Carbon dioxide explained

Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature, and as the source of available carbon in the carbon cycle, atmospheric is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater. When carbon dioxide dissolves in water, it forms carbonate and mainly bicarbonate, which causes ocean acidification as atmospheric levels increase.[1]

It is a trace gas in Earth's atmosphere at 421 parts per million (ppm), or about 0.04% (as of May 2022) having risen from pre-industrial levels of 280 ppm or about 0.025%.[2] [3] Burning fossil fuels is the primary cause of these increased concentrations and also the primary cause of climate change.[4]

Its concentration in Earth's pre-industrial atmosphere since late in the Precambrian was regulated by organisms and geological phenomena. Plants, algae and cyanobacteria use energy from sunlight to synthesize carbohydrates from carbon dioxide and water in a process called photosynthesis, which produces oxygen as a waste product.[5] In turn, oxygen is consumed and is released as waste by all aerobic organisms when they metabolize organic compounds to produce energy by respiration.[6] is released from organic materials when they decay or combust, such as in forest fires.

Carbon dioxide is 53% more dense than dry air, but is long lived and thoroughly mixes in the atmosphere. About half of excess emissions to the atmosphere are absorbed by land and ocean carbon sinks.[7] These sinks can become saturated and are volatile, as decay and wildfires result in the being released back into the atmosphere.[8] is eventually sequestered (stored for the long term) in rocks and organic deposits like coal, petroleum and natural gas. Sequestered is released into the atmosphere through burning fossil fuels or naturally by volcanoes, hot springs, geysers, and when carbonate rocks dissolve in water or react with acids.

is a versatile industrial material, used, for example, as an inert gas in welding and fire extinguishers, as a pressurizing gas in air guns and oil recovery, and as a supercritical fluid solvent in decaffeination and supercritical drying.[9] It is a byproduct of fermentation of sugars in bread, beer and wine making, and is added to carbonated beverages like seltzer and beer for effervescence. It has a sharp and acidic odor and generates the taste of soda water in the mouth, but at normally encountered concentrations it is odorless.

Chemical and physical properties

Carbon dioxide cannot be liquefied at atmospheric pressure. Low-temperature carbon dioxide is commercially used in its solid form, commonly known as "dry ice". The solid-to-gas phase transition occurs at 194.7 Kelvin and is called sublimation.

Structure, bonding and molecular vibrations

The symmetry of a carbon dioxide molecule is linear and centrosymmetric at its equilibrium geometry. The length of the carbon–oxygen bond in carbon dioxide is 116.3 pm, noticeably shorter than the roughly 140 pm length of a typical single C–O bond, and shorter than most other C–O multiply bonded functional groups such as carbonyls. Since it is centrosymmetric, the molecule has no electric dipole moment.

As a linear triatomic molecule, has four vibrational modes as shown in the diagram. In the symmetric and the antisymmetric stretching modes, the atoms move along the axis of the molecule. There are two bending modes, which are degenerate, meaning that they have the same frequency and same energy, because of the symmetry of the molecule. When a molecule touches a surface or touches another molecule, the two bending modes can differ in frequency because the interaction is different for the two modes. Some of the vibrational modes are observed in the infrared (IR) spectrum: the antisymmetric stretching mode at wavenumber 2349 cm−1 (wavelength 4.25 μm) and the degenerate pair of bending modes at 667 cm−1 (wavelength 15 μm). The symmetric stretching mode does not create an electric dipole so is not observed in IR spectroscopy, but it is detected in Raman spectroscopy at 1388 cm−1 (wavelength 7.2 μm).[10]

In the gas phase, carbon dioxide molecules undergo significant vibrational motions and do not keep a fixed structure. However, in a Coulomb explosion imaging experiment, an instantaneous image of the molecular structure can be deduced. Such an experiment[11] has been performed for carbon dioxide. The result of this experiment, and the conclusion of theoretical calculations[12] based on an ab initio potential energy surface of the molecule, is that none of the molecules in the gas phase are ever exactly linear. This counter-intuitive result is trivially due to the fact that the nuclear motion volume element vanishes for linear geometries.[12] This is so for all molecules except diatomic molecules.

In aqueous solution

See also: Carbonic acid. Carbon dioxide is soluble in water, in which it reversibly forms (carbonic acid), which is a weak acid, because its ionization in water is incomplete.

The hydration equilibrium constant of carbonic acid is, at 25 °C:

K_\mathrm = \frac = 1.70 \times 10^Hence, the majority of the carbon dioxide is not converted into carbonic acid, but remains as molecules, not affecting the pH.

The relative concentrations of,, and the deprotonated forms (bicarbonate) and (carbonate) depend on the pH. As shown in a Bjerrum plot, in neutral or slightly alkaline water (pH > 6.5), the bicarbonate form predominates (>50%) becoming the most prevalent (>95%) at the pH of seawater. In very alkaline water (pH > 10.4), the predominant (>50%) form is carbonate. The oceans, being mildly alkaline with typical pH = 8.2–8.5, contain about 120 mg of bicarbonate per liter.

Being diprotic, carbonic acid has two acid dissociation constants, the first one for the dissociation into the bicarbonate (also called hydrogen carbonate) ion :

Ka1 = 2.5 × 10−4 mol/L; pKa1 = 3.6 at 25 °C.This is the true first acid dissociation constant, defined as

K_\mathrm = \fracwhere the denominator includes only covalently bound and does not include hydrated (aq). The much smaller and often-quoted value near 4.16 × 10−7 (or pKa1 = 6.38) is an apparent value calculated on the (incorrect) assumption that all dissolved is present as carbonic acid, so that

K_\mathrm=\fracSince most of the dissolved remains as molecules, Ka1(apparent) has a much larger denominator and a much smaller value than the true Ka1.[13]

The bicarbonate ion is an amphoteric species that can act as an acid or as a base, depending on pH of the solution. At high pH, it dissociates significantly into the carbonate ion :

Ka2 = 4.69 × 10−11 mol/L; pKa2 = 10.329

In organisms, carbonic acid production is catalysed by the enzyme known as carbonic anhydrase.

In addition to altering its acidity, the presence of carbon dioxide in water also affects its electrical properties. When carbon dioxide dissolves in desalinated water, the electrical conductivity increases significantly from below 1 μS/cm to nearly 30 μS/cm. When heated, the water begins to gradually lose the conductivity induced by the presence of

CO2
, especially noticeable as temperatures exceed 30 °C.

The temperature dependence of the electrical conductivity of fully deionized water without

CO2
saturation is comparably low in relation to these data.

Chemical reactions

is a potent electrophile having an electrophilic reactivity that is comparable to benzaldehyde or strongly electrophilic α,β-unsaturated carbonyl compounds. However, unlike electrophiles of similar reactivity, the reactions of nucleophiles with are thermodynamically less favored and are often found to be highly reversible.[14] The reversible reaction of carbon dioxide with amines to make carbamates is used in scrubbers and has been suggested as a possible starting point for carbon capture and storage by amine gas treating.Only very strong nucleophiles, like the carbanions provided by Grignard reagents and organolithium compounds react with to give carboxylates:

where M = Li or MgBr and R = alkyl or aryl.

In metal carbon dioxide complexes, serves as a ligand, which can facilitate the conversion of to other chemicals.[15]

The reduction of to CO is ordinarily a difficult and slow reaction:

The redox potential for this reaction near pH 7 is about −0.53 V versus the standard hydrogen electrode. The nickel-containing enzyme carbon monoxide dehydrogenase catalyses this process.[16]

Photoautotrophs (i.e. plants and cyanobacteria) use the energy contained in sunlight to photosynthesize simple sugars from absorbed from the air and water:

Physical properties

Carbon dioxide is colorless. At low concentrations, the gas is odorless; however, at sufficiently high concentrations, it has a sharp, acidic odor.[17] At standard temperature and pressure, the density of carbon dioxide is around 1.98 kg/m3, about 1.53 times that of air.[18]

Carbon dioxide has no liquid state at pressures below 0.51795(10) MPa (5.11177(99) atm). At a pressure of 1 atm (0.101325 MPa), the gas deposits directly to a solid at temperatures below 194.6855(30) K (−78.4645(30) °C) and the solid sublimes directly to a gas above this temperature. In its solid state, carbon dioxide is commonly called dry ice.

Liquid carbon dioxide forms only at pressures above 0.51795(10) MPa (5.11177(99) atm); the triple point of carbon dioxide is 216.592(3) K (−56.558(3) °C) at 0.51795(10) MPa (5.11177(99) atm) (see phase diagram). The critical point is 304.128(15) K (30.978(15) °C) at 7.3773(30) MPa (72.808(30) atm). Another form of solid carbon dioxide observed at high pressure is an amorphous glass-like solid.[19] This form of glass, called carbonia, is produced by supercooling heated at extreme pressures (40–48 GPa, or about 400,000 atmospheres) in a diamond anvil. This discovery confirmed the theory that carbon dioxide could exist in a glass state similar to other members of its elemental family, like silicon dioxide (silica glass) and germanium dioxide. Unlike silica and germania glasses, however, carbonia glass is not stable at normal pressures and reverts to gas when pressure is released.

At temperatures and pressures above the critical point, carbon dioxide behaves as a supercritical fluid known as supercritical carbon dioxide.

Table of thermal and physical properties of saturated liquid carbon dioxide:[20] [21]

Temperature (°C)Density (kg/m3)Specific heat (kJ/(kg⋅K))Kinematic viscosity (m2/s)Thermal conductivity (W/(m⋅K))Thermal diffusivity (m2/s)Prandtl NumberBulk modulus (K^-1)
−501156.341.841.19 × 10−70.08554.02 × 10−82.96
−401117.771.881.18 × 10−70.10114.81 × 10−82.46
−301076.761.971.17 × 10−70.11165.27 × 10−82.22
−201032.392.051.15 × 10−70.11515.45 × 10−82.12
−10983.382.181.13 × 10−70.10995.13 × 10−82.2
0926.992.471.08 × 10−70.10454.58 × 10−82.38
10860.033.141.01 × 10−70.09713.61 × 10−82.8
20772.5759.10 × 10−80.08722.22 × 10−84.11.40 × 10−2
30597.8136.48.00 × 10−80.07030.279 × 10−828.7
Table of thermal and physical properties of carbon dioxide at atmospheric pressure:[20] [21]
Temperature (K)Density (kg/m3)Specific heat (kJ/(kg⋅°C))Dynamic viscosity (kg/(m⋅s))Kinematic viscosity (m2/s)Thermal conductivity (W/(m⋅°C))Thermal diffusivity (m2/s)Prandtl Number
2202.47330.7831.11 × 10−54.49 × 10−60.0108055.92 × 10−60.818
2502.16570.8041.26 × 10−55.81 × 10−60.0128847.40 × 10−60.793
3001.79730.8711.50 × 10−58.32 × 10−60.0165721.06 × 10−50.77
3501.53620.91.72 × 10−51.12 × 10−50.020471.48 × 10−50.755
4001.34240.9421.93 × 10−51.44 × 10−50.024611.95 × 10−50.738
4501.19180.982.13 × 10−51.79 × 10−50.028972.48 × 10−50.721
5001.07321.0132.33 × 10−52.17 × 10−50.033523.08 × 10−50.702
5500.97391.0472.51 × 10−52.57 × 10−50.038213.75 × 10−50.685
6000.89381.0762.68 × 10−53.00 × 10−50.043114.48 × 10−50.668
6500.81431.12.88 × 10−53.54 × 10−50.04454.97 × 10−50.712
7000.75641.133.05 × 10−54.03 × 10−50.04815.63 × 10−50.717
7500.70571.153.21 × 10−54.55 × 10−50.05176.37 × 10−50.714
8000.66141.173.37 × 10−55.10 × 10−50.05517.12 × 10−50.716

Biological role

Carbon dioxide is an end product of cellular respiration in organisms that obtain energy by breaking down sugars, fats and amino acids with oxygen as part of their metabolism. This includes all plants, algae and animals and aerobic fungi and bacteria. In vertebrates, the carbon dioxide travels in the blood from the body's tissues to the skin (e.g., amphibians) or the gills (e.g., fish), from where it dissolves in the water, or to the lungs from where it is exhaled. During active photosynthesis, plants can absorb more carbon dioxide from the atmosphere than they release in respiration.

Photosynthesis and carbon fixation

Carbon fixation is a biochemical process by which atmospheric carbon dioxide is incorporated by plants, algae and cyanobacteria into energy-rich organic molecules such as glucose, thus creating their own food by photosynthesis. Photosynthesis uses carbon dioxide and water to produce sugars from which other organic compounds can be constructed, and oxygen is produced as a by-product.

Ribulose-1,5-bisphosphate carboxylase oxygenase, commonly abbreviated to RuBisCO, is the enzyme involved in the first major step of carbon fixation, the production of two molecules of 3-phosphoglycerate from and ribulose bisphosphate, as shown in the diagram at left.

RuBisCO is thought to be the single most abundant protein on Earth.[22]

Phototrophs use the products of their photosynthesis as internal food sources and as raw material for the biosynthesis of more complex organic molecules, such as polysaccharides, nucleic acids, and proteins. These are used for their own growth, and also as the basis of the food chains and webs that feed other organisms, including animals such as ourselves. Some important phototrophs, the coccolithophores synthesise hard calcium carbonate scales.[23] A globally significant species of coccolithophore is Emiliania huxleyi whose calcite scales have formed the basis of many sedimentary rocks such as limestone, where what was previously atmospheric carbon can remain fixed for geological timescales.

Plants can grow as much as 50% faster in concentrations of 1,000 ppm when compared with ambient conditions, though this assumes no change in climate and no limitation on other nutrients.[24] Elevated levels cause increased growth reflected in the harvestable yield of crops, with wheat, rice and soybean all showing increases in yield of 12–14% under elevated in FACE experiments.[25] [26]

Increased atmospheric concentrations result in fewer stomata developing on plants[27] which leads to reduced water usage and increased water-use efficiency.[28] Studies using FACE have shown that enrichment leads to decreased concentrations of micronutrients in crop plants.[29] This may have knock-on effects on other parts of ecosystems as herbivores will need to eat more food to gain the same amount of protein.[30]

The concentration of secondary metabolites such as phenylpropanoids and flavonoids can also be altered in plants exposed to high concentrations of .[31] [32]

Plants also emit during respiration, and so the majority of plants and algae, which use C3 photosynthesis, are only net absorbers during the day. Though a growing forest will absorb many tons of each year, a mature forest will produce as much from respiration and decomposition of dead specimens (e.g., fallen branches) as is used in photosynthesis in growing plants.[33] Contrary to the long-standing view that they are carbon neutral, mature forests can continue to accumulate carbon[34] and remain valuable carbon sinks, helping to maintain the carbon balance of Earth's atmosphere. Additionally, and crucially to life on earth, photosynthesis by phytoplankton consumes dissolved in the upper ocean and thereby promotes the absorption of from the atmosphere.[35]

Toxicity

See also: Carbon dioxide poisoning.

Carbon dioxide content in fresh air (averaged between sea-level and 10 kPa level, i.e., about altitude) varies between 0.036% (360 ppm) and 0.041% (412 ppm), depending on the location.[36]

is an asphyxiant gas and not classified as toxic or harmful in accordance with Globally Harmonized System of Classification and Labelling of Chemicals standards of United Nations Economic Commission for Europe by using the OECD Guidelines for the Testing of Chemicals. In concentrations up to 1% (10,000 ppm), it will make some people feel drowsy and give the lungs a stuffy feeling. Concentrations of 7% to 10% (70,000 to 100,000 ppm) may cause suffocation, even in the presence of sufficient oxygen, manifesting as dizziness, headache, visual and hearing dysfunction, and unconsciousness within a few minutes to an hour.[37] The physiological effects of acute carbon dioxide exposure are grouped together under the term hypercapnia, a subset of asphyxiation.

Because it is heavier than air, in locations where the gas seeps from the ground (due to sub-surface volcanic or geothermal activity) in relatively high concentrations, without the dispersing effects of wind, it can collect in sheltered/pocketed locations below average ground level, causing animals located therein to be suffocated. Carrion feeders attracted to the carcasses are then also killed. Children have been killed in the same way near the city of Goma by emissions from the nearby volcano Mount Nyiragongo.[38] The Swahili term for this phenomenon is Swahili: [[mazuku]].

Adaptation to increased concentrations of occurs in humans, including modified breathing and kidney bicarbonate production, in order to balance the effects of blood acidification (acidosis). Several studies suggested that 2.0 percent inspired concentrations could be used for closed air spaces (e.g. a submarine) since the adaptation is physiological and reversible, as deterioration in performance or in normal physical activity does not happen at this level of exposure for five days.[39] [40] Yet, other studies show a decrease in cognitive function even at much lower levels.[41] [42] Also, with ongoing respiratory acidosis, adaptation or compensatory mechanisms will be unable to reverse the condition.

Below 1%

There are few studies of the health effects of long-term continuous exposure on humans and animals at levels below 1%. Occupational exposure limits have been set in the United States at 0.5% (5000 ppm) for an eight-hour period.[43] At this concentration, International Space Station crew experienced headaches, lethargy, mental slowness, emotional irritation, and sleep disruption.[44] Studies in animals at 0.5% have demonstrated kidney calcification and bone loss after eight weeks of exposure.[45] A study of humans exposed in 2.5 hour sessions demonstrated significant negative effects on cognitive abilities at concentrations as low as 0.1% (1000ppm) likely due to induced increases in cerebral blood flow. Another study observed a decline in basic activity level and information usage at 1000 ppm, when compared to 500 ppm.

However a review of the literature found that a reliable subset of studies on the phenomenon of carbon dioxide induced cognitive impairment to only show a small effect on high-level decision making (for concentrations below 5000 ppm). Most of the studies were confounded by inadequate study designs, environmental comfort, uncertainties in exposure doses and differing cognitive assessments used.[46] Similarly a study on the effects of the concentration of in motorcycle helmets has been criticized for having dubious methodology in not noting the self-reports of motorcycle riders and taking measurements using mannequins. Further when normal motorcycle conditions were achieved (such as highway or city speeds) or the visor was raised the concentration of declined to safe levels (0.2%).[47] [48]

General guidelines on indoor concentration effects! Concentration !! Note
280 ppm Pre-industrial levels
421 ppm Current (May 2022) levels
700 ppm ASHRAE recommendation[49]
5,000 ppm USA 8h exposure limit
10,000 ppm Cognitive impairment, Canada's long term exposure limit
10,000-20,000 ppm Drowsiness
20,000-50,000 ppm Headaches, sleepiness; poor concentration, loss of attention, slight nausea also possible

Ventilation

Poor ventilation is one of the main causes of excessive concentrations in closed spaces, leading to poor indoor air quality. Carbon dioxide differential above outdoor concentrations at steady state conditions (when the occupancy and ventilation system operation are sufficiently long that concentration has stabilized) are sometimes used to estimate ventilation rates per person.[50] Higher concentrations are associated with occupant health, comfort and performance degradation.[51] [52] ASHRAE Standard 62.1–2007 ventilation rates may result in indoor concentrations up to 2,100 ppm above ambient outdoor conditions. Thus if the outdoor concentration is 400 ppm, indoor concentrations may reach 2,500 ppm with ventilation rates that meet this industry consensus standard. Concentrations in poorly ventilated spaces can be found even higher than this (range of 3,000 or 4,000 ppm).

Miners, who are particularly vulnerable to gas exposure due to insufficient ventilation, referred to mixtures of carbon dioxide and nitrogen as "blackdamp", "choke damp" or "stythe". Before more effective technologies were developed, miners would frequently monitor for dangerous levels of blackdamp and other gases in mine shafts by bringing a caged canary with them as they worked. The canary is more sensitive to asphyxiant gases than humans, and as it became unconscious would stop singing and fall off its perch. The Davy lamp could also detect high levels of blackdamp (which sinks, and collects near the floor) by burning less brightly, while methane, another suffocating gas and explosion risk, would make the lamp burn more brightly.

In February 2020, three people died from suffocation at a party in Moscow when dry ice (frozen) was added to a swimming pool to cool it down.[53] A similar accident occurred in 2018 when a woman died from fumes emanating from the large amount of dry ice she was transporting in her car.[54]

Indoor air

Humans spend more and more time in a confined atmosphere (around 80-90% of the time in a building or vehicle). According to the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) and various actors in France, the rate in the indoor air of buildings (linked to human or animal occupancy and the presence of combustion installations), weighted by air renewal, is "usually between about 350 and 2,500 ppm".[55]

In homes, schools, nurseries and offices, there are no systematic relationships between the levels of and other pollutants, and indoor is statistically not a good predictor of pollutants linked to outdoor road (or air, etc.) traffic.[56] is the parameter that changes the fastest (with hygrometry and oxygen levels when humans or animals are gathered in a closed or poorly ventilated room). In poor countries, many open hearths are sources of and CO emitted directly into the living environment.[57]

Outdoor areas with elevated concentrations

Local concentrations of carbon dioxide can reach high values near strong sources, especially those that are isolated by surrounding terrain. At the Bossoleto hot spring near Rapolano Terme in Tuscany, Italy, situated in a bowl-shaped depression about in diameter, concentrations of rise to above 75% overnight, sufficient to kill insects and small animals. After sunrise the gas is dispersed by convection.[58] High concentrations of produced by disturbance of deep lake water saturated with are thought to have caused 37 fatalities at Lake Monoun, Cameroon in 1984 and 1700 casualties at Lake Nyos, Cameroon in 1986.[59]

Human physiology

Content

Reference ranges or averages for partial pressures of carbon dioxide (abbreviated p)
Blood compartment(kPa) (mm Hg)
Venous blood carbon dioxideNaNorder=flipNaNorder=flip[60]
Alveolar pulmonary
gas pressures
36order=flipNaNorder=flip
Arterial blood carbon dioxideNaNorder=flipNaNorder=flip

The body produces approximately 2.3lb of carbon dioxide per day per person,[61] containing 0.63lb of carbon. In humans, this carbon dioxide is carried through the venous system and is breathed out through the lungs, resulting in lower concentrations in the arteries. The carbon dioxide content of the blood is often given as the partial pressure, which is the pressure which carbon dioxide would have had if it alone occupied the volume.[62] In humans, the blood carbon dioxide contents are shown in the adjacent table.

Transport in the blood

is carried in blood in three different ways. Exact percentages vary between arterial and venous blood.

Hemoglobin, the main oxygen-carrying molecule in red blood cells, carries both oxygen and carbon dioxide. However, the bound to hemoglobin does not bind to the same site as oxygen. Instead, it combines with the N-terminal groups on the four globin chains. However, because of allosteric effects on the hemoglobin molecule, the binding of decreases the amount of oxygen that is bound for a given partial pressure of oxygen. This is known as the Haldane Effect, and is important in the transport of carbon dioxide from the tissues to the lungs. Conversely, a rise in the partial pressure of or a lower pH will cause offloading of oxygen from hemoglobin, which is known as the Bohr effect.

Regulation of respiration

Carbon dioxide is one of the mediators of local autoregulation of blood supply. If its concentration is high, the capillaries expand to allow a greater blood flow to that tissue.[64]

Bicarbonate ions are crucial for regulating blood pH. A person's breathing rate influences the level of in their blood. Breathing that is too slow or shallow causes respiratory acidosis, while breathing that is too rapid leads to hyperventilation, which can cause respiratory alkalosis.[65]

Although the body requires oxygen for metabolism, low oxygen levels normally do not stimulate breathing. Rather, breathing is stimulated by higher carbon dioxide levels. As a result, breathing low-pressure air or a gas mixture with no oxygen at all (such as pure nitrogen) can lead to loss of consciousness without ever experiencing air hunger. This is especially perilous for high-altitude fighter pilots. It is also why flight attendants instruct passengers, in case of loss of cabin pressure, to apply the oxygen mask to themselves first before helping others; otherwise, one risks losing consciousness.

The respiratory centers try to maintain an arterial pressure of 40 mmHg. With intentional hyperventilation, the content of arterial blood may be lowered to 10–20 mmHg (the oxygen content of the blood is little affected), and the respiratory drive is diminished. This is why one can hold one's breath longer after hyperventilating than without hyperventilating. This carries the risk that unconsciousness may result before the need to breathe becomes overwhelming, which is why hyperventilation is particularly dangerous before free diving.[66]

Concentrations and role in the environment

Oceans

See main article: Carbon cycle and Ocean acidification.

Ocean acidification

Carbon dioxide dissolves in the ocean to form carbonic acid, bicarbonate, and carbonate . There is about fifty times as much carbon dioxide dissolved in the oceans as exists in the atmosphere. The oceans act as an enormous carbon sink, and have taken up about a third of emitted by human activity.[67]

Hydrothermal vents

Carbon dioxide is also introduced into the oceans through hydrothermal vents. The Champagne hydrothermal vent, found at the Northwest Eifuku volcano in the Mariana Trench, produces almost pure liquid carbon dioxide, one of only two known sites in the world as of 2004, the other being in the Okinawa Trough.[68] The finding of a submarine lake of liquid carbon dioxide in the Okinawa Trough was reported in 2006.[69]

Production

Biological processes

Carbon dioxide is a by-product of the fermentation of sugar in the brewing of beer, whisky and other alcoholic beverages and in the production of bioethanol. Yeast metabolizes sugar to produce and ethanol, also known as alcohol, as follows:

All aerobic organisms produce when they oxidize carbohydrates, fatty acids, and proteins. The large number of reactions involved are exceedingly complex and not described easily. Refer to cellular respiration, anaerobic respiration and photosynthesis. The equation for the respiration of glucose and other monosaccharides is:

Anaerobic organisms decompose organic material producing methane and carbon dioxide together with traces of other compounds.[70] Regardless of the type of organic material, the production of gases follows well defined kinetic pattern. Carbon dioxide comprises about 40–45% of the gas that emanates from decomposition in landfills (termed "landfill gas"). Most of the remaining 50–55% is methane.[71]

Industrial processes

Carbon dioxide can be obtained by distillation from air, but the method is inefficient. Industrially, carbon dioxide is predominantly an unrecovered waste product, produced by several methods which may be practiced at various scales.[72]

Combustion

The combustion of all carbon-based fuels, such as methane (natural gas), petroleum distillates (gasoline, diesel, kerosene, propane), coal, wood and generic organic matter produces carbon dioxide and, except in the case of pure carbon, water. As an example, the chemical reaction between methane and oxygen:

Iron is reduced from its oxides with coke in a blast furnace, producing pig iron and carbon dioxide:[73]

By-product from hydrogen production

Carbon dioxide is a byproduct of the industrial production of hydrogen by steam reforming and the water gas shift reaction in ammonia production. These processes begin with the reaction of water and natural gas (mainly methane).[74] This is a major source of food-grade carbon dioxide for use in carbonation of beer and soft drinks, and is also used for stunning animals such as poultry. In the summer of 2018 a shortage of carbon dioxide for these purposes arose in Europe due to the temporary shut-down of several ammonia plants for maintenance.[75]

Thermal decomposition of limestone

It is produced by thermal decomposition of limestone, by heating (calcining) at about, in the manufacture of quicklime (calcium oxide, CaO), a compound that has many industrial uses:

Acids liberate from most metal carbonates. Consequently, it may be obtained directly from natural carbon dioxide springs, where it is produced by the action of acidified water on limestone or dolomite. The reaction between hydrochloric acid and calcium carbonate (limestone or chalk) is shown below:

The carbonic acid then decomposes to water and :

Such reactions are accompanied by foaming or bubbling, or both, as the gas is released. They have widespread uses in industry because they can be used to neutralize waste acid streams.

Commercial uses

Carbon dioxide is used by the food industry, the oil industry, and the chemical industry.The compound has varied commercial uses but one of its greatest uses as a chemical is in the production of carbonated beverages; it provides the sparkle in carbonated beverages such as soda water, beer and sparkling wine.

Precursor to chemicals

See also: Sabatier reaction. In the chemical industry, carbon dioxide is mainly consumed as an ingredient in the production of urea, with a smaller fraction being used to produce methanol and a range of other products.[76] Some carboxylic acid derivatives such as sodium salicylate are prepared using by the Kolbe–Schmitt reaction.[77]

In addition to conventional processes using for chemical production, electrochemical methods are also being explored at a research level. In particular, the use of renewable energy for production of fuels from (such as methanol) is attractive as this could result in fuels that could be easily transported and used within conventional combustion technologies but have no net emissions.[78]

Agriculture

Plants require carbon dioxide to conduct photosynthesis. The atmospheres of greenhouses may (if of large size, must) be enriched with additional to sustain and increase the rate of plant growth.[79] [80] At very high concentrations (100 times atmospheric concentration, or greater), carbon dioxide can be toxic to animal life, so raising the concentration to 10,000 ppm (1%) or higher for several hours will eliminate pests such as whiteflies and spider mites in a greenhouse.[81] Some plants respond more favorably to rising carbon dioxide concentrations than others, which can lead to vegetation regime shifts like woody plant encroachment.

Foods

Carbon dioxide is a food additive used as a propellant and acidity regulator in the food industry. It is approved for usage in the EU[82] (listed as E number E290), US,[83] Australia and New Zealand[84] (listed by its INS number 290).

A candy called Pop Rocks is pressurized with carbon dioxide gas[85] at about 4000abbr=onNaNabbr=on. When placed in the mouth, it dissolves (just like other hard candy) and releases the gas bubbles with an audible pop.

Leavening agents cause dough to rise by producing carbon dioxide.[86] Baker's yeast produces carbon dioxide by fermentation of sugars within the dough, while chemical leaveners such as baking powder and baking soda release carbon dioxide when heated or if exposed to acids.

Beverages

Carbon dioxide is used to produce carbonated soft drinks and soda water. Traditionally, the carbonation of beer and sparkling wine came about through natural fermentation, but many manufacturers carbonate these drinks with carbon dioxide recovered from the fermentation process. In the case of bottled and kegged beer, the most common method used is carbonation with recycled carbon dioxide. With the exception of British real ale, draught beer is usually transferred from kegs in a cold room or cellar to dispensing taps on the bar using pressurized carbon dioxide, sometimes mixed with nitrogen.

The taste of soda water (and related taste sensations in other carbonated beverages) is an effect of the dissolved carbon dioxide rather than the bursting bubbles of the gas. Carbonic anhydrase 4 converts carbon dioxide to carbonic acid leading to a sour taste, and also the dissolved carbon dioxide induces a somatosensory response.[87]

Winemaking

Carbon dioxide in the form of dry ice is often used during the cold soak phase in winemaking to cool clusters of grapes quickly after picking to help prevent spontaneous fermentation by wild yeast. The main advantage of using dry ice over water ice is that it cools the grapes without adding any additional water that might decrease the sugar concentration in the grape must, and thus the alcohol concentration in the finished wine. Carbon dioxide is also used to create a hypoxic environment for carbonic maceration, the process used to produce Beaujolais wine.

Carbon dioxide is sometimes used to top up wine bottles or other storage vessels such as barrels to prevent oxidation, though it has the problem that it can dissolve into the wine, making a previously still wine slightly fizzy. For this reason, other gases such as nitrogen or argon are preferred for this process by professional wine makers.

Stunning animals

Carbon dioxide is often used to "stun" animals before slaughter.[88] "Stunning" may be a misnomer, as the animals are not knocked out immediately and may suffer distress.[89] [90]

Inert gas

Carbon dioxide is one of the most commonly used compressed gases for pneumatic (pressurized gas) systems in portable pressure tools. Carbon dioxide is also used as an atmosphere for welding, although in the welding arc, it reacts to oxidize most metals. Use in the automotive industry is common despite significant evidence that welds made in carbon dioxide are more brittle than those made in more inert atmospheres.[91] When used for MIG welding, use is sometimes referred to as MAG welding, for Metal Active Gas, as can react at these high temperatures. It tends to produce a hotter puddle than truly inert atmospheres, improving the flow characteristics. Although, this may be due to atmospheric reactions occurring at the puddle site. This is usually the opposite of the desired effect when welding, as it tends to embrittle the site, but may not be a problem for general mild steel welding, where ultimate ductility is not a major concern.

Carbon dioxide is used in many consumer products that require pressurized gas because it is inexpensive and nonflammable, and because it undergoes a phase transition from gas to liquid at room temperature at an attainable pressure of approximately 60abbr=onNaNabbr=on, allowing far more carbon dioxide to fit in a given container than otherwise would. Life jackets often contain canisters of pressured carbon dioxide for quick inflation. Aluminium capsules of are also sold as supplies of compressed gas for air guns, paintball markers/guns, inflating bicycle tires, and for making carbonated water. High concentrations of carbon dioxide can also be used to kill pests. Liquid carbon dioxide is used in supercritical drying of some food products and technological materials, in the preparation of specimens for scanning electron microscopy[92] and in the decaffeination of coffee beans.

Fire extinguisher

Carbon dioxide can be used to extinguish flames by flooding the environment around the flame with the gas. It does not itself react to extinguish the flame, but starves the flame of oxygen by displacing it. Some fire extinguishers, especially those designed for electrical fires, contain liquid carbon dioxide under pressure. Carbon dioxide extinguishers work well on small flammable liquid and electrical fires, but not on ordinary combustible fires, because they do not cool the burning substances significantly, and when the carbon dioxide disperses, they can catch fire upon exposure to atmospheric oxygen. They are mainly used in server rooms.[93]

Carbon dioxide has also been widely used as an extinguishing agent in fixed fire-protection systems for local application of specific hazards and total flooding of a protected space.[94] International Maritime Organization standards recognize carbon dioxide systems for fire protection of ship holds and engine rooms. Carbon dioxide-based fire-protection systems have been linked to several deaths, because it can cause suffocation in sufficiently high concentrations. A review of systems identified 51 incidents between 1975 and the date of the report (2000), causing 72 deaths and 145 injuries.[95]

Supercritical as solvent

See also: Supercritical carbon dioxide and Green chemistry.

Liquid carbon dioxide is a good solvent for many lipophilic organic compounds and is used to decaffeinate coffee. Carbon dioxide has attracted attention in the pharmaceutical and other chemical processing industries as a less toxic alternative to more traditional solvents such as organochlorides. It is also used by some dry cleaners for this reason. It is used in the preparation of some aerogels because of the properties of supercritical carbon dioxide.

Medical and pharmacological uses

In medicine, up to 5% carbon dioxide (130 times atmospheric concentration) is added to oxygen for stimulation of breathing after apnea and to stabilize the / balance in blood.

Carbon dioxide can be mixed with up to 50% oxygen, forming an inhalable gas; this is known as Carbogen and has a variety of medical and research uses.

Another medical use are the mofette, dry spas that use carbon dioxide from post-volcanic discharge for therapeutic purposes.

Energy

Supercritical is used as the working fluid in the Allam power cycle engine.

Fossil fuel recovery

Carbon dioxide is used in enhanced oil recovery where it is injected into or adjacent to producing oil wells, usually under supercritical conditions, when it becomes miscible with the oil. This approach can increase original oil recovery by reducing residual oil saturation by 7–23% additional to primary extraction.[96] It acts as both a pressurizing agent and, when dissolved into the underground crude oil, significantly reduces its viscosity, and changing surface chemistry enabling the oil to flow more rapidly through the reservoir to the removal well.[97] In mature oil fields, extensive pipe networks are used to carry the carbon dioxide to the injection points.

In enhanced coal bed methane recovery, carbon dioxide would be pumped into the coal seam to displace methane, as opposed to current methods which primarily rely on the removal of water (to reduce pressure) to make the coal seam release its trapped methane.[98]

Bio transformation into fuel

See main article: Carbon capture and utilization.

It has been proposed that from power generation be bubbled into ponds to stimulate growth of algae that could then be converted into biodiesel fuel.[99] A strain of the cyanobacterium Synechococcus elongatus has been genetically engineered to produce the fuels isobutyraldehyde and isobutanol from using photosynthesis.[100]

Researchers have developed an electrocatalytic technique using enzymes isolated from bacteria to power the chemical reactions which convert into fuels.[101] [102] [103]

Refrigerant

See also: Refrigerant and Sustainable automotive air conditioning.

Liquid and solid carbon dioxide are important refrigerants, especially in the food industry, where they are employed during the transportation and storage of ice cream and other frozen foods. Solid carbon dioxide is called "dry ice" and is used for small shipments where refrigeration equipment is not practical. Solid carbon dioxide is always below -78.5C at regular atmospheric pressure, regardless of the air temperature.

Liquid carbon dioxide (industry nomenclature R744 or R-744) was used as a refrigerant prior to the use of dichlorodifluoromethane (R12, a chlorofluorocarbon (CFC) compound).[104] might enjoy a renaissance because one of the main substitutes to CFCs, 1,1,1,2-tetrafluoroethane (R134a, a hydrofluorocarbon (HFC) compound) contributes to climate change more than does. physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a high volumetric cooling capacity. Due to the need to operate at pressures of up to 130bar, systems require highly mechanically resistant reservoirs and components that have already been developed for mass production in many sectors. In automobile air conditioning, in more than 90% of all driving conditions for latitudes higher than 50°, (R744) operates more efficiently than systems using HFCs (e.g., R134a). Its environmental advantages (GWP of 1, non-ozone depleting, non-toxic, non-flammable) could make it the future working fluid to replace current HFCs in cars, supermarkets, and heat pump water heaters, among others. Coca-Cola has fielded -based beverage coolers and the U.S. Army is interested in refrigeration and heating technology.[105] [106]

Minor uses

Carbon dioxide is the lasing medium in a carbon-dioxide laser, which is one of the earliest type of lasers.

Carbon dioxide can be used as a means of controlling the pH of swimming pools,[107] by continuously adding gas to the water, thus keeping the pH from rising. Among the advantages of this is the avoidance of handling (more hazardous) acids. Similarly, it is also used in the maintaining reef aquaria, where it is commonly used in calcium reactors to temporarily lower the pH of water being passed over calcium carbonate in order to allow the calcium carbonate to dissolve into the water more freely, where it is used by some corals to build their skeleton.

Used as the primary coolant in the British advanced gas-cooled reactor for nuclear power generation.

Carbon dioxide induction is commonly used for the euthanasia of laboratory research animals. Methods to administer include placing animals directly into a closed, prefilled chamber containing, or exposure to a gradually increasing concentration of . The American Veterinary Medical Association's 2020 guidelines for carbon dioxide induction state that a displacement rate of 30–70% of the chamber or cage volume per minute is optimal for the humane euthanasia of small rodents.[108] Percentages of vary for different species, based on identified optimal percentages to minimize distress.

Carbon dioxide is also used in several related cleaning and surface-preparation techniques.

History of discovery

Carbon dioxide was the first gas to be described as a discrete substance. In about 1640,[109] the Flemish chemist Jan Baptist van Helmont observed that when he burned charcoal in a closed vessel, the mass of the resulting ash was much less than that of the original charcoal. His interpretation was that the rest of the charcoal had been transmuted into an invisible substance he termed a "gas" (from Greek "chaos") or "wild spirit" (spiritus sylvestris).[110]

The properties of carbon dioxide were further studied in the 1750s by the Scottish physician Joseph Black. He found that limestone (calcium carbonate) could be heated or treated with acids to yield a gas he called "fixed air". He observed that the fixed air was denser than air and supported neither flame nor animal life. Black also found that when bubbled through limewater (a saturated aqueous solution of calcium hydroxide), it would precipitate calcium carbonate. He used this phenomenon to illustrate that carbon dioxide is produced by animal respiration and microbial fermentation. In 1772, English chemist Joseph Priestley published a paper entitled Impregnating Water with Fixed Air in which he described a process of dripping sulfuric acid (or oil of vitriol as Priestley knew it) on chalk in order to produce carbon dioxide, and forcing the gas to dissolve by agitating a bowl of water in contact with the gas.[111]

Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael Faraday.[112] The earliest description of solid carbon dioxide (dry ice) was given by the French inventor Adrien-Jean-Pierre Thilorier, who in 1835 opened a pressurized container of liquid carbon dioxide, only to find that the cooling produced by the rapid evaporation of the liquid yielded a "snow" of solid .[113] [114]

Carbon dioxide in combination with nitrogen was known from earlier times as Blackdamp, stythe or choke damp. Along with the other types of damp it was encountered in mining operations and well sinking. Slow oxidation of coal and biological processes replaced the oxygen to create a suffocating mixture of nitrogen and carbon dioxide.[115]

See also

External links

Notes and References

  1. Book: Ocean Acidification: A National Strategy to Meet the Challenges of a Changing Ocean . 22 April 2010 . National Academies Press . 978-0-309-15359-1 . Washington, DC . 23–24 . 10.17226/12904 . 29 February 2016 . https://web.archive.org/web/20160205175823/http://www.nap.edu/catalog/12904/ocean-acidification-a-national-strategy-to-meet-the-challenges-of . 5 February 2016 . live.
  2. Book: Eggleton T . A Short Introduction to Climate Change. 2013. Cambridge University Press. 52. 9781107618763. 9 November 2020.
  3. Web site: Carbon dioxide now more than 50% higher than pre-industrial levels National Oceanic and Atmospheric Administration . 2022-06-14 . www.noaa.gov. 3 June 2022.
  4. IPCC (2022) Summary for policy makers in Climate Change 2022: Mitigation of Climate Change. Contribution of Working Group III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, United Kingdom and New York, NY, US
  5. Book: Kaufman DG, Franz CM . Biosphere 2000: protecting our global environment . 1996 . Kendall/Hunt Pub. Co. . 978-0-7872-0460-0 .
  6. Web site: Food Factories . www.legacyproject.org . 10 October 2011 . 12 August 2017 . https://web.archive.org/web/20170812043852/http://www.legacyproject.org/activities/foodfactories.html . live.
  7. Book: Summary for Policymakers . https://www.ipcc.ch/report/ar6/wg1/downloads/report/IPCC_AR6_WGI_SPM_final.pdf . https://ghostarchive.org/archive/20221010/https://www.ipcc.ch/report/ar6/wg1/downloads/report/IPCC_AR6_WGI_SPM_final.pdf . 2022-10-10 . live . IPCC . IPCC . 2021 . Climate Change 2021: The Physical Science Basis . 20.
  8. Web site: Myles . Allen . September 2020 . The Oxford Principles for Net Zero Aligned Carbon Offsetting . live . https://web.archive.org/web/20201002083510/https://www.smithschool.ox.ac.uk/publications/reports/Oxford-Offsetting-Principles-2020.pdf . October 2, 2020 . 10 December 2021.
  9. Book: Tsotsas E, Mujumdar AS . Modern drying technology . Vol. 3: Product quality and formulation . 2011 . John Wiley & Sons . 978-3-527-31558-1 . 3 December 2019 . https://web.archive.org/web/20200321173739/https://books.google.com/books?id=5210HQIwxzsC&pg=PA185 . 21 March 2020 . live.
  10. Book: Atkins P, de Paula J . Physical Chemistry . 8th . W.H. Freeman . 2006 . 461, 464 . 978-0-7167-8759-4.
  11. Siegmann B, Werner U, Lutz HO, Mann R . Complete Coulomb fragmentation of in collisions with 5.9 MeV u−1 Xe18+ and Xe43+ . J Phys B Atom Mol Opt Phys . 35 . 17 . 3755 . 2002 . 10.1088/0953-4075/35/17/311 . 2002JPhB...35.3755S . 250782825.
  12. Jensen P, Spanner M, Bunker PR . The molecule is never linear− . J Mol Struct . 1212 . 128087 . 2020 . 10.1016/j.molstruc.2020.128087 . 2020JMoSt121228087J . 2142/107329 . free .
  13. Book: Jolly WL . Modern Inorganic Chemistry . McGraw-Hill . 1984 . 196 . 978-0-07-032760-3.
  14. Li Z, Mayer RJ, Ofial AR, Mayr H . From Carbodiimides to Carbon Dioxide: Quantification of the Electrophilic Reactivities of Heteroallenes . Journal of the American Chemical Society . 142 . 18 . 8383–8402 . May 2020 . 32338511 . 10.1021/jacs.0c01960 . 216557447.
  15. Book: Aresta M . 2010 . Carbon Dioxide as a Chemical Feedstock . Wiley-VCH . Weinheim . 978-3-527-32475-0.
  16. Finn C, Schnittger S, Yellowlees LJ, Love JB . Molecular approaches to the electrochemical reduction of carbon dioxide . Chemical Communications . 48 . 10 . 1392–1399 . February 2012 . 22116300 . 10.1039/c1cc15393e . 6 December 2019 . live . free . 19 April 2021 . https://web.archive.org/web/20210419185431/https://www.pure.ed.ac.uk/ws/files/10852481/Molecular_approaches_to_the_electrochemical_reduction_of_carbon_dioxide.pdf . 20.500.11820/b530915d-451c-493c-8251-da2ea2f50912 . 14356014.
  17. Web site: Carbon Dioxide . Air Products . 28 April 2017 . 29 July 2020 . https://web.archive.org/web/20200729131131/http://www.airproducts.com/~/media/Files/PDF/company/product-summary-carbon-dioxide.pdf?la=en . dead.
  18. Web site: Gases – Densities . Engineering Toolbox . 21 November 2020 . 2 March 2006 . https://web.archive.org/web/20060302054722/https://www.engineeringtoolbox.com/gas-density-d_158.html . live.
  19. Santoro M, Gorelli FA, Bini R, Ruocco G, Scandolo S, Crichton WA . Amorphous silica-like carbon dioxide . Nature . 441 . 7095 . 857–860 . June 2006 . 16778885 . 10.1038/nature04879 . 4363092 . 2006Natur.441..857S.
  20. Book: Holman, Jack P. . Heat Transfer . McGraw-Hill Companies, Inc. . 2002 . 9780072406559 . 9th . New York, NY . 600–606 . English.
  21. Book: Incropera . Dewitt . Bergman . Lavigne . Frank P. . David P. . Theodore L. . Adrienne S. . Fundamentals of Heat and Mass Transfer . John Wiley and Sons, Inc. . 2007 . 9780471457282 . 6th . Hoboken, NJ . 941–950 . English.
  22. Dhingra A, Portis AR, Daniell H . April 2004 . Enhanced translation of a chloroplast-expressed RbcS gene restores small subunit levels and photosynthesis in nuclear RbcS antisense plants . Proceedings of the National Academy of Sciences of the United States of America . 101 . 16 . 6315–6320 . 2004PNAS..101.6315D . 10.1073/pnas.0400981101 . 395966 . 15067115 . (Rubisco) is the most prevalent enzyme on this planet, accounting for 30–50% of total soluble protein in the chloroplast . free.
  23. Book: Evolution of primary producers in the sea . Falkowski P, Knoll AH . 1 January 2007 . Elsevier, Academic Press . 978-0-12-370518-1 . 845654016.
  24. Web site: December 2002 . Carbon Dioxide In Greenhouses . live . https://web.archive.org/web/20190429202513/http://www.omafra.gov.on.ca/english/crops/facts/00-077.htm . 29 April 2019 . 12 June 2007 . Blom TJ, Straver WA, Ingratta FJ, Khosla S, Brown W.
  25. Ainsworth EA . 2008 . Rice production in a changing climate: a meta-analysis of responses to elevated carbon dioxide and elevated ozone concentration . Global Change Biology . 14 . 7 . 1642–1650 . 2008GCBio..14.1642A . 10.1111/j.1365-2486.2008.01594.x . https://web.archive.org/web/20110719130608/http://www.plant-biotech.dk/Meetings/PBD_Symposium_Plant%20Stress_litterature/LisaAinsworth_pdf2.pdf . 19 July 2011 . 19200429.
  26. Long SP, Ainsworth EA, Leakey AD, Nösberger J, Ort DR . June 2006 . Food for thought: lower-than-expected crop yield stimulation with rising concentrations . live . Science . 312 . 5782 . 1918–1921 . 2006Sci...312.1918L . 10.1.1.542.5784 . 10.1126/science.1114722 . 16809532 . https://web.archive.org/web/20161020165354/http://www.as.wvu.edu/biology/bio463/Long%20et%20al%202006%20Lower%20yield%20than%20expected%20under%20increased%20CO2.pdf . 20 October 2016 . 27 October 2017 . 2232629.
  27. Woodward F, Kelly C . 1995 . The influence of concentration on stomatal density . New Phytologist . 131 . 3 . 311–327 . 10.1111/j.1469-8137.1995.tb03067.x . free.
  28. Drake BG, Gonzalez-Meler MA, Long SP . June 1997 . More Efficient Plants: A Consequence of Rising Atmospheric ? . Annual Review of Plant Physiology and Plant Molecular Biology . 48 . 1 . 609–639 . 10.1146/annurev.arplant.48.1.609 . 15012276 . 33415877.
  29. Loladze I . 2002 . Rising atmospheric and human nutrition: toward globally imbalanced plant stoichiometry? . Trends in Ecology & Evolution . 17 . 10 . 457–461 . 10.1016/S0169-5347(02)02587-9 . 16074723.
  30. Coviella CE, Trumble JT . 1999 . Effects of Elevated Atmospheric Carbon Dioxide on Insect-Plant Interactions . Conservation Biology . 13 . 4 . 700–712 . 10.1046/j.1523-1739.1999.98267.x . 2641685 . 1999ConBi..13..700C . 52262618.
  31. Davey MP, Harmens H, Ashenden TW, Edwards R, Baxter R . 2007 . Species-specific effects of elevated on resource allocation in Plantago maritima and Armeria maritima . Biochemical Systematics and Ecology . 35 . 3 . 121–129 . 10.1016/j.bse.2006.09.004.
  32. Davey MP, Bryant DN, Cummins I, Ashenden TW, Gates P, Baxter R, Edwards R . August 2004 . Effects of elevated on the vasculature and phenolic secondary metabolism of Plantago maritima . Phytochemistry . 65 . 15 . 2197–2204 . 10.1016/j.phytochem.2004.06.016 . 15587703. 2004PChem..65.2197D.
  33. Web site: Global Environment Division Greenhouse Gas Assessment Handbook – A Practical Guidance Document for the Assessment of Project-level Greenhouse Gas Emissions . dead . https://web.archive.org/web/20160603011630/http://www-wds.worldbank.org/external/default/WDSContentServer/WDSP/IB/2002/09/07/000094946_02081604154234/Rendered/INDEX/multi0page.txt . 3 June 2016 . 10 November 2007 . World Bank.
  34. 6 . Luyssaert S, Schulze ED, Börner A, Knohl A, Hessenmöller D, Law BE, Ciais P, Grace J . September 2008 . Old-growth forests as global carbon sinks . Nature . 455 . 7210 . 213–215 . 2008Natur.455..213L . 10.1038/nature07276 . 18784722 . 4424430.
  35. 6 . Falkowski P, Scholes RJ, Boyle E, Canadell J, Canfield D, Elser J, Gruber N, Hibbard K, Högberg P, Linder S, Mackenzie FT, Moore B, Pedersen T, Rosenthal Y, Seitzinger S, Smetacek V, Steffen W . October 2000 . The global carbon cycle: a test of our knowledge of earth as a system . Science . 290 . 5490 . 291–296 . 2000Sci...290..291F . 10.1126/science.290.5490.291 . 11030643 . 1779934.
  36. Web site: CarbonTracker CT2011_oi (Graphical map of) . live . https://web.archive.org/web/20210213080315/https://www.esrl.noaa.gov/gmd/ccgg/carbontracker/ . 13 February 2021 . 20 April 2007 . esrl.noaa.gov.
  37. News: Carbon Dioxide as a Fire Suppressant: Examining the Risks . U.S. Environmental Protection Agency . https://web.archive.org/web/20151002093443/http://www.epa.gov/ozone/snap/fire/co2/co2report.html . 2 October 2015.
  38. Web site: 1 November 2005 . Volcano Under the City . https://web.archive.org/web/20110405155241/http://www.pbs.org/wgbh/nova/transcripts/3215_volcanoc.html . 5 April 2011 . A NOVA Production by Bonne Pioche and Greenspace for WGBH/Boston . Public Broadcasting System. .
  39. Carbon Dioxide Tolerance Studies . SAM-TR-67-77 . 2 May 2008 . https://web.archive.org/web/20080509072828/http://archive.rubicon-foundation.org/6045 . 9 May 2008 . usurped . Glatte Jr HA, Motsay GJ, Welch BE . 1967 . Brooks AFB, TX School of Aerospace Medicine Technical Report.
  40. Carbon Dioxide Tolerance and Toxicity . Environmental Biomedical Stress Data Center, Institute for Environmental Medicine, University of Pennsylvania Medical Center . No. 2-71 . 2 May 2008 . https://web.archive.org/web/20110724044527/http://archive.rubicon-foundation.org/3861 . 24 July 2011 . usurped . Lambertsen CJ . 1971 . IFEM Report.
  41. Satish U, Mendell MJ, Shekhar K, Hotchi T, Sullivan D, Streufert S, Fisk WJ . December 2012 . Is an indoor pollutant? Direct effects of low-to-moderate concentrations on human decision-making performance . dead . Environmental Health Perspectives . 120 . 12 . 1671–1677 . 10.1289/ehp.1104789 . 3548274 . 23008272 . https://web.archive.org/web/20160305212909/http://ehp.niehs.nih.gov/wp-content/uploads/2012/09/ehp.1104789.pdf . 5 March 2016 . 11 December 2014.
  42. Joseph G. Allen . Allen JG, MacNaughton P, Satish U, Santanam S, Vallarino J, Spengler JD . June 2016 . Associations of Cognitive Function Scores with Carbon Dioxide, Ventilation, and Volatile Organic Compound Exposures in Office Workers: A Controlled Exposure Study of Green and Conventional Office Environments . Environmental Health Perspectives . 124 . 6 . 805–812 . 10.1289/ehp.1510037 . 4892924 . 26502459.
  43. Web site: Exposure Limits for Carbon Dioxide Gas – Limits . live . https://web.archive.org/web/20180916235612/https://inspectapedia.com/hazmat/CO2_Exposure_Limits.htm . 16 September 2018 . 19 October 2014 . InspectAPedia.com.
  44. In-Flight Carbon Dioxide Exposures and Related Symptoms: Associations, Susceptibility and Operational Implications . TP–2010–216126 . 26 August 2014 . https://web.archive.org/web/20110627061502/http://ston.jsc.nasa.gov/collections/TRS/_techrep/TP-2010-216126.pdf . 27 June 2011 . dead . Law J, Watkins S, Alexander D . 2010 . NASA Technical Report.
  45. Schaefer KE, Douglas WH, Messier AA, Shea ML, Gohman PA . 1979 . Effect of prolonged exposure to 0.5% on kidney calcification and ultrastructure of lungs . dead . Undersea Biomedical Research . 6 . Suppl . S155–S161 . 505623 . https://web.archive.org/web/20141019131035/http://handle.dtic.mil/100.2/ADA075625 . 19 October 2014 . 19 October 2014.
  46. Du B, Tandoc MC, Mack ML, Siegel JA . November 2020 . Indoor concentrations and cognitive function: A critical review . Indoor Air . 30 . 6 . 1067–1082 . 10.1111/ina.12706 . 32557862 . 2020InAir..30.1067D . 219915861. free.
  47. Web site: 4 June 2019 . Ask the doc: Does my helmet make me stupid? - RevZilla . live . https://web.archive.org/web/20210522081133/https://www.revzilla.com/common-tread/ask-the-doc-does-my-helmet-make-me-stupid . 22 May 2021 . 2021-05-22 . www.revzilla.com . Kaplan L.
  48. Brühwiler PA, Stämpfli R, Huber R, Camenzind M . September 2005 . and concentrations in integral motorcycle helmets . Applied Ergonomics . 36 . 5 . 625–633 . 10.1016/j.apergo.2005.01.018 . 15893291.
  49. Web site: 2018 . Ventilation for Acceptable Indoor Air Quality . live . 2023-08-10 . 1041-2336 . https://web.archive.org/web/20221026132957/https://www.ashrae.org/File%20Library/Technical%20Resources/Standards%20and%20Guidelines/Standards%20Addenda/62.1-2016/62_1_2016_d_20180302.pdf . Oct 26, 2022.
  50. Web site: Standard Guide for Using Indoor Carbon Dioxide Concentrations to Evaluate Indoor Air Quality and Ventilation . 2024-06-12 . www.astm.org . en.
  51. Allen JG, MacNaughton P, Satish U, Santanam S, Vallarino J, Spengler JD . June 2016 . Associations of Cognitive Function Scores with Carbon Dioxide, Ventilation, and Volatile Organic Compound Exposures in Office Workers: A Controlled Exposure Study of Green and Conventional Office Environments . Environmental Health Perspectives . 124 . 6 . 805–812 . 10.1289/ehp.1510037 . 4892924 . 26502459.
  52. Web site: 26 October 2015 . Exclusive: Elevated Levels Directly Affect Human Cognition, New Harvard Study Shows . live . https://web.archive.org/web/20191009092140/https://thinkprogress.org/exclusive-elevated-co2-levels-directly-affect-human-cognition-new-harvard-study-shows-2748e7378941/ . 9 October 2019 . 14 October 2019 . ThinkProgress . Romm J.
  53. Web site: 29 February 2020 . Three die in dry-ice incident at Moscow pool party . https://web.archive.org/web/20200229151448/https://www.bbc.co.uk/news/world-europe-51680049 . 29 February 2020 . BBC News . The victims were connected to Instagram influencer Yekaterina Didenko..
  54. Web site: 2 August 2018 . A Woman Died from Dry Ice Fumes. Here's How It Can Happen . live . https://web.archive.org/web/20210522082215/https://www.livescience.com/63241-dry-ice-death.html . 22 May 2021 . 2021-05-22 . Live Science . en . Rettner R.
  55. Concentrations de CO2 dans l'air intérieur et effets sur la santé . July 2013 . ANSES . 294 . fr.
  56. Chatzidiakou . Lia . Mumovic . Dejan . Summerfield . Alex . March 2015 . Is CO 2 a good proxy for indoor air quality in classrooms? Part 1: The interrelationships between thermal conditions, CO 2 levels, ventilation rates and selected indoor pollutants . Building Services Engineering Research and Technology . en . 36 . 2 . 129–161 . 10.1177/0143624414566244 . 111182451 . 0143-6244.
  57. Cetin . Mehmet . Sevik . Hakan . 2016 . INDOOR QUALITY ANALYSIS OF CO2 FOR KASTAMONU UNIVERSITY . Conference of the International Journal of Arts & Sciences . 9 . 3 . 71.
  58. Book: Plant responses to elevated : Evidence from natural springs . van Gardingen PR, Grace J, Jeffree CE, Byari SH, Miglietta F, Raschi A, Bettarini I . Cambridge University Press . 1997 . 978-0-521-58203-2 . Raschi A, Miglietta F, Tognetti R, van Gardingen PR . Cambridge . 69–86 . Long-term effects of enhanced concentrations on leaf gas exchange: research opportunities using springs.
  59. Book: Plant responses to elevated : Evidence from natural springs . Martini M . Cambridge University Press . 1997 . 978-0-521-58203-2 . Raschi A, Miglietta F, Tognetti R, van Gardingen PR . Cambridge . 69–86 . emissions in volcanic areas: case histories and hazards.
  60. Web site: ABG (Arterial Blood Gas) . Brookside Associates . 2 January 2017 . 12 August 2017 . https://web.archive.org/web/20170812201558/http://www.brooksidepress.org/Products/OperationalMedicine/DATA/operationalmed/Lab/ABG_ArterialBloodGas.htm . live.
  61. Web site: How much carbon dioxide do humans contribute through breathing? . https://web.archive.org/web/20110202140715/http://www.epa.gov/climatechange/fq/emissions.html . 2 February 2011 . 30 April 2009 . EPA.gov.
  62. Book: Chemistry . Henrickson C . Cliffs Notes . 2005 . 978-0-7645-7419-1.
  63. Web site: Carbon dioxide . dead . https://web.archive.org/web/20080914125551/http://www.solarnavigator.net/solar_cola/carbon_dioxide.htm . 14 September 2008 . 12 October 2007 . solarnavigator.net.
  64. Battisti-Charbonney . A. . Fisher . J. . Duffin . J. . 15 Jun 2011 . The cerebrovascular response to carbon dioxide in humans . J. Physiol. . 589 . 12 . 3039–3048 . 10.1113/jphysiol.2011.206052 . 3139085 . 21521758.
  65. Patel . S. . Miao . J.H. . Yetiskul . E. . Anokhin . A. . Majmunder . S.H. . 2022 . Physiology, Carbon Dioxide Retention . National Center for Biotechnology Information, NIH . 29494063 . 20 August 2022 . National Library of Medicine.
  66. Wilmshurst . Peter . 1998 . ABC of oxygen . BMJ . 317 . 7164 . 996–999 . 10.1136/bmj.317.7164.996 . 1114047 . 9765173.
  67. Web site: 29 November 2006 . How Long Can the Ocean Slow Global Warming? . live . https://web.archive.org/web/20080104004633/http://www.whoi.edu/oceanus/viewArticle.do?id=17726 . 4 January 2008 . 21 November 2007 . Oceanus . Doney SC, Levine NM.
  68. 6 . Lupton J, Lilley M, Butterfield D, Evans L, Embley R, Olson E, Proskurowski G, Resing J, Roe K, Greene R, Lebon G . 2004 . Liquid Carbon Dioxide Venting at the Champagne Hydrothermal Site, NW Eifuku Volcano, Mariana Arc . American Geophysical Union . 2004 . Fall Meeting . V43F–08 . 2004AGUFM.V43F..08L.
  69. 6 . Inagaki F, Kuypers MM, Tsunogai U, Ishibashi J, Nakamura K, Treude T, Ohkubo S, Nakaseama M, Gena K, Chiba H, Hirayama H, Nunoura T, Takai K, Jørgensen BB, Horikoshi K, Boetius A . September 2006 . Microbial community in a sediment-hosted lake of the southern Okinawa Trough hydrothermal system . Proceedings of the National Academy of Sciences of the United States of America . 103 . 38 . 14164–14169 . 2006PNAS..10314164I . 10.1073/pnas.0606083103 . 1599929 . 16959888 . free. Videos can be downloaded at Web site: Supporting Information . https://web.archive.org/web/20181019001732/http://www.pnas.org/content/103/38/14164.full?tab=ds . 19 October 2018.
  70. Web site: 11 January 2017 . Collecting and using biogas from landfills . live . https://web.archive.org/web/20180711073415/https://www.eia.gov/Energyexplained/?page=biomass_biogas . 11 July 2018 . 22 November 2015 . U.S. Energy Information Administration.
  71. Web site: January 2000 . Facts About Landfill Gas . live . https://web.archive.org/web/20150923213448/http://www.dem.ri.gov/programs/benviron/waste/central/lfgfact.pdf . 23 September 2015 . 4 September 2015 . U.S. Environmental Protection Agency.
  72. Encyclopedia: Pierantozzi R . Kirk-Othmer Encyclopedia of Chemical Technology. Wiley. 2001. 10.1002/0471238961.0301180216090518.a01.pub2. Carbon Dioxide. 978-0-471-23896-6.
  73. Book: Strassburger J . Blast Furnace Theory and Practice . American Institute of Mining, Metallurgical, and Petroleum Engineers . New York . 1969 . 978-0-677-10420-1.
  74. Book: 10.1002/14356007.a05_165. Carbon Dioxide. Ullmann's Encyclopedia of Industrial Chemistry. 2000. Topham S . 3527306730.
  75. News: shortage: Food industry calls for government action . BBC . 21 June 2018 . 24 June 2018 . 23 May 2021 . https://web.archive.org/web/20210523150103/https://www.bbc.com/news/business-44559669 . live.
  76. Web site: IPCC Special Report on Carbon dioxide Capture and Storage. The Intergovernmental Panel on Climate Change. 4 September 2015. https://web.archive.org/web/20150924115331/http://www.ipcc.ch/pdf/special-reports/srccs/srccs_chapter7.pdf. 24 September 2015. dead.
  77. Book: Morrison RT, Boyd RN . Organic Chemistry . 4th . Allyn and Bacon . 1983 . 978-0-205-05838-9 . 976–977 .
  78. Badwal SP, Giddey SS, Munnings C, Bhatt AI, Hollenkamp AF . Emerging electrochemical energy conversion and storage technologies . Frontiers in Chemistry . 2 . 79 . 24 September 2014 . 25309898 . 4174133 . 10.3389/fchem.2014.00079 . 2014FrCh....2...79B . free.
  79. Web site: Plant Growth Factors: Photosynthesis, Respiration, and Transpiration . CMG GardenNotes . Whiting D, Roll M, Vickerman L . Colorado Master Gardener Program . August 2010 . 10 October 2011 . https://web.archive.org/web/20140902192633/http://www.ext.colostate.edu/mg/gardennotes/141.html . 2 September 2014.
  80. Book: http://www-formal.stanford.edu/jmc/nature/node21.html . Carbon dioxide . How Much Land Can Ten Billion People Spare for Nature? . Waggoner PE . February 1994 . 10 October 2011 . 12 October 2011 . https://web.archive.org/web/20111012165809/http://www-formal.stanford.edu/jmc/nature/nature.html . live.
  81. Stafford N . Future crops: the other greenhouse effect . Nature . 448 . 7153 . 526–528 . August 2007 . 17671477 . 10.1038/448526a . 2007Natur.448..526S . 9845813 . free.
  82. UK Food Standards Agency: Web site: Current EU approved additives and their E Numbers . 27 October 2011 . 7 October 2010 . https://web.archive.org/web/20101007124435/http://www.food.gov.uk/safereating/chemsafe/additivesbranch/enumberlist . live.
  83. US Food and Drug Administration: Web site: Food Additive Status List . . 13 June 2015 . 4 November 2017 . https://web.archive.org/web/20171104061606/https://www.fda.gov/Food/IngredientsPackagingLabeling/FoodAdditivesIngredients/ucm091048.htm . live.
  84. Australia New Zealand Food Standards CodeWeb site: Standard 1.2.4 – Labelling of ingredients . 8 September 2011 . 27 October 2011 . 19 January 2012 . https://web.archive.org/web/20120119082034/http://www.comlaw.gov.au/Details/F2011C00827 . live.
  85. Book: Futurific Leading Indicators Magazine . 1 . CRAES LLC . 978-0-9847670-1-4 . 9 November 2020 . 15 August 2021 . https://web.archive.org/web/20210815224429/https://books.google.com/books?id=0XeSJLflq90C&q=Pop+Rocks+is+pressurized+with+carbon+dioxide+gas&pg=PA7-IA3 . live.
  86. Book: Indian Breads: A Comprehensive Guide to Traditional and Innovative Indian Breads . Vijay GP . 25 September 2015 . Westland . 978-93-85724-46-6.
  87. Web site: Scientists Discover Protein Receptor For Carbonation Taste . . 16 October 2009 . 29 March 2020 . 29 March 2020 . https://web.archive.org/web/20200329042900/https://www.sciencedaily.com/releases/2009/10/091015141510.htm . live.
  88. Coghlan A . A more humane way of slaughtering chickens might get EU approval . New Scientist . 3 February 2018 . 24 June 2018 . 24 June 2018 . https://web.archive.org/web/20180624204842/https://www.newscientist.com/article/2159895-a-more-humane-way-of-slaughtering-chickens-might-get-eu-approval/ . live.
  89. Web site: What is stunning? . https://web.archive.org/web/20140409003755/http://kb.rspca.org.au/What-is-CO2-stunning_118.html . dead . 9 April 2014 . RSPCA.
  90. Campbell A . Humane execution and the fear of the tumbril . New Scientist . 10 March 2018 . 24 June 2018 . 24 June 2018 . https://web.archive.org/web/20180624204708/https://www.newscientist.com/letter/mg23731680-900-humane-execution-and-the-fear-of-the-tumbril-3/ . live.
  91. Book: International, Petrogav . Production Course for Hiring on Offshore Oil and Gas Rigs . Petrogav International . 214 . en.
  92. Nordestgaard BG, Rostgaard J . Critical-point drying versus freeze drying for scanning electron microscopy: a quantitative and qualitative study on isolated hepatocytes . Journal of Microscopy . 137 . Pt 2 . 189–207 . February 1985 . 3989858 . 10.1111/j.1365-2818.1985.tb02577.x . 32065173.
  93. Web site: Types of Fire Extinguishers . live . 2021-06-28 . The Fire Safety Advice Centre . 28 June 2021 . https://web.archive.org/web/20210628185630/https://www.firesafe.org.uk/types-use-and-colours-of-portable-fire-extinguishers/.
  94. National Fire Protection Association Code 12.
  95. Carbon Dioxide as a Fire Suppressant: Examining the Risks, US EPA. 2000.
  96. Book: 20 December 2011 . Accelerating the uptake of CCS: industrial use of captured carbon dioxide . http://hub.globalccsinstitute.com/publications/accelerating-uptake-ccs-industrial-use-captured-carbon-dioxide/appendix-co2-use . Appendix A: for use in enhanced oil recovery (EOR) . Global CCS Institute . 2 January 2017 . 28 April 2017 . https://web.archive.org/web/20170428013833/http://www.globalccsinstitute.com/publications/accelerating-uptake-ccs-industrial-use-captured-carbon-dioxide . live.
  97. Austell JM . 2005 . for Enhanced Oil Recovery Needs – Enhanced Fiscal Incentives . Exploration & Production: The Oil & Gas Review . https://web.archive.org/web/20120207071349/http://www.touchoilandgas.com/enhanced-recovery-needs-enhanced-a423-1.html . 7 February 2012 . 28 September 2007.
  98. Web site: Enhanced coal bed methane recovery. 31 August 2006. ETH Zurich. dead. https://web.archive.org/web/20110706232006/http://www.ipe.ethz.ch/laboratories/spl/research/adsorption/project03. 6 July 2011.
  99. News: Clayton M . Algae – like a breath mint for smokestacks. 11 January 2006. The Christian Science Monitor. 11 October 2007. 14 September 2008. https://web.archive.org/web/20080914134926/http://www.csmonitor.com/2006/0111/p01s03-sten.html. live.
  100. Atsumi S, Higashide W, Liao JC . Direct photosynthetic recycling of carbon dioxide to isobutyraldehyde . Nature Biotechnology . 27 . 12 . 1177–1180 . December 2009 . 19915552 . 10.1038/nbt.1586 . 1492698.
  101. Cobb S, Badiani V, Dharani A, Wagner A, Zacarias S, Oliveira AR, Pereira I, Reisner E . 6 . 2022-02-28 . Fast hydration kinetics impair heterogeneous but improve enzymatic reduction catalysis . Nature Chemistry . 14 . 4 . en . 417–424 . 10.1038/s41557-021-00880-2 . 35228690 . 7612589 . 2022NatCh..14..417C . 247160910 . 1755-4349.
  102. Edwardes Moore E, Cobb SJ, Coito AM, Oliveira AR, Pereira IA, Reisner E . Understanding the local chemical environment of bioelectrocatalysis . Proceedings of the National Academy of Sciences of the United States of America . 119 . 4 . e2114097119 . January 2022 . 35058361 . 8795565 . 10.1073/pnas.2114097119 . free . 2022PNAS..11914097E.
  103. Web site: 2022-03-01 . Clean Way To Turn Into Fuel Inspired by Nature . 2022-03-02 . Applied Sciences from Technology Networks . en.
  104. Web site: Pearson . S. Forbes . Refrigerants Past, Present and Future . dead . https://web.archive.org/web/20180713171048/http://www.r744.com/files/pdf_597.pdf . 2018-07-13 . 2021-03-30 . R744.
  105. Web site: The Coca-Cola Company Announces Adoption of HFC-Free Insulation in Refrigeration Units to Combat Global Warming . 11 October 2007 . 5 June 2006 . The Coca-Cola Company . 1 November 2013 . https://web.archive.org/web/20131101195654/http://www.coca-colacompany.com/cooling-equipment-pushing-forward-with-hfc-free . live.
  106. News: Modine reinforces its research efforts. https://web.archive.org/web/20080210194203/http://www.r744.com/news/news_ida145.php. dead. 10 February 2008. 28 June 2007. R744.com.
  107. Book: TCE, the Chemical Engineer . 1990 . Institution of Chemical Engineers . 2 June 2020 . 17 August 2021 . https://web.archive.org/web/20210817030754/https://books.google.com/books?id=IWpWAAAAMAAJ&q=%C2%A0%C2%A0Carbon+dioxide+can+be+used+as+a+means+of+controlling+the+pH+of+swimming+pool . live.
  108. Web site: AVMA guidelines for the euthanasia of animals: 2020 Edition . 2020 . . August 13, 2021 . 1 February 2014 . https://web.archive.org/web/20140201174132/https://www.avma.org/KB/Policies/Documents/euthanasia.pdf . live.
  109. Harris D . September 1910 . The Pioneer in the Hygiene of Ventilation . live . The Lancet . 176 . 4542 . 906–908 . 10.1016/S0140-6736(00)52420-9 . https://web.archive.org/web/20200317181844/https://zenodo.org/record/2088803 . 17 March 2020 . 6 December 2019.
  110. Book: History of industrial gases . Almqvist E . 2003 . Springer . 978-0-306-47277-0 . 93.
  111. Joseph Priestley . Priestley J, Hey W . 1772 . Observations on Different Kinds of Air . live . Philosophical Transactions . 62 . 147–264 . 10.1098/rstl.1772.0021 . https://web.archive.org/web/20100607170541/http://web.lemoyne.edu/%7Egiunta/priestley.html . 7 June 2010 . 11 October 2007 . 186210131.
  112. Humphry Davy . Davy H . 1823 . On the Application of Liquids Formed by the Condensation of Gases as Mechanical Agents . Philosophical Transactions . 113 . 199–205 . 10.1098/rstl.1823.0020 . 107649 . free.
  113. Thilorier AJ . 1835 . Solidification de l'Acide carbonique . live . Comptes Rendus . 1 . 194–196 . https://web.archive.org/web/20170902172202/http://gallica.bnf.fr/ark:/12148/bpt6k29606/f194.item . 2 September 2017 . 1 September 2017.
  114. Thilorier AJ . 1836 . Solidification of carbonic acid . live . The London and Edinburgh Philosophical Magazine . 8 . 48 . 446–447 . 10.1080/14786443608648911 . https://web.archive.org/web/20160502065711/https://books.google.com/books?id=4GwqAAAAYAAJ&pg=PA446 . 2 May 2016 . 15 November 2015.
  115. Notes of an Enquiry into the Nature and Physiological Action of Black-Damp, as Met with in Podmore Colliery, Staffordshire, and Lilleshall Colliery, Shropshire . 115391 . Haldane . John . Proceedings of the Royal Society of London . 1894 . 57 . 249–257 . 1894RSPS...57..249H.