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A greenhouse gas (sometimes abbreviated GHG) is a gas that absorbs and emits radiant energy within the thermal infrared range, causing the greenhouse effect. The primary greenhouse gases in Earth's atmosphere are water vapor (), carbon dioxide (), methane (), nitrous oxide (), and ozone (). Without greenhouse gases, the average temperature of Earth's surface would be about , rather than the present average of . The atmospheres of Venus, Mars and Titan also contain greenhouse gases. Human activities since the beginning of the Industrial Revolution (around 1750) have produced a 45% increase in the atmospheric concentration of carbon dioxide, from 280 ppm in 1750 to 415 ppm in 2019. The last time the atmospheric concentration of carbon dioxide was this high was over 3 million years ago. This increase has occurred despite the uptake of more than half of the emissions by various natural "sinks" involved in the carbon cycle. At current greenhouse gas emission rates, temperatures could increase by 2 °C (3.6 °F), which the United Nations' Intergovernmental Panel on Climate Change (IPCC) designated as the upper limit to avoid "dangerous" levels, by 2036. The vast majority of anthropogenic carbon dioxide emissions come from combustion of fossil fuels, principally coal, petroleum (including oil) and natural gas, with additional contributions coming from deforestation and other changes in land use.

Gases in Earth's atmosphere

Non-greenhouse gases

The major constituents of Earth's atmosphere, nitrogen ()(78%), oxygen ()(21%), and argon (Ar)(0.9%), are not greenhouse gases because molecules containing two atoms of the same element such as and have no net change in the distribution of their electrical charges when they vibrate, and monatomic gases such as Ar do not have vibrational modes. Hence they are almost totally unaffected by infrared radiation. Some molecules containing just two atoms of different elements, such as carbon monoxide (CO) and hydrogen chloride (HCl), do absorb infrared radiation, but these molecules are short-lived in the atmosphere owing to their reactivity or solubility. Therefore, they do not contribute significantly to the greenhouse effect and often are omitted when discussing greenhouse gases.

Greenhouse gases

Greenhouse gases are those that absorb and emit infrared radiation in the wavelength range emitted by Earth. Carbon dioxide (0.04%), nitrous oxide, methane, and ozone are trace gases that account for almost 0.1% of Earth's atmosphere and have an appreciable greenhouse effect. In order, the most abundant greenhouse gases in Earth's atmosphere are: * Water vapor () * Carbon dioxide () * Methane () * Nitrous oxide () * Ozone () * Chlorofluorocarbons (CFCs) * Hydrofluorocarbons (includes HCFCs and HFCs) Atmospheric concentrations are determined by the balance between sources (emissions of the gas from human activities and natural systems) and sinks (the removal of the gas from the atmosphere by conversion to a different chemical compound or absorption by bodies of water). in The proportion of an emission remaining in the atmosphere after a specified time is the "airborne fraction" (AF). The ''annual airborne fraction'' is the ratio of the atmospheric increase in a given year to that year's total emissions. As of 2006 the annual airborne fraction for was about 0.45. The annual airborne fraction increased at a rate of 0.25 ± 0.21% per year over the period 1959–2006.

Contribution of clouds to Earth's greenhouse effect

The major non-gas contributor to Earth's greenhouse effect, clouds, also absorb and emit infrared radiation and thus have an effect on greenhouse gas radiative properties. Clouds are water droplets or ice crystals suspended in the atmosphere.

Impacts on the overall greenhouse effect

The contribution of each gas to the greenhouse effect is determined by the characteristics of that gas, its abundance, and any indirect effects it may cause. For example, the direct radiative effect of a mass of methane is about 84 times stronger than the same mass of carbon dioxide over a 20-year time frame but it is present in much smaller concentrations so that its total direct radiative effect has so far been smaller, in part due to its shorter atmospheric lifetime in the absence of additional carbon sequestration. On the other hand, in addition to its direct radiative impact, methane has a large, indirect radiative effect because it contributes to ozone formation. Shindell et al. (2005) argues that the contribution to climate change from methane is at least double previous estimates as a result of this effect. When ranked by their direct contribution to the greenhouse effect, the most important are: In addition to the main greenhouse gases listed above, other greenhouse gases include sulfur hexafluoride, hydrofluorocarbons and perfluorocarbons (see IPCC list of greenhouse gases). Some greenhouse gases are not often listed. For example, nitrogen trifluoride has a high global warming potential (GWP) but is only present in very small quantities.

Proportion of direct effects at a given moment

It is not possible to state that a certain gas causes an exact percentage of the greenhouse effect. This is because some of the gases absorb and emit radiation at the same frequencies as others, so that the total greenhouse effect is not simply the sum of the influence of each gas. The higher ends of the ranges quoted are for each gas alone; the lower ends account for overlaps with the other gases. In addition, some gases, such as methane, are known to have large indirect effects that are still being quantified.

Aside from water vapor, which has a residence time of about nine days, major greenhouse gases are well mixed and take many years to leave the atmosphere. Although it is not easy to know with precision how long it takes greenhouse gases to leave the atmosphere, there are estimates for the principal greenhouse gases. Jacob (1999) defines the lifetime $\tau$ of an atmospheric species X in a one-box model as the average time that a molecule of X remains in the box. Mathematically $\tau$ can be defined as the ratio of the mass $m$ (in kg) of X in the box to its removal rate, which is the sum of the flow of X out of the box ($F_$), chemical loss of X ($L$), and deposition of X ($D$) (all in kg/s): $\tau = \frac$. If input of this gas into the box ceased, then after time $\tau$, its concentration would decrease by about 63%. The atmospheric lifetime of a species therefore measures the time required to restore equilibrium following a sudden increase or decrease in its concentration in the atmosphere. Individual atoms or molecules may be lost or deposited to sinks such as the soil, the oceans and other waters, or vegetation and other biological systems, reducing the excess to background concentrations. The average time taken to achieve this is the mean lifetime. Carbon dioxide has a variable atmospheric lifetime, and cannot be specified precisely. Although more than half of the emitted is removed from the atmosphere within a century, some fraction (about 20%) of emitted remains in the atmosphere for many thousands of years.See also: See also: Similar issues apply to other greenhouse gases, many of which have longer mean lifetimes than , e.g. N2O has a mean atmospheric lifetime of 121 years.

Radiative forcing and annual greenhouse gas index

/ref> The Annual Greenhouse Gas Index (AGGI) is defined by atmospheric scientists at NOAA as the ratio of total direct radiative forcing due to long-lived and well-mixed greenhouse gases for any year for which adequate global measurements exist, to that present in year 1990. These radiative forcing levels are relative to those present in year 1750 (i.e. prior to the start of the industrial era). 1990 is chosen because it is the baseline year for the Kyoto Protocol, and is the publication year of the first IPCC Scientific Assessment of Climate Change. As such, NOAA states that the AGGI "measures the commitment that (global) society has already made to living in a changing climate. It is based on the highest quality atmospheric observations from sites around the world. Its uncertainty is very low."

Global warming potential

Natural and anthropogenic sources

Aside from purely human-produced synthetic halocarbons, most greenhouse gases have both natural and human-caused sources. During the pre-industrial Holocene, concentrations of existing gases were roughly constant, because the large natural sources and sinks roughly balanced. In the industrial era, human activities have added greenhouse gases to the atmosphere, mainly through the burning of fossil fuels and clearing of forests. The 2007 Fourth Assessment Report compiled by the IPCC (AR4) noted that "changes in atmospheric concentrations of greenhouse gases and aerosols, land cover and solar radiation alter the energy balance of the climate system", and concluded that "increases in anthropogenic greenhouse gas concentrations is very likely to have caused most of the increases in global average temperatures since the mid-20th century". In AR4, "most of" is defined as more than 50%. ''Abbreviations used in the two tables below: ppm = parts-per-million; ppb = parts-per-billion; ppt = parts-per-trillion; W/m2 = watts per square metre'' Ice cores provide evidence for greenhouse gas concentration variations over the past 800,000 years (see the following section). Both and vary between glacial and interglacial phases, and concentrations of these gases correlate strongly with temperature. Direct data does not exist for periods earlier than those represented in the ice core record, a record that indicates mole fractions stayed within a range of 180 ppm to 280 ppm throughout the last 800,000 years, until the increase of the last 250 years. However, various proxies and modeling suggests larger variations in past epochs; 500 million years ago levels were likely 10 times higher than now. Indeed, higher concentrations are thought to have prevailed throughout most of the Phanerozoic eon, with concentrations four to six times current concentrations during the Mesozoic era, and ten to fifteen times current concentrations during the early Palaeozoic era until the middle of the Devonian period, about 400 Ma. The spread of land plants is thought to have reduced concentrations during the late Devonian, and plant activities as both sources and sinks of have since been important in providing stabilising feedbacks. Earlier still, a 200-million year period of intermittent, widespread glaciation extending close to the equator (Snowball Earth) appears to have been ended suddenly, about 550 Ma, by a colossal volcanic outgassing that raised the concentration of the atmosphere abruptly to 12%, about 350 times modern levels, causing extreme greenhouse conditions and carbonate deposition as limestone at the rate of about 1 mm per day. This episode marked the close of the Precambrian eon, and was succeeded by the generally warmer conditions of the Phanerozoic, during which multicellular animal and plant life evolved. No volcanic carbon dioxide emission of comparable scale has occurred since. In the modern era, emissions to the atmosphere from volcanoes are approximately 0.645 billion tonnes of per year, whereas humans contribute 29 billion tonnes of each year.

Ice cores

Measurements from Antarctic ice cores show that before industrial emissions started atmospheric mole fractions were about 280 parts per million (ppm), and stayed between 260 and 280 during the preceding ten thousand years. Carbon dioxide mole fractions in the atmosphere have gone up by approximately 35 percent since the 1900s, rising from 280 parts per million by volume to 387 parts per million in 2009. One study using evidence from stomata of fossilized leaves suggests greater variability, with carbon dioxide mole fractions above 300 ppm during the period seven to ten thousand years ago, though others have argued that these findings more likely reflect calibration or contamination problems rather than actual variability. Because of the way air is trapped in ice (pores in the ice close off slowly to form bubbles deep within the firn) and the time period represented in each ice sample analyzed, these figures represent averages of atmospheric concentrations of up to a few centuries rather than annual or decadal levels.

Changes since the Industrial Revolution

Since the beginning of the Industrial Revolution, the concentrations of many of the greenhouse gases have increased. For example, the mole fraction of carbon dioxide has increased from 280 ppm to 415 ppm, or 120 ppm over modern pre-industrial levels. The first 30 ppm increase took place in about 200 years, from the start of the Industrial Revolution to 1958; however the next 90 ppm increase took place within 56 years, from 1958 to 2014. Recent data also shows that the concentration is increasing at a higher rate. In the 1960s, the average annual increase was only 37% of what it was in 2000 through 2007. Total cumulative emissions from 1870 to 2017 were 425±20 GtC (1539 GtCO2) from fossil fuels and industry, and 180±60 GtC (660 GtCO2) from land use change. Land-use change, such as deforestation, caused about 31% of cumulative emissions over 1870–2017, coal 32%, oil 25%, and gas 10%. Today, the stock of carbon in the atmosphere increases by more than 3 million tonnes per annum (0.04%) compared with the existing stock. This increase is the result of human activities by burning fossil fuels, deforestation and forest degradation in tropical and boreal regions. (webpage has a translation button) The other greenhouse gases produced from human activity show similar increases in both amount and rate of increase. Many observations are available online in a variety of Atmospheric Chemistry Observational Databases.

Role of water vapor

Water vapor accounts for the largest percentage of the greenhouse effect, between 36% and 66% for clear sky conditions and between 66% and 85% when including clouds. Water vapor concentrations fluctuate regionally, but human activity does not directly affect water vapor concentrations except at local scales, such as near irrigated fields. Indirectly, human activity that increases global temperatures will increase water vapor concentrations, a process known as water vapor feedback. The atmospheric concentration of vapor is highly variable and depends largely on temperature, from less than 0.01% in extremely cold regions up to 3% by mass in saturated air at about 32 °C. (See Relative humidity#Other important facts.) The average residence time of a water molecule in the atmosphere is only about nine days, compared to years or centuries for other greenhouse gases such as and . Water vapor responds to and amplifies effects of the other greenhouse gases. The Clausius–Clapeyron relation establishes that more water vapor will be present per unit volume at elevated temperatures. This and other basic principles indicate that warming associated with increased concentrations of the other greenhouse gases also will increase the concentration of water vapor (assuming that the relative humidity remains approximately constant; modeling and observational studies find that this is indeed so). Because water vapor is a greenhouse gas, this results in further warming and so is a "positive feedback" that amplifies the original warming. Eventually other earth processes offset these positive feedbacks, stabilizing the global temperature at a new equilibrium and preventing the loss of Earth's water through a Venus-like runaway greenhouse effect.

Anthropogenic greenhouse gas emissions

Removal from the atmosphere

Natural processes

Greenhouse gases can be removed from the atmosphere by various processes, as a consequence of: * a physical change (condensation and precipitation remove water vapor from the atmosphere). * a chemical reaction within the atmosphere. For example, methane is oxidized by reaction with naturally occurring hydroxyl radical, OH· and degraded to and water vapor ( from the oxidation of methane is not included in the methane Global warming potential). Other chemical reactions include solution and solid phase chemistry occurring in atmospheric aerosols. * a physical exchange between the atmosphere and the other components of the planet. An example is the mixing of atmospheric gases into the oceans. * a chemical change at the interface between the atmosphere and the other components of the planet. This is the case for , which is reduced by photosynthesis of plants, and which, after dissolving in the oceans, reacts to form carbonic acid and bicarbonate and carbonate ions (see ocean acidification). * a photochemical change. Halocarbons are dissociated by UV light releasing Cl· and F· as free radicals in the stratosphere with harmful effects on ozone (halocarbons are generally too stable to disappear by chemical reaction in the atmosphere).

Negative emissions

A number of technologies remove greenhouse gases emissions from the atmosphere. Most widely analysed are those that remove carbon dioxide from the atmosphere, either to geologic formations such as bio-energy with carbon capture and storage and carbon dioxide air capture, or to the soil as in the case with biochar. The IPCC has pointed out that many long-term climate scenario models require large-scale man-made negative emissions to avoid serious climate change. in

History of scientific research

In the late 19th century scientists experimentally discovered that and do not absorb infrared radiation (called, at that time, "dark radiation"), while water (both as true vapor and condensed in the form of microscopic droplets suspended in clouds) and and other poly-atomic gaseous molecules do absorb infrared radiation. In the early 20th century researchers realized that greenhouse gases in the atmosphere made Earth's overall temperature higher than it would be without them. During the late 20th century, a scientific consensus evolved that increasing concentrations of greenhouse gases in the atmosphere cause a substantial rise in global temperatures and changes to other parts of the climate system, with consequences for the environment and for human health.

References

Bibliography

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The official greenhouse gas emissions data of developed countries
from the UNFCCC *
Annual Greenhouse Gas Index (AGGI)
from NOAA
Atmospheric spectra of GHGs and other trace gases
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