Hydrogen  Sulfide
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Hydrogen sulfide is a chemical compound with the
formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
. It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The underground mine gas term for foul-smelling hydrogen sulfide-rich gas mixtures is ''stinkdamp''. Swedish chemist Carl Wilhelm Scheele is credited with having discovered the chemical composition of purified hydrogen sulfide in 1777. The British English spelling of this compound is hydrogen sulphide, a spelling no longer recommended by the Royal Society of Chemistry or the International Union of Pure and Applied Chemistry. Hydrogen sulfide is toxic to humans and most other animals by inhibiting cellular respiration in a manner similar to
hydrogen cyanide Hydrogen cyanide, sometimes called prussic acid, is a chemical compound with the formula HCN and structure . It is a colorless, extremely poisonous, and flammable liquid that boils slightly above room temperature, at . HCN is produced on an ...
. When it is inhaled or it or its salts are ingested in high amounts, damage to organs occurs rapidly with symptoms ranging from breathing difficulties to convulsions and death. Despite this, the
human body The human body is the structure of a Human, human being. It is composed of many different types of Cell (biology), cells that together create Tissue (biology), tissues and subsequently organ systems. They ensure homeostasis and the life, viabi ...
produces small amounts of this sulfide and its mineral salts, and uses it as a signalling molecule. Hydrogen sulfide is often produced from the
microbial A microorganism, or microbe,, ''mikros'', "small") and ''organism'' from the el, ὀργανισμός, ''organismós'', "organism"). It is usually written as a single word but is sometimes hyphenated (''micro-organism''), especially in olde ...
breakdown of
organic matter Organic matter, organic material, or natural organic matter refers to the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have c ...
in the absence of oxygen, such as in
swamps A swamp is a forested wetland.Keddy, P.A. 2010. Wetland Ecology: Principles and Conservation (2nd edition). Cambridge University Press, Cambridge, UK. 497 p. Swamps are considered to be transition zones because both land and water play a role in ...
and sewers; this process is commonly known as anaerobic digestion, which is done by sulfate-reducing microorganisms. It also occurs in volcanic gases, natural gas deposits, and sometimes in well-drawn water.


Properties

Hydrogen sulfide is slightly denser than air. A mixture of and air can be explosive. Hydrogen sulfide burns in oxygen with a blue flame to form
sulfur dioxide Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic activ ...
() and water. In general, hydrogen sulfide acts as a reducing agent, although in the presence of a base, it can act as an acid by donating a proton and forming SH. At high temperatures or in the presence of catalysts, sulfur dioxide reacts with hydrogen sulfide to form elemental
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
and water. This reaction is exploited in the
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 chemist Carl Friedrich Claus, the Claus process has become the industry standard. Th ...
, an important industrial method to dispose of hydrogen sulfide. Hydrogen sulfide is slightly soluble in water and acts as a weak acid ( p''K''a = 6.9 in 0.01–0.1 mol/litre solutions at 18 °C), giving the hydrosulfide ion (also written ). Hydrogen sulfide and its solutions are colorless. When exposed to air, it slowly oxidizes to form elemental sulfur, which is not soluble in water. The
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds lar ...
anion is not formed in aqueous solution. Hydrogen sulfide reacts with metal ions to form metal sulfides, which are insoluble, often dark colored solids. Lead(II) acetate paper is used to detect hydrogen sulfide because it readily converts to lead(II) sulfide, which is black. Treating metal sulfides with strong acid or electrolysis often liberates hydrogen sulfide. Hydrogen sulfide is also responsible for tarnishing on various metals including copper and silver; the chemical responsible for black toning found on silver coins is
silver sulfide Silver sulfide is an inorganic compound with the formula . A dense black solid, it is the only sulfide of silver. It is useful as a photosensitizer in photography. It constitutes the tarnish that forms over time on silverware and other silver obje ...
(Ag2S), which is produced when the silver on the surface of the coin reacts with atmospheric hydrogen sulfide. At pressures above 90 GPa ( gigapascal), hydrogen sulfide becomes a metallic conductor of electricity. When cooled below a
critical temperature Critical or Critically may refer to: *Critical, or critical but stable, medical states **Critical, or intensive care medicine *Critical juncture, a discontinuous change studied in the social sciences. *Critical Software, a company specializing in ...
this high-pressure phase exhibits
superconductivity Superconductivity is a set of physical properties observed in certain materials where electrical resistance vanishes and magnetic flux fields are expelled from the material. Any material exhibiting these properties is a superconductor. Unlike ...
. The critical temperature increases with pressure, ranging from 23 K at 100 GPa to 150 K at 200 GPa. If hydrogen sulfide is pressurized at higher temperatures, then cooled, the critical temperature reaches , the highest accepted superconducting critical temperature as of 2015. By substituting a small part of sulfur with phosphorus and using even higher pressures, it has been predicted that it may be possible to raise the critical temperature to above and achieve room-temperature superconductivity. Hydrogen sulfide decomposes without a presence of a catalyst under atmospheric pressure around 1200 °C into hydrogen and sulfur.


Production

Hydrogen sulfide is most commonly obtained by its separation from
sour gas Sour gas is natural gas or any other gas containing significant amounts of hydrogen sulfide (H2S). 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 approxim ...
, which is natural gas with a high content of . It can also be produced by treating hydrogen with molten elemental sulfur at about 450 °C. Hydrocarbons can serve as a source of hydrogen in this process.
Sulfate-reducing Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria (SRB) and sulfate-reducing archaea (SRA), both of which can perform anaerobic respiration utilizing sulfate () as term ...
(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. A standard lab preparation is to treat
ferrous sulfide Iron(II) sulfide or ferrous sulfide (Br.E. sulphide) is one of a family chemical compounds and minerals with the approximate formula . Iron sulfides are often iron-deficient non-stoichiometric. All are black, water-insoluble solids. Preparation ...
with a strong acid in a
Kipp generator Kipp's apparatus, also called Kipp generator, is an apparatus designed for preparation of small volumes of gases. It was invented around 1844 by the Dutch pharmacist Petrus Jacobus Kipp and widely used in chemical laboratories and for demonstrati ...
: :FeS + 2 HCl → FeCl2 + H2S For use in qualitative inorganic analysis, thioacetamide is used to generate : :CH3C(S)NH2 + H2O → CH3C(O)NH2 + H2S Many metal and nonmetal sulfides, e.g.
aluminium sulfide Aluminum sulfide or aluminium sulphide is a chemical compound with the formula Al2 S3. This colorless species has an interesting structural chemistry, existing in several forms. The material is sensitive to moisture, hydrolyzing to hydrated alumi ...
, phosphorus pentasulfide,
silicon disulfide Silicon disulfide is the inorganic compound with the formula Silicon, SiSulfur, S2. Like silicon dioxide, this material is polymeric, but it adopts a 1-dimensional structure quite different from the usual polymorphism (materials science), forms o ...
liberate hydrogen sulfide upon exposure to 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. Water heaters can aid the conversion of sulfate in water to hydrogen sulfide gas. This is due to providing a warm environment sustainable for sulfur bacteria and maintaining the reaction which interacts between sulfate in the water and the water heater anode, which is usually made from magnesium metal.


Biosynthesis in the body

Hydrogen sulfide can be generated in cells via enzymatic or non-enzymatic pathways. in the body acts as a
gaseous signaling molecule Gaseous signaling molecules are gaseous molecules that are either synthesized internally ( endogenously) in the organism, tissue or cell or are received by the organism, tissue or cell from outside (say, from the atmosphere or hydrosphere, as in ...
which is known to inhibit Complex IV of the mitochondrial electron transport chain which effectively reduces ATP generation and biochemical activity within cells. Three enzymes are known to synthesize : cystathionine γ-lyase (CSE), cystathionine β-synthetase (CBS) and
3-mercaptopyruvate sulfurtransferase In enzymology, a 3-mercaptopyruvate sulfurtransferase () is an enzyme that catalyzes the chemical reactions of 3-mercaptopyruvate. This enzyme belongs to the family of transferases, specifically the sulfurtransferases. This enzyme participate ...
(3-MST). These enzymes have been identified in a breadth of biological cells and tissues, and their activity has been observed to be induced by a number of disease states. It is becoming increasingly clear that is an important mediator of a wide range of cell functions in health and in diseases. CBS and CSE are the main proponents of biogenesis, which follows the trans-sulfuration pathway. These enzymes are characterized by the transfer of a sulfur atom from methionine to serine to form a cysteine molecule. 3-MST also contributes to hydrogen sulfide production by way of the cysteine catabolic pathway. Dietary amino acids, such as methionine and cysteine serve as the primary substrates for the transulfuration pathways and in the production of hydrogen sulfide. Hydrogen sulfide can also be synthesized by non-enzymatic pathway, which is derived from proteins such as
ferredoxin Ferredoxins (from Latin ''ferrum'': iron + redox, often abbreviated "fd") are iron–sulfur proteins that mediate electron transfer in a range of metabolic reactions. The term "ferredoxin" was coined by D.C. Wharton of the DuPont Co. and applied t ...
s and Rieske proteins. There has been continuing interest in exploiting such knowledge of hydrogen sulfide's role in signaling through development of mechanistically related therapeutic agents. Hydrogen sulfide has been shown to be involved in physiological processes such as vasodilation in animals, as well as in increasing seed germination and stress responses in plants. Hydrogen sulfide signaling is also innately intertwined with physiological processes that are known to be moderated by reactive oxygen species (ROS) and reactive nitrogen species (RNS). has been shown to interact with NO resulting in several different cellular effects, as well as the formation of a new signal called nitrosothiol. Hydrogen sulfide is also known to increase the levels of glutathione which acts to reduce or disrupt ROS levels in cells. The field of H2S biology has advanced from environmental toxicology to investigate the roles of endogenously produced H2S in physiological conditions and in various pathophysiological states. According to a current classification, pathophysiological states with H2S overproduction (such as cancer and Down syndrome) and pathophysiological states with H2S deficit (e.g. vascular disease) can be identified. Although the understanding of H2S biology has significantly advanced over the last decade, many questions remain, for instance related to the quantification of endogenous H2S levels.


Uses


Production of sulfur, thioorganic compounds, and alkali metal sulfides

The main use of hydrogen sulfide is as a precursor to elemental sulfur. Several
organosulfur compound Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfu ...
s are produced using hydrogen sulfide. These include methanethiol, ethanethiol, and
thioglycolic acid Thioglycolic acid (TGA) is the organic compound HSCH2CO2H. TGA is often called mercaptoacetic acid (MAA). It contains both a thiol ( mercaptan) and carboxylic acid functional groups. It is a colorless liquid with a strongly unpleasant odor. TGA i ...
. Upon combining with
alkali metal The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
bases, hydrogen sulfide converts to alkali hydrosulfides such as sodium hydrosulfide and
sodium sulfide Sodium sulfide is a chemical compound with the formula Na2 S, or more commonly its hydrate Na2S·9 H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are gener ...
: :H2S + NaOH → NaSH + H2O :NaSH + NaOH → Na2S + H2O These compounds are used in the
paper making Papermaking is the manufacture of paper and cardboard, which are used widely for printing, writing, and packaging, among many other purposes. Today almost all paper is made using industrial machinery, while handmade paper survives as a speciali ...
industry. Specifically, salts of SH break bonds between lignin and cellulose components of pulp in the
Kraft process The kraft process (also known as kraft pulping or sulfate process) is a process for conversion of wood into wood pulp, which consists of almost pure cellulose fibres, the main component of paper. The kraft process involves treatment of wood chip ...
. Reversibly sodium sulfide in the presence of acids turns into hydrosulfides and hydrogen sulfide; this supplies hydrosulfides in organic solutions and is utilized in the production of thiophenol.


Analytical chemistry

For well over a century hydrogen sulfide was important in analytical chemistry in the qualitative inorganic analysis of metal ions. In these analyses, heavy metal (and
nonmetal In chemistry, a nonmetal is a chemical element that generally lacks a predominance of metallic properties; they range from colorless gases (like hydrogen) to shiny solids (like carbon, as graphite). The electrons in nonmetals behave differentl ...
) 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, and are thus identified.


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 metals, by forming metal sulfides. In the purification of metal ores 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 Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of remov ...
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.


Miscellaneous applications

Hydrogen sulfide is used to separate deuterium oxide, or heavy water, from normal water via the
Girdler sulfide process The Girdler sulfide (GS) process, also known as the GeibSpevack (GS) process, is an industrial production method for filtering out of natural water the heavy water (deuterium oxide = D2O) which is used in particle research, in deuterium NMR sp ...
. Scientists from the University of Exeter discovered that cell exposure to small amounts of hydrogen sulfide gas can prevent
mitochondria A mitochondrion (; ) is an organelle found in the Cell (biology), cells of most Eukaryotes, such as animals, plants and Fungus, fungi. Mitochondria have a double lipid bilayer, membrane structure and use aerobic respiration to generate adenosi ...
l damage. When the cell is stressed with disease, enzymes are drawn into the cell to produce small amounts of hydrogen sulfide. This study could have further implications on preventing
stroke A stroke is a medical condition in which poor blood flow to the brain causes cell death. There are two main types of stroke: ischemic, due to lack of blood flow, and hemorrhagic, due to bleeding. Both cause parts of the brain to stop functionin ...
s, heart disease and
arthritis Arthritis is a term often used to mean any disorder that affects joints. Symptoms generally include joint pain and stiffness. Other symptoms may include redness, warmth, swelling, and decreased range of motion of the affected joints. In som ...
. Depending on the level of toning present, coins that have been subject to toning by hydrogen sulfide and other sulfur-containing compounds may add to the numismatic value of a coin based on the toning's aesthetics. Coins can also be intentionally treated with hydrogen sulfide to induce toning, though artificial toning can be distinguished from natural toning, and is generally criticised among collectors. A suspended animation-like state has been induced in rodents with the use of hydrogen sulfide, resulting in hypothermia with a concomitant reduction in metabolic rate. Oxygen demand was also reduced, thereby protecting against
hypoxia Hypoxia means a lower than normal level of oxygen, and may refer to: Reduced or insufficient oxygen * Hypoxia (environmental), abnormally low oxygen content of the specific environment * Hypoxia (medical), abnormally low level of oxygen in the tis ...
. In addition, hydrogen sulfide has been shown to reduce inflammation in various situations.


Occurrence

Volcanoes and some hot springs (as well as
cold springs Cold is the presence of low temperature, especially in the atmosphere. In common usage, cold is often a subjective perception. A lower bound to temperature is absolute zero, defined as 0.00K on the Kelvin scale, an absolute thermodynamic ...
) emit some , where it probably arises via the hydrolysis of sulfide minerals, i.e. MS + → MO + . Hydrogen sulfide can be present naturally in well water, often as a result of the action of sulfate-reducing bacteria. Hydrogen sulfide is produced by the human body in small quantities through bacterial breakdown of proteins containing sulfur in the intestinal tract, therefore it contributes to the characteristic odor of flatulence. It is also produced in the mouth ( halitosis). A portion of global emissions are due to human activity. By far the largest industrial source of is
petroleum refineries An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into useful products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefie ...
: The
hydrodesulfurization Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of remov ...
process liberates sulfur from petroleum by the action of hydrogen. The resulting is converted to elemental sulfur by partial combustion via the
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 chemist Carl Friedrich Claus, the Claus process has become the industry standard. Th ...
, which is a major source of elemental sulfur. Other anthropogenic sources of hydrogen sulfide include coke ovens,
paper mill A paper mill is a factory devoted to making paper from vegetable fibres such as wood pulp, old rags, and other ingredients. Prior to the invention and adoption of the Fourdrinier machine and other types of paper machine that use an endless belt, ...
s (using the Kraft process), tanneries and
sewerage Sewerage (or sewage system) is the infrastructure that conveys sewage or surface runoff (stormwater, meltwater, rainwater) using sewers. It encompasses components such as receiving drainage, drains, manholes, pumping stations, storm overflows, a ...
. arises from virtually anywhere where elemental sulfur comes in contact with organic material, especially at high temperatures. Depending on environmental conditions, it is responsible for deterioration of material through the action of some sulfur oxidizing microorganisms. It is called biogenic sulfide corrosion. In 2011 it was reported that increased concentrations of were observed in the
Bakken formation The Bakken Formation () is a rock unit from the Late Devonian to Early Mississippian age occupying about of the subsurface of the Williston Basin, underlying parts of Montana, North Dakota, Saskatchewan and Manitoba. The formation was initi ...
crude, possibly due to oil field practices, and presented challenges such as "health and environmental risks, corrosion of wellbore, added expense with regard to materials handling and pipeline equipment, and additional refinement requirements". Besides living near gas and oil drilling operations, ordinary citizens can be exposed to hydrogen sulfide by being near
waste water treatment Wastewater treatment is a process used to remove contaminants from wastewater and convert it into an effluent that can be returned to the water cycle. Once returned to the water cycle, the effluent creates an acceptable impact on the environme ...
facilities,
landfill A landfill site, also known as a tip, dump, rubbish dump, garbage dump, or dumping ground, is a site for the disposal of waste materials. Landfill is the oldest and most common form of waste disposal, although the systematic burial of the waste ...
s and farms with manure storage. Exposure occurs through breathing contaminated air or drinking contaminated water. In municipal waste landfill sites, the burial of organic material rapidly leads to the production of anaerobic digestion within the waste mass and, with the humid atmosphere and relatively high temperature that accompanies biodegradation, biogas is produced as soon as the air within the waste mass has been reduced. If there is a source of sulfate bearing material, such as plasterboard or natural gypsum (calcium sulphate dihydrate), under anaerobic conditions sulfate reducing bacteria converts this to hydrogen sulfide. These bacteria cannot survive in air but the moist, warm, anaerobic conditions of buried waste that contains a high source of carbon – in inert landfills, paper and glue used in the fabrication of products such as plasterboard can provide a rich source of carbon – is an excellent environment for the formation of hydrogen sulfide. In industrial anaerobic digestion processes, such as
waste water treatment Wastewater treatment is a process used to remove contaminants from wastewater and convert it into an effluent that can be returned to the water cycle. Once returned to the water cycle, the effluent creates an acceptable impact on the environme ...
or the digestion of organic waste from agriculture, hydrogen sulfide can be formed from the reduction of sulfate and the degradation of amino acids and proteins within organic compounds. Sulfates are relatively non-inhibitory to methane forming bacteria but can be reduced to H2S by sulfate reducing bacteria, of which there are several genera.


Removal from water

A number of processes have been designed to remove hydrogen sulfide from drinking water. ;Continuous chlorination: For levels up to 75 mg/L chlorine is used in the purification process as an oxidizing chemical to react with hydrogen sulfide. This reaction yields insoluble solid sulfur. Usually the chlorine used is in the form of sodium hypochlorite. ;Aeration: For concentrations of hydrogen sulfide less than 2 mg/L aeration is an ideal treatment process. Oxygen is added to water and a reaction between oxygen and hydrogen sulfide react to produce odorless sulfate. ;Nitrate addition: Calcium nitrate can be used to prevent hydrogen sulfide formation in wastewater streams.


Removal from fuel gases

Hydrogen sulfide is commonly found in raw natural gas and biogas. It is typically removed by amine gas treating technologies. In such processes, the hydrogen sulfide is first converted to an ammonium salt, whereas the natural gas is unaffected. :RNH2 + H2S RNH + SH The bisulfide anion is subsequently regenerated by heating of the amine sulfide solution. Hydrogen sulfide generated in this process is typically converted to elemental sulfur using the
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 chemist Carl Friedrich Claus, the Claus process has become the industry standard. Th ...
.


Safety

Hydrogen sulfide is a highly toxic and flammable gas ( flammable range: 4.3–46%). Being heavier than air, it tends to accumulate at the bottom of poorly ventilated spaces. Although very pungent at first (it smells like rotten eggs), it quickly deadens the sense of smell, creating temporary anosmia, so victims may be unaware of its presence until it is too late. Safe handling procedures are provided by its safety data sheet (SDS).


Toxicity

Hydrogen sulfide is a broad-spectrum poison, meaning that it can poison several different systems in the body, although the nervous system is most affected. The toxicity of is comparable with that of carbon monoxide. It binds with iron in the
mitochondria A mitochondrion (; ) is an organelle found in the Cell (biology), cells of most Eukaryotes, such as animals, plants and Fungus, fungi. Mitochondria have a double lipid bilayer, membrane structure and use aerobic respiration to generate adenosi ...
l cytochrome enzymes, thus preventing cellular respiration. Its toxic properties were described in detail in 1843 by
Justus von Liebig Justus Freiherr von Liebig (12 May 1803 – 20 April 1873) was a German scientist who made major contributions to agricultural and biological chemistry, and is considered one of the principal founders of organic chemistry. As a professor at t ...
.


Low-level exposure

Since hydrogen sulfide occurs naturally in the body, the environment, and the gut, enzymes exist to detoxify it. 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. Detoxification is effected by oxidation to sulfate, which is harmless. Hence, low levels of hydrogen sulfide may be tolerated indefinitely. Exposure to lower concentrations can result in
eye Eyes are organs of the visual system. They provide living organisms with vision, the ability to receive and process visual detail, as well as enabling several photo response functions that are independent of vision. Eyes detect light and conv ...
irritation, a sore throat and cough, nausea, shortness of breath, and fluid in the
lung The lungs are the primary organs of the respiratory system in humans and most other animals, including some snails and a small number of fish. In mammals and most other vertebrates, two lungs are located near the backbone on either side of t ...
s ( pulmonary edema). These effects are believed to be due to hydrogen sulfide combining with
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
present in moist surface tissues to form
sodium sulfide Sodium sulfide is a chemical compound with the formula Na2 S, or more commonly its hydrate Na2S·9 H2O. Both the anhydrous and the hydrated salts in pure crystalline form are colorless solids, although technical grades of sodium sulfide are gener ...
, a
caustic Caustic most commonly refers to: * Causticity, a property of various corrosive substances ** Sodium hydroxide, sometimes called ''caustic soda'' ** Potassium hydroxide, sometimes called ''caustic potash'' ** Calcium oxide, sometimes called ''caus ...
. These symptoms usually subside in a few weeks. Long-term, low-level exposure may result in
fatigue Fatigue describes a state of tiredness that does not resolve with rest or sleep. In general usage, fatigue is synonymous with extreme tiredness or exhaustion that normally follows prolonged physical or mental activity. When it does not resolve ...
, loss of appetite,
headache Headache is the symptom of pain in the face, head, or neck. It can occur as a migraine, tension-type headache, or cluster headache. There is an increased risk of depression in those with severe headaches. Headaches can occur as a result ...
s, 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 1995) been replicated.


High-level exposure

Short-term, high-level exposure can induce immediate collapse, with loss of breathing and a high probability of death. If death does not occur, high exposure to hydrogen sulfide can lead to
cortical pseudolaminar necrosis Cortical pseudolaminar necrosis, also known as cortical laminar necrosis and simply laminar necrosis, is the (uncontrolled) death of cells in the (cerebral) cortex of the brain in a band-like pattern,Hypoxic and Ischemic Encephalopathy. neuropat ...
, degeneration of the basal ganglia and cerebral edema. Although respiratory paralysis may be immediate, it can also be delayed up to 72 hours. Diagnostic of extreme poisoning by is the discolouration of copper coins in the pockets of the victim. Inhalation of H2S resulted in about 7 workplace deaths per year in the U.S. (2011–2017 data), second only to carbon monoxide (17 deaths per year) for workplace chemical inhalation deaths.


Exposure thresholds

* Exposure limits stipulated by the United States government: **10 ppm REL-Ceiling (
NIOSH The National Institute for Occupational Safety and Health (NIOSH, ) is the United States federal agency responsible for conducting research and making recommendations for the prevention of work-related injury and illness. NIOSH is part of the C ...
): recommended permissible exposure ceiling (the recommended level that must not be exceeded, except once for 10 min. in an 8-hour shift, if no other measurable exposure occurs) **20 ppm PEL-Ceiling ( OSHA): permissible exposure ceiling (the level that must not be exceeded, except once for 10 min. in an 8-hour shift, if no other measurable exposure occurs) **50 ppm PEL-Peak (OSHA): peak permissible exposure (the level that must never be exceeded) **100 ppm IDLH (NIOSH): immediately dangerous to life and health (the level that interferes with the ability to escape) * 0.00047 ppm or 0.47  ppb is the odor threshold, the point at which 50% of a human panel can detect the presence of an odor without being able to identify it. * 10–20 ppm is the borderline concentration for eye irritation. * 50–100 ppm leads to eye damage. * At 100–150 ppm the
olfactory nerve The olfactory nerve, also known as the first cranial nerve, cranial nerve I, or simply CN I, is a cranial nerve that contains sensory nerve fibers relating to the sense of smell. The afferent nerve fibers of the olfactory receptor neurons tr ...
is paralyzed after a few inhalations, and the sense of smell disappears, often together with awareness of danger. * 320–530 ppm leads to pulmonary edema with the possibility of death. * 530–1000 ppm causes strong stimulation of the central nervous system 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.


Treatment

Treatment involves immediate inhalation of amyl nitrite, injections of sodium nitrite, or administration of 4-dimethylaminophenol in combination with inhalation of pure oxygen, administration of bronchodilators to overcome eventual bronchospasm, and in some cases hyperbaric oxygen therapy (HBOT). HBOT has clinical and anecdotal support.


Incidents

Hydrogen sulfide was used by the British Army as a chemical weapon 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. In 1975, a hydrogen sulfide release from an oil drilling operation in Denver City, Texas, killed nine people and caused the
state legislature A state legislature is a legislative branch or body of a political subdivision in a federal system. Two federations literally use the term "state legislature": * The legislative branches of each of the fifty state governments of the United Sta ...
to focus on the deadly hazards of the gas.
State Representative A state legislature is a legislative branch or body of a political subdivision in a federal system. Two federations literally use the term "state legislature": * The legislative branches of each of the fifty state governments of the United Sta ...
E L Short 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. An exposed person may die from a second exposure to the gas, and a warning itself may be too late. On September 2, 2005, a leak in the propeller room of a Royal Caribbean Cruise Liner docked in Los Angeles resulted in the deaths of 3 crewmen due to a sewage line leak. As a result, all such compartments are now required to have a ventilation system. A dump of toxic waste containing hydrogen sulfide is believed to have caused 17 deaths and thousands of illnesses in Abidjan, on the West African coast, in the
2006 Côte d'Ivoire toxic waste dump The 2006 Ivory Coast toxic waste dump was a health crisis in Ivory Coast in which a ship registered in Panama, the ''Probo Koala'', chartered by the Singaporean-based oil and commodity shipping company Trafigura Beheer BV, offloaded toxic waste ...
. In September 2008, three workers were killed and two suffered serious injury, including long term brain damage, at a mushroom growing company in
Langley Langley may refer to: People * Langley (surname), a common English surname, including a list of notable people with the name * Dawn Langley Simmons (1922–2000), English author and biographer * Elizabeth Langley (born 1933), Canadian perfor ...
, British Columbia. A valve to a pipe that carried chicken manure, straw and gypsum to the compost fuel for the mushroom growing operation became clogged, and as workers unclogged the valve in a confined space without proper ventilation the hydrogen sulfide that had built up due to anaerobic decomposition of the material was released, poisoning the workers in the surrounding area. Investigator said there could have been more fatalities if the pipe had been fully cleared and/or if the wind had changed directions. In 2014, levels of hydrogen sulfide as high as 83 ppm were detected at a recently built mall in Thailand called Siam Square One at the Siam Square area. Shop tenants at the mall reported health complications such as sinus inflammation, breathing difficulties and eye irritation. After investigation it was determined that the large amount of gas originated from imperfect treatment and disposal of waste water in the building. In November 2014, a substantial amount of hydrogen sulfide gas shrouded the central, eastern and southeastern parts of Moscow. Residents living in the area were urged to stay indoors by the emergencies ministry. Although the exact source of the gas was not known, blame had been placed on a Moscow oil refinery. In June 2016, a mother and her daughter were found deceased in their still-running 2006 Porsche Cayenne SUV against a guardrail on
Florida's Turnpike Florida's Turnpike, designated as unsigned State Road 91 (SR 91), is a toll road in the U.S. state of Florida, maintained by Florida's Turnpike Enterprise (FTE). Spanning approximately along a northwest–southeast axis, the turnpike is in two s ...
, initially thought to be victims of carbon monoxide poisoning. Their deaths remained unexplained as the medical examiner waited for results of toxicology tests on the victims, until urine tests revealed that hydrogen sulfide was the cause of death. A report from the Orange-Osceola Medical Examiner's Office indicated that toxic fumes came from the Porsche's starter battery, located under the front passenger seat. In January 2017, three utility workers in Key Largo, Florida, died one by one within seconds of descending into a narrow space beneath a manhole cover to check a section of paved street. In an attempt to save the men, a firefighter who entered the hole without his air tank (because he could not fit through the hole with it) collapsed within seconds and had to be rescued by a colleague. The firefighter was airlifted to
Jackson Memorial Hospital Jackson Memorial Hospital (also known as "Jackson" or abbreviated "MJMH") is a non-profit, tertiary care hospital, the primary teaching hospital of the University of Miami's School of Medicine, and the largest hospital in the United States with 1,5 ...
and later recovered. A Monroe County Sheriff officer initially determined that the space contained hydrogen sulfide and methane gas produced by decomposing vegetation. On May 24, 2018, two workers were killed, another seriously injured, and 14 others hospitalized by hydrogen sulfide inhalation at a Norske Skog paper mill in Albury, New South Wales. An investigation by SafeWork NSW found that the gas was released from a tank used to hold process water. The workers were exposed at the end of a 3-day maintenance period. Hydrogen sulfide had built up in an upstream tank, which had been left stagnant and untreated with
biocide A biocide is defined in the European legislation as a chemical substance or microorganism intended to destroy, deter, render harmless, or exert a controlling effect on any harmful organism. The US Environmental Protection Agency (EPA) uses a slig ...
during the maintenance period. These conditions allowed sulfate-reducing bacteria to grow in the upstream tank, as the water contained small quantities of wood pulp and fiber. The high rate of pumping from this tank into the tank involved in the incident caused hydrogen sulfide gas to escape from various openings around its top when pumping was resumed at the end of the maintenance period. The area above it was sufficiently enclosed for the gas to pool there, despite not being identified as a confined space by Norske Skog. One of the workers who was killed was exposed while investigating an apparent fluid leak in the tank, while the other who was killed and the worker who was badly injured were attempting to rescue the first after he collapsed on top of it. In a resulting
criminal case Criminal law is the body of law that relates to crime. It prescribes conduct perceived as threatening, harmful, or otherwise endangering to the property, health, safety, and moral welfare of people inclusive of one's self. Most criminal law i ...
, Norske Skog was accused of failing to ensure the health and safety of its workforce at the plant to a reasonably practicable extent. It plead guilty, and was fined AU$1,012,500 and ordered to fund the production of an anonymized educational video about the incident. In October 2019, an Odessa, Texas employee of Aghorn Operating Inc. and his wife were killed due to a water pump failure. Produced water with a high concentration of hydrogen sulfide was released by the pump. The worker died while responding to an automated phone call he had received alerting him to a mechanical failure in the pump, while his wife died after driving to the facility to check on him. A CSB investigation cited lax safety practices at the facility, such as an informal lockout-tagout procedure and a nonfunctioning hydrogen sulfide alert system.


Suicides

The gas, produced by mixing certain household ingredients, was used in a
suicide Suicide is the act of intentionally causing one's own death. Mental disorders (including depression, bipolar disorder, schizophrenia, personality disorders, anxiety disorders), physical disorders (such as chronic fatigue syndrome), and s ...
wave in 2008 in Japan. The wave prompted staff at Tokyo's
suicide prevention Suicide prevention is a collection of efforts to reduce the risk of suicide. Suicide is often preventable, and the efforts to prevent it may occur at the individual, relationship, community, and society level. Suicide is a serious public health ...
center to set up a special hotline 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, 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 or injury from inhaling the gas, or by fire. Local governments have also initiated campaigns to prevent such suicides. In 2020, H2S ingestion was used as a suicide method by Japanese pro wrestler Hana Kimura.


Hydrogen sulfide in the natural environment


Microbial: The sulfur cycle

Hydrogen sulfide is a central participant in the
sulfur cycle The sulfur cycle is a biogeochemical cycle in which the sulfur moves between rocks, waterways and living systems. It is important in geology as it affects many minerals and in life because sulfur is an essential element ( CHNOPS), being a const ...
, the
biogeochemical cycle A biogeochemical cycle (or more generally a cycle of matter) is the pathway by which a chemical substance cycles (is turned over or moves through) the biotic and the abiotic compartments of Earth. The biotic compartment is the biosphere and the ...
of sulfur on Earth. In the absence of oxygen, sulfur-reducing and
sulfate-reducing Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria (SRB) and sulfate-reducing archaea (SRA), both of which can perform anaerobic respiration utilizing sulfate () as term ...
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 acids; this gives rise to the odor of rotten eggs and contributes to the odor of
flatulence Flatulence, in humans, is the expulsion of gas from the intestines via the anus, commonly referred to as farting. "Flatus" is the medical word for gas generated in the stomach or bowels. A proportion of intestinal gas may be swallowed environm ...
. 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., iron oxyhydroxides and manganese oxides), or nitrate as electron acceptors. The purple sulfur bacteria and the green sulfur bacteria use hydrogen sulfide as an electron donor in photosynthesis, thereby producing elemental sulfur. This mode of photosynthesis is older than the mode of
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...
,
algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular mic ...
, and plants, which uses water as electron donor and liberates oxygen. The biochemistry of hydrogen sulfide is a key part of the chemistry of the iron-sulfur world. In this model of the origin of life on Earth, geologically produced hydrogen sulfide is postulated as an electron donor driving the reduction of carbon dioxide.


Animals

Hydrogen sulfide is lethal to most animals, but a few highly specialized species ( extremophiles) do thrive in habitats that are rich in this compound. In the deep sea,
hydrothermal vent A hydrothermal vent is a fissure on the seabed from which geothermally heated water discharges. They are commonly found near volcanically active places, areas where tectonic plates are moving apart at mid-ocean ridges, ocean basins, and hotspot ...
s and cold seeps with high levels of hydrogen sulfide are home to a number of extremely specialized lifeforms, ranging from bacteria to fish. Because of the absence of sunlight at these depths, these ecosystems rely on chemosynthesis rather than photosynthesis. Freshwater springs rich in hydrogen sulfide are mainly home to invertebrates, but also include a small number of fish: ''
Cyprinodon bobmilleri ''Cyprinodon'' is a genus of pupfishes found in waters that range from fresh to hypersaline. The genus is primarily found in Mexico, the Caribbean Islands and southern United States (Arizona, California, Florida, Nevada, New Mexico, Oklahoma and ...
'' (a pupfish from Mexico), '' Limia sulphurophila'' (a poeciliid from the Dominican Republic), ''
Gambusia eurystoma The widemouth gambusia (''Gambusia eurystoma'') is a species of fish in the family Poeciliidae of the order Cyprinodontiformes. It is endemic to Mexico, specifically to the Baños del Azufre (Grijalva River basin) near Teapa, Tabasco Tabasc ...
'' (a poeciliid from Mexico), and a few '' Poecilia'' (poeciliids from Mexico). Invertebrates and microorganisms in some cave systems, such as Movile Cave, are adapted to high levels of hydrogen sulfide.


Interstellar and planetary occurrence

Hydrogen sulfide has often been detected in the interstellar medium. It also occurs in the clouds of planets in our solar system.


Mass extinctions

Hydrogen sulfide has been implicated in several mass extinctions that have occurred in the Earth's past. In particular, a buildup of hydrogen sulfide in the atmosphere may have caused, or at least contributed to, 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 The Dead Sea ( he, יַם הַמֶּלַח, ''Yam hamMelaḥ''; ar, اَلْبَحْرُ الْمَيْتُ, ''Āl-Baḥrū l-Maytū''), also known by other names, is a salt lake bordered by Jordan to the east and Israel and the West Bank ...
and in the Atlantic ocean off the coast of Namibia.


See also

* *
Hydrogen sulfide chemosynthesis Hydrogen sulfide chemosynthesis is a form of chemosynthesis which uses hydrogen sulfide. It is common in hydrothermal vent microbial communities Due to the lack of light in these environments this is predominant over photosynthesis Giant tube wo ...
* * * Marsh gas


References


Additional resources

* *


External links


International Chemical Safety Card 0165







NACE (National Association of Corrosion Epal)
{{DEFAULTSORT:Hydrogen Sulfide Acids Foul-smelling chemicals Hydrogen compounds Industrial gases Airborne pollutants Sulfides Flatulence Gaseous signaling molecules Blood agents