in hydrodesulfurization
Hydrodesulfurization
Hydrodesulfurization is a catalytic chemical process widely used to remove sulfur from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils...
are routinely activated with hydrogen sulfide, and the behavior of metallic catalysts used in other parts of a refinery
Refinery
A refinery is a production facility composed of a group of chemical engineering unit processes and unit operations refining certain materials or converting raw material into products of value.-Types of refineries:Different types of refineries are as follows:...
is also modified using hydrogen sulfide.
Miscellaneous applications
Hydrogen sulfide is used to separate deuterium oxide, or heavy waterHeavy water
Heavy water is water highly enriched in the hydrogen isotope deuterium; e.g., heavy water used in CANDU reactors is 99.75% enriched by hydrogen atom-fraction...
, from normal water via the Girdler Sulfide process
Girdler sulfide process
The Girdler sulfide process, also known as the Geib–Spevack process, is an industrial production method for making heavy water , an important component of many nuclear reactors because it acts as a neutron moderator. It takes its name from Karl-Hermann Geib and Jerome S...
.
Removal from fuel gases
Hydrogen sulfide is commonly found in natural gasNatural gas
Natural gas is a naturally occurring gas mixture consisting primarily of methane, typically with 0–20% higher hydrocarbons . It is found associated with other hydrocarbon fuel, in coal beds, as methane clathrates, and is an important fuel source and a major feedstock for fertilizers.Most natural...
, biogas
Biogas
Biogas typically refers to a gas produced by the biological breakdown of organic matter in the absence of oxygen. Organic waste such as dead plant and animal material, animal dung, and kitchen waste can be converted into a gaseous fuel called biogas...
, and LPG. It can be removed in a number of ways.
Reaction with iron oxide
Gas is pumped through a container of hydrated iron(III) oxideIron(III) oxide
Iron oxide or ferric oxide is the inorganic compound with the formula Fe2O3. It is one of the three main oxides of iron, the other two being iron oxide , which is rare, and iron oxide , which also occurs naturally as the mineral magnetite. As the mineral known as hematite, Fe2O3 is the main...
, which combines with hydrogen sulfide.
- Fe2O3(s) + H2O(l) + 3 H2S(g) → Fe2S3(s) + 4 H2O(l)
In order to regenerate iron(III) oxide, the container must be taken out of service, flooded with water and aerated.
- 2 Fe2S3(s) + 3 O2(g) + 2 H2O(l) → 2 Fe2O3(s) + 2H2O(l) + 6 S(s)
On completion of the regeneration reaction the container is drained of water and can be returned to service.
The advantage of this system is that it is completely passive during the extraction phase.
Hydrodesulfurization
HydrodesulfurizationHydrodesulfurization
Hydrodesulfurization is a catalytic chemical process widely used to remove sulfur from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils...
is a more complex method of removing sulfur from fuels.
Safety
Hydrogen sulfide is a highly toxic and flammable gas (flammable rangeFlammability limit
Flammability limits, also called flammable limits, give the proportion of combustible gases in a mixture, between which limits this mixture is flammable. Gas mixtures consisting of combustible, oxidizing, and inert gases are only flammable under certain conditions. The lower flammable limit ...
: 4.3–46%). Being heavier than air, it tends to accumulate at the bottom of poorly ventilated spaces. Although very pungent at first, it quickly deadens the sense of smell, so potential victims may be unaware of its presence until it is too late. For safe handling procedures, a hydrogen sulfide material safety data sheet (MSDS) should be consulted.
In 1975, a hydrogen sulfide explosion in Denver City
Denver City, Texas
Denver City is a town in Gaines and Yoakum counties in the U.S. state of Texas, just a short distance from the New Mexico boundary that is named for the petroleum company, Denver Productions. The population was 3,985 at the 2000 census. The town is located at the intersection of Texas State...
, located in Yoakum and Gaines counties, Texas
Texas
Texas is the second largest U.S. state by both area and population, and the largest state by area in the contiguous United States.The name, based on the Caddo word "Tejas" meaning "friends" or "allies", was applied by the Spanish to the Caddo themselves and to the region of their settlement in...
, caused the state legislature to focus on the deadly hazards of the gas. State Representative
Texas House of Representatives
The Texas House of Representatives is the lower house of the Texas Legislature. The House is composed of 150 members elected from single-member districts across the state. The average district has about 150,000 people. Representatives are elected to two-year terms with no term limits...
E L Short
E L Short
E L Short is a farmer, rancher, and businessman from Tahoka in Lynn County, Texas, who is a former Democratic member of both houses of the Texas State Legislature.-Background:...
of Tahoka
Tahoka, Texas
Tahoka is a city in and the county seat of Lynn County, Texas, United States. The population was 2,910 at the 2000 census.-Geography:Tahoka is located at ....
in Lynn County, took the lead in endorsing an investigation by the Texas Railroad Commission
Railroad Commission of Texas
The Railroad Commission of Texas is the state agency that regulates the oil and gas industry, gas utilities, pipeline safety, safety in the liquefied petroleum gas industry, and surface coal and uranium mining .Established by the Texas Legislature in 1891, it is the state's oldest regulatory...
and urged that residents be warned "by knocking on doors if necessary" of the imminent danger stemming from the gas. One may die from the second inhalation of the gas, and a warning itself may be too late.
Toxicity
Hydrogen sulfide is considered a broad-spectrum poison, meaning that it can poison several different systems in the body, although the nervous systemNervous system
The nervous system is an organ system containing a network of specialized cells called neurons that coordinate the actions of an animal and transmit signals between different parts of its body. In most animals the nervous system consists of two parts, central and peripheral. The central nervous...
is most affected. The toxicity of is comparable with that of hydrogen cyanide. It forms a complex bond with iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...
in the mitochondrial cytochrome
Cytochrome
Cytochromes are, in general, membrane-bound hemoproteins that contain heme groups and carry out electron transport.They are found either as monomeric proteins or as subunits of bigger enzymatic complexes that catalyze redox reactions....
enzyme
Enzyme
Enzymes are proteins that catalyze chemical reactions. In enzymatic reactions, the molecules at the beginning of the process, called substrates, are converted into different molecules, called products. Almost all chemical reactions in a biological cell need enzymes in order to occur at rates...
s, thus preventing cellular respiration
Cellular respiration
Cellular respiration is the set of the metabolic reactions and processes that take place in the cells of organisms to convert biochemical energy from nutrients into adenosine triphosphate , and then release waste products. The reactions involved in respiration are catabolic reactions that involve...
.
Since hydrogen sulfide occurs naturally in the body, the environment and the gut, enzymes exist in the body capable of detoxifying it by oxidation to (harmless) sulfate. Hence, low levels of hydrogen sulfide may be tolerated indefinitely.
At some threshold level, believed to average around 300–350 ppm, the oxidative enzymes become overwhelmed. Many personal safety gas detectors, such as those used by utility, sewage and petrochemical workers, are set to alarm at as low as 5 to 10 ppm and to go into high alarm at 15 ppm.
An interesting diagnostic clue of extreme poisoning by is the discoloration of copper
Copper
Copper is a chemical element with the symbol Cu and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; an exposed surface has a reddish-orange tarnish...
coins in the pockets of the victim. Treatment involves immediate inhalation of amyl nitrite
Amyl nitrite
Amyl nitrite is the chemical compound with the formula C5H11ONO. A variety of isomers are known, but they all feature an amyl group attached to the nitrito functional group. The alkyl group is unreactive and the chemical and biological properties are mainly due to the nitrite group...
, injections of sodium nitrite
Sodium nitrite
Sodium nitrite is the inorganic compound with the chemical formula NaNO2. It is a white to slight yellowish crystalline powder that is very soluble in water and is hygroscopic...
, inhalation of pure oxygen, administration of bronchodilator
Bronchodilator
A bronchodilator is a substance that dilates the bronchi and bronchioles, decreasing resistance in the respiratory airway and increasing airflow to the lungs. Bronchodilators may be endogenous , or they may be medications administered for the treatment of breathing difficulties...
s to overcome eventual bronchospasm
Bronchospasm
Bronchospasm or a bronchial spasm is a sudden constriction of the muscles in the walls of the bronchioles. It is caused by the release of substances from mast cells or basophils under the influence of anaphylatoxins...
, and in some cases hyperbaric oxygen therapy
Hyperbaric oxygen therapy
Hyperbaric medicine, also known as hyperbaric oxygen therapy , is the medical use of oxygen at a level higher than atmospheric pressure. The equipment required consists of a pressure chamber, which may be of rigid or flexible construction, and a means of delivering 100% oxygen...
(HBO). HBO therapy has anecdotal support and remains controversial.
Exposure to lower concentrations can result in eye
Human eye
The human eye is an organ which reacts to light for several purposes. As a conscious sense organ, the eye allows vision. Rod and cone cells in the retina allow conscious light perception and vision including color differentiation and the perception of depth...
irritation, a sore throat and cough
Cough
A cough is a sudden and often repetitively occurring reflex which helps to clear the large breathing passages from secretions, irritants, foreign particles and microbes...
, nausea, shortness of breath, and fluid in the lung
Lung
The lung is the essential respiration organ in many air-breathing animals, including most tetrapods, a few fish and a few snails. In mammals and the more complex life forms, the two lungs are located near the backbone on either side of the heart...
s. These effects are believed to be due to the fact that hydrogen sulfide combines with alkali
Alkali
In chemistry, an alkali is a basic, ionic salt of an alkali metal or alkaline earth metal element. Some authors also define an alkali as a base that dissolves in water. A solution of a soluble base has a pH greater than 7. The adjective alkaline is commonly used in English as a synonym for base,...
present in moist surface tissues to form sodium sulfide
Sodium sulfide
Sodium sulfide is the name used to refer to the chemical compound Na2S, but more commonly it refers to the hydrate Na2S·9H2O. Both are colorless water-soluble salts that give strongly alkaline solutions...
, a caustic. These symptoms usually go away in a few weeks.
Long-term, low-level exposure may result in fatigue
Fatigue (physical)
Fatigue is a state of awareness describing a range of afflictions, usually associated with physical and/or mental weakness, though varying from a general state of lethargy to a specific work-induced burning sensation within one's muscles...
, loss of appetite, headaches, irritability, poor memory, and dizziness
Dizziness
Dizziness refers to an impairment in spatial perception and stability. The term is somewhat imprecise. It can be used to mean vertigo, presyncope, disequilibrium, or a non-specific feeling such as giddiness or foolishness....
. Chronic exposure to low level (around 2 ppm) has been implicated in increased miscarriage and reproductive health issues among Russian and Finnish wood pulp workers, but the reports have not (as of circa 1995) been replicated.
- 0.00047 ppm is the recognition threshold, the concentration at which 50% of humans can detect the characteristic odor of hydrogen sulfide, normally described as resembling "a rotten egg".
- Less than 10 ppm has an exposure limit of 8 hours per day.
- 10–20 ppm is the borderline concentration for eye irritation.
- 50–100 ppm leads to eye damage.
- At 100–150 ppm the olfactory nerveOlfactory nerveThe olfactory nerve, or cranial nerve I, is the first of twelve cranial nerves. It is instrumental in the sense of smell. Derived from the embryonic nasal placode, the olfactory nerve is capable of regeneration.-Anatomy:...
is paralyzed after a few inhalations, and the sense of smell disappears, often together with awareness of danger. - 320–530 ppm leads to pulmonary edemaPulmonary edemaPulmonary edema , or oedema , is fluid accumulation in the air spaces and parenchyma of the lungs. It leads to impaired gas exchange and may cause respiratory failure...
with the possibility of death. - 530–1000 ppm causes strong stimulation of the central nervous systemCentral nervous systemThe central nervous system is the part of the nervous system that integrates the information that it receives from, and coordinates the activity of, all parts of the bodies of bilaterian animals—that is, all multicellular animals except sponges and radially symmetric animals such as jellyfish...
and rapid breathing, leading to loss of breathing. - 800 ppm is the lethal concentration for 50% of humans for 5 minutes exposure (LC50).
- Concentrations over 1000 ppm cause immediate collapse with loss of breathing, even after inhalation of a single breath.
Although respiratory paralysis may be immediate, it can also be delayed up to 72 hours.
Hydrogen sulfide was used by the British as a chemical agent during World War I
World War I
World War I , which was predominantly called the World War or the Great War from its occurrence until 1939, and the First World War or World War I thereafter, was a major war centred in Europe that began on 28 July 1914 and lasted until 11 November 1918...
. It was not considered to be an ideal war gas, but, while other gases were in short supply, it was used on two occasions in 1916.
A dump of toxic waste containing hydrogen sulfide is believed to have caused 17 deaths and thousands of illnesses in Abidjan, on the West Africa coast, in the 2006 Côte d'Ivoire toxic waste dump.
Suicides
The gas, produced by mixing certain household ingredients, was used in a suicideSuicide
Suicide is the act of intentionally causing one's own death. Suicide is often committed out of despair or attributed to some underlying mental disorder, such as depression, bipolar disorder, schizophrenia, alcoholism, or drug abuse...
wave in 2008 in Japan. The wave prompted staff at Tokyo's suicide prevention
Suicide prevention
Suicide prevention is an umbrella term for the collective efforts of local citizen organizations, mental health practitioners and related professionals to reduce the incidence of suicide....
center to set up a special hot line during "Golden Week", as they received an increase in calls from people wanting to kill themselves during the annual May holiday.
As of 2010, this phenomenon has occurred in a number of US cities (and in Putney West London, England), prompting warnings to those arriving at the site of the suicide. These first responders, such as emergency services workers or family members are at risk of death from inhaling lethal quantities of the gas, or by fire. Local governments have also initiated campaigns to prevent such suicides.
Function in the body
Hydrogen sulfide is produced in small amounts by some cells of the mammalMammal
Mammals are members of a class of air-breathing vertebrate animals characterised by the possession of endothermy, hair, three middle ear bones, and mammary glands functional in mothers with young...
ian body and has a number of biological signaling functions. (Only two other such gases are currently known: nitric oxide
Nitric oxide
Nitric oxide, also known as nitrogen monoxide, is a diatomic molecule with chemical formula NO. It is a free radical and is an important intermediate in the chemical industry...
(NO) and carbon monoxide
Carbon monoxide
Carbon monoxide , also called carbonous oxide, is a colorless, odorless, and tasteless gas that is slightly lighter than air. It is highly toxic to humans and animals in higher quantities, although it is also produced in normal animal metabolism in low quantities, and is thought to have some normal...
(CO).)
The gas is produced from cysteine
Cysteine
Cysteine is an α-amino acid with the chemical formula HO2CCHCH2SH. It is a non-essential amino acid, which means that it is biosynthesized in humans. Its codons are UGU and UGC. The side chain on cysteine is thiol, which is polar and thus cysteine is usually classified as a hydrophilic amino acid...
by the enzyme
Enzyme
Enzymes are proteins that catalyze chemical reactions. In enzymatic reactions, the molecules at the beginning of the process, called substrates, are converted into different molecules, called products. Almost all chemical reactions in a biological cell need enzymes in order to occur at rates...
s cystathionine beta-synthase and cystathionine gamma-lyase
Cystathionine gamma-lyase
Cystathionine gamma-lyase is an enzyme which breaks down cystathionine into cysteine and α-ketobutyrate. Pyridoxal phosphate is a prosthetic group of this enzyme....
. It acts as a relaxant of smooth muscle
Smooth muscle
Smooth muscle is an involuntary non-striated muscle. It is divided into two sub-groups; the single-unit and multiunit smooth muscle. Within single-unit smooth muscle tissues, the autonomic nervous system innervates a single cell within a sheet or bundle and the action potential is propagated by...
and as a vasodilator and is also active in the brain
Brain
The brain is the center of the nervous system in all vertebrate and most invertebrate animals—only a few primitive invertebrates such as sponges, jellyfish, sea squirts and starfishes do not have one. It is located in the head, usually close to primary sensory apparatus such as vision, hearing,...
, where it increases the response of the NMDA receptor
NMDA receptor
The NMDA receptor , a glutamate receptor, is the predominant molecular device for controlling synaptic plasticity and memory function....
and facilitates long term potentiation, which is involved in the formation of memory.
Eventually the gas is converted to sulfite in the mitochondria by thiosulfate reductase, and the sulfite is further oxidized to thiosulfate
Thiosulfate
Thiosulfate is an oxyanion of sulfur. The prefix thio indicates that thiosulfate ion is a sulfate ion with one oxygen replaced by a sulfur. Thiosulfate occurs naturally and is produced by certain biochemical processes...
and sulfate
Sulfate
In inorganic chemistry, a sulfate is a salt of sulfuric acid.-Chemical properties:...
by sulfite oxidase
Sulfite oxidase
Sulfite oxidase is an enzyme in the mitochondria of all eukaryotes. It oxidizes sulfite to sulfate and, via cytochrome c, transfers the electrons produced to the electron transport chain, allowing generation of ATP in oxidative phosphorylation...
. The sulfates are excreted in the urine.
Due to its effects similar to nitric oxide
Nitric oxide
Nitric oxide, also known as nitrogen monoxide, is a diatomic molecule with chemical formula NO. It is a free radical and is an important intermediate in the chemical industry...
(without its potential to form peroxides by interacting with superoxide
Superoxide
A superoxide, also known by the obsolete name hyperoxide, is a compound that possesses the superoxide anion with the chemical formula O2−. The systematic name of the anion is dioxide. It is important as the product of the one-electron reduction of dioxygen O2, which occurs widely in nature...
), hydrogen sulfide is now recognized as potentially protecting against cardiovascular disease. The cardioprotective role effect of garlic
Garlic
Allium sativum, commonly known as garlic, is a species in the onion genus, Allium. Its close relatives include the onion, shallot, leek, chive, and rakkyo. Dating back over 6,000 years, garlic is native to central Asia, and has long been a staple in the Mediterranean region, as well as a frequent...
is caused by catabolism
Catabolism
Catabolism is the set of metabolic pathways that break down molecules into smaller units and release energy. In catabolism, large molecules such as polysaccharides, lipids, nucleic acids and proteins are broken down into smaller units such as monosaccharides, fatty acids, nucleotides, and amino...
of the polysulfide group in allicin to , a reaction that could depend on reduction mediated by glutathione
Glutathione
Glutathione is a tripeptide that contains an unusual peptide linkage between the amine group of cysteine and the carboxyl group of the glutamate side-chain...
.
Though both nitric oxide
Nitric oxide
Nitric oxide, also known as nitrogen monoxide, is a diatomic molecule with chemical formula NO. It is a free radical and is an important intermediate in the chemical industry...
and hydrogen sulfide have been shown to relax blood vessels, their mechanisms of action are different: while NO activates the enzyme guanylyl cyclase, activates ATP-sensitive potassium channel in smooth muscle cells. Researchers are not clear how the vessel-relaxing responsibilities are shared between nitric oxide and hydrogen sulfide. However there exists some evidence to suggest that nitric oxide does most of the vessel-relaxing work in large vessels and hydrogen sulfide is responsible for similar action in smaller blood vessels.
Like nitric oxide, hydrogen sulfide is involved in the relaxation of smooth muscle that causes erection
Erection
Penile erection is a physiological phenomenon where the penis becomes enlarged and firm. Penile erection is the result of a complex interaction of psychological, neural, vascular and endocrine factors, and is usually, though not exclusively, associated with sexual arousal...
of the penis, presenting possible new therapy opportunities for erectile dysfunction
Erectile dysfunction
Erectile dysfunction is sexual dysfunction characterized by the inability to develop or maintain an erection of the penis during sexual performance....
.
In Alzheimer's disease
Alzheimer's disease
Alzheimer's disease also known in medical literature as Alzheimer disease is the most common form of dementia. There is no cure for the disease, which worsens as it progresses, and eventually leads to death...
the brain's hydrogen sulfide concentration is severely decreased. In trisomy 21 (the most common form of Down syndrome) the body produces an excess of hydrogen sulfide. Hydrogen sulfide is also involved in the disease process of type 1 diabetes
Diabetes mellitus type 1
Diabetes mellitus type 1 is a form of diabetes mellitus that results from autoimmune destruction of insulin-producing beta cells of the pancreas. The subsequent lack of insulin leads to increased blood and urine glucose...
. The beta cells of the pancreas
Pancreas
The pancreas is a gland organ in the digestive and endocrine system of vertebrates. It is both an endocrine gland producing several important hormones, including insulin, glucagon, and somatostatin, as well as a digestive organ, secreting pancreatic juice containing digestive enzymes that assist...
in type 1 diabetes produce an excess of the gas, leading to the death of beta cells and to a reduced production of insulin by those that remain.
Induced hypothermia/suspended animation
In 2005, it was shown that mice can be put into a state of suspended animationSuspended animation
Suspended animation is the slowing of life processes by external means without termination. Breathing, heartbeat, and other involuntary functions may still occur, but they can only be detected by artificial means. Extreme cold can be used to precipitate the slowing of an individual's functions; use...
-like hypothermia
Hypothermia
Hypothermia is a condition in which core temperature drops below the required temperature for normal metabolism and body functions which is defined as . Body temperature is usually maintained near a constant level of through biologic homeostasis or thermoregulation...
by applying a low dosage of hydrogen sulfide (81 ppm ) in the air. The breathing rate of the animals sank from 120 to 10 breaths per minute and their temperature fell from 37 °C to just 2 °C above ambient temperature (in effect, they had become cold-blooded
Poikilotherm
A poikilotherm is an organism whose internal temperature varies considerably. It is the opposite of a homeotherm, an organism which maintains thermal homeostasis. Usually the variation is a consequence of variation in the ambient environmental temperature...
). The mice survived this procedure for 6 hours and afterwards showed no negative health consequences. In 2006 it was shown that the blood pressure
Blood pressure
Blood pressure is the pressure exerted by circulating blood upon the walls of blood vessels, and is one of the principal vital signs. When used without further specification, "blood pressure" usually refers to the arterial pressure of the systemic circulation. During each heartbeat, BP varies...
of mice treated in this fashion with hydrogen sulfide did not significantly decrease.
A similar process known as hibernation
Hibernation
Hibernation is a state of inactivity and metabolic depression in animals, characterized by lower body temperature, slower breathing, and lower metabolic rate. Hibernating animals conserve food, especially during winter when food supplies are limited, tapping energy reserves, body fat, at a slow rate...
occurs naturally in many mammal
Mammal
Mammals are members of a class of air-breathing vertebrate animals characterised by the possession of endothermy, hair, three middle ear bones, and mammary glands functional in mothers with young...
s and also in toad
Toad
A toad is any of a number of species of amphibians in the order Anura characterized by dry, leathery skin , short legs, and snoat-like parotoid glands...
s, but not in mice. (Mice can fall into a state called clinical torpor
Torpor
Torpor, sometimes called temporary hibernation is a state of decreased physiological activity in an animal, usually characterized by a reduced body temperature and rate of metabolism. Animals that go through torpor include birds and some mammals such as mice and bats...
when food shortage occurs). If the -induced hibernation can be made to work in humans, it could be useful in the emergency management of severely injured patients, and in the conservation of donated organs. In 2008, hypothermia induced by hydrogen sulfide for 48 hours was shown to reduce the extent of brain damage caused by experimental stroke
Stroke
A stroke, previously known medically as a cerebrovascular accident , is the rapidly developing loss of brain function due to disturbance in the blood supply to the brain. This can be due to ischemia caused by blockage , or a hemorrhage...
in rats.
As mentioned above, hydrogen sulfide binds to cytochrome oxidase
Cytochrome c oxidase
The enzyme cytochrome c oxidase or Complex IV is a large transmembrane protein complex found in bacteria and the mitochondrion.It is the last enzyme in the respiratory electron transport chain of mitochondria located in the mitochondrial membrane...
and thereby prevents oxygen from binding, which leads to the dramatic slowdown of metabolism
Metabolism
Metabolism is the set of chemical reactions that happen in the cells of living organisms to sustain life. These processes allow organisms to grow and reproduce, maintain their structures, and respond to their environments. Metabolism is usually divided into two categories...
. Animals and humans naturally produce some hydrogen sulfide in their body; researchers have proposed that the gas is used to regulate metabolic activity and body temperature, which would explain the above findings.
Two recent studies cast doubt that the effect can be achieved in larger mammals. A 2008 study failed to reproduce the effect in pigs, concluding that the effects seen in mice were not present in larger mammals. Likewise a paper by Haouzi et al. noted that there is no induction of hypometabolism in sheep, either.
However, at a February 2010 TED
TED (conference)
TED is a global set of conferences owned by the private non-profit Sapling Foundation, formed to disseminate "ideas worth spreading"....
conference, Mark Roth
Mark Roth (scientist)
Mark Roth is an American biochemist, and director of the Roth Lab at the Fred Hutchinson Cancer Research Center. He is a professor at the University of Washington....
announced that hydrogen sulfide induced hypothermia had completed Phase I clinical trials. He estimated that further trials would take 'a few years.'
Participant in the sulfur cycle
Hydrogen sulfide is a central participant in the sulfur cycleSulfur cycle
The sulfur cycle are the collection of processes by which sulfur moves to and from minerals and living systems. Such biogeochemical cycles are important in geology because they affect many minerals...
, the biogeochemical cycle
Biogeochemical cycle
In ecology and Earth science, a biogeochemical cycle or substance turnover or cycling of substances is a pathway by which a chemical element or molecule moves through both biotic and abiotic compartments of Earth. A cycle is a series of change which comes back to the starting point and which can...
of sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
on Earth.
In the absence of oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
, sulfur-reducing
Sulfur-reducing bacteria
Sulfur-reducing bacteria get their energy by reducing elemental sulfur to hydrogen sulfide. They couple this reaction with the oxidation of acetate, succinate or other organic compounds....
and sulfate-reducing bacteria
Sulfate-reducing bacteria
Sulfate-reducing bacteria are those bacteria and archaea that can obtain energy by oxidizing organic compounds or molecular hydrogen while reducing sulfate to hydrogen sulfide...
derive energy from oxidizing
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
hydrogen or organic molecules by reducing elemental sulfur or sulfate
Sulfate
In inorganic chemistry, a sulfate is a salt of sulfuric acid.-Chemical properties:...
to hydrogen sulfide. Other bacteria liberate hydrogen sulfide from sulfur-containing amino acid
Amino acid
Amino acids are molecules containing an amine group, a carboxylic acid group and a side-chain that varies between different amino acids. The key elements of an amino acid are carbon, hydrogen, oxygen, and nitrogen...
s; this gives rise to the odor of rotten eggs and contributes to the odor of flatulence
Flatulence
Flatulence is the expulsion through the rectum of a mixture of gases that are byproducts of the digestion process of mammals and other animals. The medical term for the mixture of gases is flatus, informally known as a fart, or simply gas...
.
As organic matter decays under low-oxygen (or hypoxic
Hypoxia (environmental)
Hypoxia, or oxygen depletion, is a phenomenon that occurs in aquatic environments as dissolved oxygen becomes reduced in concentration to a point where it becomes detrimental to aquatic organisms living in the system...
) conditions (such as in swamps, eutrophic lakes or dead zones
Dead zone (ecology)
Dead zones are hypoxic areas in the world's oceans, the observed incidences of which have been increasing since oceanographers began noting them in the 1970s. These occur near inhabited coastlines, where aquatic life is most concentrated...
of oceans), sulfate-reducing bacteria will use the sulfates present in the water to oxidize the organic matter, producing hydrogen sulfide as waste. Some of the hydrogen sulfide will react with metal ions in the water to produce metal sulfides, which are not water soluble. These metal sulfides, such as ferrous sulfide
Iron(II) sulfide
Iron sulfide or ferrous sulfide is a chemical compound with the formula . In practice, iron sulfides are often non-stoichiometric. Powdered iron sulfide is pyrophoric Iron(II) sulfide or ferrous sulfide (Br.E. sulphide) is a chemical compound with the formula . In practice, iron sulfides are...
FeS, are often black or brown, leading to the dark color of sludge.
Several groups of bacteria can use hydrogen sulfide as fuel, oxidizing it to elemental sulfur or to sulfate by using dissolved oxygen, metal oxides (e.g., Fe oxyhydroxides and Mn oxides) or nitrate as oxidant.
The purple sulfur bacteria
Purple sulfur bacteria
The purple sulfur bacteria are a group of Proteobacteria capable of photosynthesis, collectively referred to as purple bacteria. They are anaerobic or microaerophilic, and are often found in hot springs or stagnant water. Unlike plants, algae, and cyanobacteria, they do not use water as their...
and the green sulfur bacteria
Green sulfur bacteria
The green sulfur bacteria are a family of obligately anaerobic photoautotrophic bacteria. Most closely related to the distant Bacteroidetes, they are accordingly assigned their own phylum....
use hydrogen sulfide as electron donor
Electron donor
An electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process....
in photosynthesis
Photosynthesis
Photosynthesis is a chemical process that converts carbon dioxide into organic compounds, especially sugars, using the energy from sunlight. Photosynthesis occurs in plants, algae, and many species of bacteria, but not in archaea. Photosynthetic organisms are called photoautotrophs, since they can...
, thereby producing elemental sulfur. (In fact, this mode of photosynthesis is older than the mode of cyanobacteria, algae
Algae
Algae are a large and diverse group of simple, typically autotrophic organisms, ranging from unicellular to multicellular forms, such as the giant kelps that grow to 65 meters in length. They are photosynthetic like plants, and "simple" because their tissues are not organized into the many...
, and plant
Plant
Plants are living organisms belonging to the kingdom Plantae. Precise definitions of the kingdom vary, but as the term is used here, plants include familiar organisms such as trees, flowers, herbs, bushes, grasses, vines, ferns, mosses, and green algae. The group is also called green plants or...
s, which uses water as electron donor and liberates oxygen.)
Mass extinctions
Hydrogen sulfide has been implicated in some of the several mass extinctionsExtinction event
An extinction event is a sharp decrease in the diversity and abundance of macroscopic life. They occur when the rate of extinction increases with respect to the rate of speciation...
that have occurred in the Earth's past. In particular, a buildup of hydrogen sulfide in the atmosphere may have caused the Permian-Triassic extinction event
Permian-Triassic extinction event
The Permian–Triassic extinction event, informally known as the Great Dying, was an extinction event that occurred 252.28 Ma ago, forming the boundary between the Permian and Triassic geologic periods, as well as the Paleozoic and Mesozoic eras...
252 million years ago.
Organic residues from these extinction boundaries indicate that the oceans were anoxic (oxygen-depleted) and had species of shallow plankton that metabolized . The formation of may have been initiated by massive volcanic eruptions, which emitted carbon dioxide
Carbon dioxide
Carbon dioxide is a naturally occurring chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom...
and methane
Methane
Methane is a chemical compound with the chemical formula . It is the simplest alkane, the principal component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel...
into the atmosphere, which warmed the oceans, lowering their capacity to absorb oxygen that would otherwise oxidize . The increased levels of hydrogen sulfide could have killed oxygen-generating plants as well as depleted the ozone layer, causing further stress. Small blooms have been detected in modern times in the Dead Sea
Dead Sea
The Dead Sea , also called the Salt Sea, is a salt lake bordering Jordan to the east and Israel and the West Bank to the west. Its surface and shores are below sea level, the lowest elevation on the Earth's surface. The Dead Sea is deep, the deepest hypersaline lake in the world...
and in the Atlantic ocean off the coast of Namibia.
See also
- Amine gas treatingAmine gas treatingAmine gas treating, also known as gas sweetening and acid gas removal, refers to a group of processes that use aqueous solutions of various alkylamines to remove hydrogen sulfide and carbon dioxide from gases...
- Sewer gasSewer gasSewer gas is a complex mixture of toxic and non-toxic gases produced and collected in sewage systems by the decomposition of organic household or industrial wastes, typical components of Sewage....
- Induced hypothermia
- JenkemJenkemJenkem is a purportedly hallucinogenic inhalant created from fermented human waste. In the mid-1990s, it was reported to be a popular street drug among Zambian street children....
- GasotransmittersGasotransmittersGasotransmitters are gaseous molecules synthesized in the body. They include nitric oxide, hydrogen sulfide, carbon monoxide, and possibly nitrous oxide.-Overview:...
Additional resources
- "Hydrogen Sulfide", Committee on Medical and Biological Effects of Environmental Pollutants, University Park Press, 1979, Baltimore. ISBN 0-8391-0127-9