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Hydrogen sulfide is a
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
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 betwe ...
. 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 Carl Wilhelm Scheele (, ; 9 December 1742 – 21 May 1786) was a Swedish German pharmaceutical chemist. Scheele discovered oxygen (although Joseph Priestley published his findings first), and identified molybdenum, tungsten, barium, hydr ...
is credited with having discovered the chemical composition of purified hydrogen sulfide in 1777. The
British English British English (BrE, en-GB, or BE) is, according to Oxford Dictionaries, "English as used in Great Britain, as distinct from that used elsewhere". More narrowly, it can refer specifically to the English language in England, or, more broadl ...
spelling of this compound is hydrogen sulphide, a spelling no longer recommended by the
Royal Society of Chemistry The Royal Society of Chemistry (RSC) is a learned society (professional association) in the United Kingdom with the goal of "advancing the chemical sciences". It was formed in 1980 from the amalgamation of the Chemical Society, the Royal Inst ...
or the
International Union of Pure and Applied Chemistry The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
. Hydrogen sulfide is toxic to humans and most other animals by inhibiting
cellular respiration Cellular respiration is the process by which biological fuels are oxidised in the presence of an inorganic electron acceptor such as oxygen to produce large amounts of energy, to drive the bulk production of ATP. Cellular respiration may be des ...
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 a ...
. 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 being. It is composed of many different types of cells that together create tissues and subsequently organ systems. They ensure homeostasis and the viability of the human body. It comprises a hea ...
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 breakdown of organic matter in the absence of oxygen, such as in swamps and sewers; this process is commonly known as
anaerobic digestion Anaerobic digestion is a sequence of processes by which microorganisms break down biodegradable material in the absence of oxygen. The process is used for industrial or domestic purposes to manage waste or to produce fuels. Much of the ferm ...
, which is done by sulfate-reducing microorganisms. It also occurs in volcanic gases,
natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbon d ...
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 a ...
() and
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
. In general, hydrogen sulfide acts as a
reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth met ...
, 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
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s, 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 formul ...
and
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...
. This reaction is exploited in the Claus process, an important industrial method to dispose of hydrogen sulfide. Hydrogen sulfide is slightly soluble in water and acts as a
weak acid Acid strength is the tendency of an acid, symbolised by the chemical formula HA, to dissociate into a proton, H+, and an anion, A-. The dissociation of a strong acid in solution is effectively complete, except in its most concentrated solutions ...
( 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 la ...
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 Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
and
silver Silver is a chemical element with the symbol Ag (from the Latin ', derived from the Proto-Indo-European ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, white, lustrous transition metal, it exhibits the highest electrical ...
; the chemical responsible for black toning found on silver coins is silver sulfide (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 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, which is natural gas with a high content of . It can also be produced by treating
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
with molten elemental sulfur at about 450 °C. Hydrocarbons can serve as a source of hydrogen in this process. Sulfate-reducing (resp. sulfur-reducing) bacteria generate usable energy under low-oxygen conditions by using sulfates (resp. elemental sulfur) to
oxidize Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
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: :FeS + 2 HCl → FeCl2 + H2S For use in
qualitative inorganic analysis Classical qualitative inorganic analysis is a method of analytical chemistry which seeks to find the elemental composition of inorganic compounds. It is mainly focused on detecting ions in an aqueous solution, therefore materials in other forms m ...
, 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 Si S2. Like silicon dioxide, this material is polymeric, but it adopts a 1-dimensional structure quite different from the usual forms of SiO2. Synthesis, structure, and properties Th ...
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 Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ...
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 (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 ferredoxins 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 compounds are produced using hydrogen sulfide. These include methanethiol, ethanethiol, and thioglycolic acid. 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: :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. 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 Classical qualitative inorganic analysis is a method of analytical chemistry which seeks to find the elemental composition of inorganic compounds. It is mainly focused on detecting ions in an aqueous solution, therefore materials in other forms m ...
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, 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 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. Scientists from the
University of Exeter , mottoeng = "We Follow the Light" , established = 1838 - St Luke's College1855 - Exeter School of Art1863 - Exeter School of Science 1955 - University of Exeter (received royal charter) , type = Public , ...
discovered that cell exposure to small amounts of hydrogen sulfide gas can prevent
mitochondria A mitochondrion (; ) is an organelle found in the cells of most Eukaryotes, such as animals, plants and fungi. Mitochondria have a double membrane structure and use aerobic respiration to generate adenosine triphosphate (ATP), which is used ...
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 disease, medical condition in which poor cerebral circulation, blood flow to the brain causes cell death. There are two main types of stroke: brain ischemia, ischemic, due to lack of blood flow, and intracranial hemorrhage, hemorr ...
s, heart disease and arthritis. 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 Hypothermia is defined as a body core temperature below in humans. Symptoms depend on the temperature. In mild hypothermia, there is shivering and mental confusion. In moderate hypothermia, shivering stops and confusion increases. In severe ...
with a concomitant reduction in metabolic rate. Oxygen demand was also reduced, thereby protecting against hypoxia. In addition, hydrogen sulfide has been shown to reduce inflammation in various situations.


Occurrence

Volcano A volcano is a rupture in the crust of a planetary-mass object, such as Earth, that allows hot lava, volcanic ash, and gases to escape from a magma chamber below the surface. On Earth, volcanoes are most often found where tectonic plates ...
es and some
hot spring A hot spring, hydrothermal spring, or geothermal spring is a spring produced by the emergence of geothermally heated groundwater onto the surface of the Earth. The groundwater is heated either by shallow bodies of magma (molten rock) or by circ ...
s (as well as cold springs) emit some , where it probably arises via the
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysi ...
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 Bad breath, also known as halitosis, is a symptom in which a noticeably unpleasant breath odour is present. It can result in anxiety among those affected. It is also associated with depression and symptoms of obsessive compulsive disorder. ...
). A portion of global emissions are due to human activity. By far the largest industrial source of is petroleum refineries: The hydrodesulfurization process liberates sulfur from
petroleum Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crud ...
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 mills (using the Kraft process), tanneries and sewerage. 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 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 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 wast ...
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 Anaerobic digestion is a sequence of processes by which microorganisms break down biodegradable material in the absence of oxygen. The process is used for industrial or domestic purposes to manage waste or to produce fuels. Much of the ferm ...
within the waste mass and, with the humid atmosphere and relatively high temperature that accompanies
biodegradation Biodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. It is generally assumed to be a natural process, which differentiates it from composting. Composting is a human-driven process in which biodegra ...
, 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 Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywa ...
(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 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 Drinking water is water that is used in drink or food preparation; potable water is water that is safe to be used as drinking water. The amount of drinking water required to maintain good health varies, and depends on physical activity level, ...
. ;Continuous chlorination: For levels up to 75 mg/L
chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
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.


Safety

Hydrogen sulfide is a highly
toxic Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a sub ...
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 In biology, the nervous system is the highly complex part of an animal that coordinates its actions and sensory information by transmitting signals to and from different parts of its body. The nervous system detects environmental changes ...
is most affected. The toxicity of is comparable with that of
carbon monoxide Carbon monoxide ( chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...
. It binds with
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
in the
mitochondria A mitochondrion (; ) is an organelle found in the cells of most Eukaryotes, such as animals, plants and fungi. Mitochondria have a double membrane structure and use aerobic respiration to generate adenosine triphosphate (ATP), which is used ...
l
cytochrome Cytochromes are redox-active proteins containing a heme, with a central Fe atom at its core, as a cofactor. They are involved in electron transport chain and redox catalysis. They are classified according to the type of heme and its mode of ...
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
s, thus preventing
cellular respiration Cellular respiration is the process by which biological fuels are oxidised in the presence of an inorganic electron acceptor such as oxygen to produce large amounts of energy, to drive the bulk production of ATP. Cellular respiration may be des ...
. Its toxic properties were described in detail in 1843 by Justus von Liebig.


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 irritation, a sore throat and cough, nausea, shortness of breath, and fluid in the lungs (
pulmonary edema Pulmonary edema, also known as pulmonary congestion, is excessive liquid accumulation in the tissue and air spaces (usually alveoli) of the lungs. It leads to impaired gas exchange and may cause hypoxemia and respiratory failure. It is due ...
). These effects are believed to be due to hydrogen sulfide combining with alkali present in moist surface tissues to form sodium sulfide, 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 ''caust ...
. These symptoms usually subside in a few weeks. Long-term, low-level exposure may result in fatigue, loss of appetite, headaches, irritability, poor memory, and
dizziness Dizziness is an imprecise term that can refer to a sense of disorientation in space, vertigo, or lightheadedness. It can also refer to disequilibrium or a non-specific feeling, such as giddiness or foolishness. Dizziness is a common medical c ...
. 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 The basal ganglia (BG), or basal nuclei, are a group of subcortical nuclei, of varied origin, in the brains of vertebrates. In humans, and some primates, there are some differences, mainly in the division of the globus pallidus into an ext ...
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 Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pink ...
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): 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 The term immediately dangerous to life or health (IDLH) is defined by the US National Institute for Occupational Safety and Health (NIOSH) as exposure to airborne contaminants that is "likely to cause death or immediate or delayed permanent advers ...
(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 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 Pulmonary edema, also known as pulmonary congestion, is excessive liquid accumulation in the tissue and air spaces (usually alveoli) of the lungs. It leads to impaired gas exchange and may cause hypoxemia and respiratory failure. It is due ...
with the possibility of death. * 530–1000 ppm causes strong stimulation of the
central nervous system The central nervous system (CNS) is the part of the nervous system consisting primarily of the brain and spinal cord. The CNS is so named because the brain integrates the received information and coordinates and influences the activity of all p ...
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 Sodium nitrite is an inorganic compound with the chemical formula NaNO2. It is a white to slightly yellowish crystalline powder that is very soluble in water and is hygroscopic. From an industrial perspective, it is the most important 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 The British Army is the principal land warfare force of the United Kingdom, a part of the British Armed Forces along with the Royal Navy and the Royal Air Force. , the British Army comprises 79,380 regular full-time personnel, 4,090 Gurkha ...
as a chemical weapon during
World War I World War I (28 July 1914 11 November 1918), often abbreviated as WWI, was List of wars and anthropogenic disasters by death toll, one of the deadliest global conflicts in history. Belligerents included much of Europe, the Russian Empire, ...
. 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 Texas State Legislature, state legislature to focus on the deadly hazards of the gas. Texas House of Representatives, State Representative E L Short took the lead in endorsing an investigation by the Railroad Commission of Texas, 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. In September 2008, three workers were killed and two suffered serious injury, including long term brain damage, at a mushroom growing company in Langley, British Columbia (city), Langley, 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#Ft. Pierce to Wildwood, Florida's Turnpike, 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 Automotive battery, 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 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 Safe Work Australia, SafeWork NSW found that the gas was released from a tank used to hold Paper machine#Forming section or wet end, 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 during the maintenance period. These conditions allowed sulfate-reducing bacteria to grow in the upstream tank, as the water contained small quantities of Pulp (paper)#Wood pulp, wood pulp and Wood fibre, 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, 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 U.S. Chemical Safety and Hazard Investigation Board, 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 wave in 2008 in Japan. The wave prompted staff at Tokyo's suicide prevention center to set up a special hotline during "Golden Week (Japan), 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 biogeochemical cycle of sulfur on Earth. In the absence of oxygen, sulfur-reducing and Sulfate-reducing bacteria, sulfate-reducing bacteria derive energy from redox, 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. As organic matter decays under low-oxygen (or Hypoxia (environmental), hypoxic) conditions (such as in swamps, eutrophic lakes or Dead zone (ecology), 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(III) oxide-hydroxide, 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, algae, 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 theory, 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 vents 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'' (a pupfish from Mexico), ''Limia sulphurophila'' (a poeciliid from the Dominican Republic), ''Gambusia eurystoma'' (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 Extinction event, 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 and in the Atlantic ocean off the coast of Namibia.


See also

* *Hydrogen sulfide chemosynthesis * * *Marsh gas


References


Additional resources

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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